沸腾氯化法制备四氯化钛过程热力学分析
|
摘要
为进一步研究沸腾氯化法制备四氯化钛的反应过程,以攀枝花典型高钛渣为原料,利用FactSage软件中的Reaction模块和Equilib模块对该体系进行热力学分析和化学平衡计算,通过综合分析反应过程中的温度、氯气配比、配碳比、压力等因素对四氯化钛、碳氧化物及其他金属氯化物的影响,确定反应过程的最佳物料配比和生产控制参数。根据模拟计算结果分析并参考多个企业的生产情况,确定了最佳温度区间为1 000～1 050℃,氯钛比3.0,配碳比100∶35,建议采用常压操作。对各个影响因素所产生的热力学影响结果的讨论,弥补了实际生产和已有实验分析中的不足,较全面地分析了物料配比与控制条件的具体影响结果,可为现有生产过程的优化改进提供一定参考。
In order to further study the reaction process of preparing titanium tetrachloride by boiling chlorination method,the typical high titanium slag of Panzhihua was used as raw material,amd the thermodynamic analysis and chemical equilibrium calculation of the system were carried out by using the Reaction module and Equilib module in FactSage software.The effects of temperature,chlorine ratio,carbon ratio,pressure and other factors in the reaction process on the titanium tetrachloride,carbon oxides and other metal chlorides were analyzed to determine the optimum material ratio and production control parameters of the reaction process.According to simulation calculation results and reference to the production situation of multiple enterprises,it is determined that the optimal temperature range is 1 000—1 050℃,the chlorine ratio is 3.0,and the carbon ratio is 100∶35.It is suggested to operate under atmospheric pressure.The discussion on the thermodynamic effects of various influencing factors compensates for the deficiency in actual production and existing experimental analysis,and comprehensively analyzes the specific influence results of the material ratio and control conditions.It can provide some reference for the optimization and improvement of the existing production process.
In order to further study the reaction process of preparing titanium tetrachloride by boiling chlorination method,the typical high titanium slag of Panzhihua was used as raw material,amd the thermodynamic analysis and chemical equilibrium calculation of the system were carried out by using the Reaction module and Equilib module in FactSage software.The effects of temperature,chlorine ratio,carbon ratio,pressure and other factors in the reaction process on the titanium tetrachloride,carbon oxides and other metal chlorides were analyzed to determine the optimum material ratio and production control parameters of the reaction process.According to simulation calculation results and reference to the production situation of multiple enterprises,it is determined that the optimal temperature range is 1 000—1 050℃,the chlorine ratio is 3.0,and the carbon ratio is 100∶35.It is suggested to operate under atmospheric pressure.The discussion on the thermodynamic effects of various influencing factors compensates for the deficiency in actual production and existing experimental analysis,and comprehensively analyzes the specific influence results of the material ratio and control conditions.It can provide some reference for the optimization and improvement of the existing production process.
引文
[1]江书安,刘建良,李雪刚.中国氯化钛白现状及发展趋势[J].有色金属设计,2016,43(3):60-64.JIANG Shu’an,LIU Jianliang,LI Xuegang.Current situations and development tendencies of titanium dioxide with chloride process of China[J].Nonferrous Metals Design,2016,43(3):60-64.
[2]刘立文.四氯化钛生产工艺探讨[J].无机盐工业,2013,45(2):36-38.LIU Liwen.Research on manufacturing technology of titanium tetrachloride[J].Inorganic chemicals industry,2013,45(2):36-38.
[3]居殿春,严定鎏,李向阳,等.高钛渣加碳氯化反应热力学在熔盐氯化中的应用[J].钢铁钒钛,2010,31(2):32-36.JU Dianchun,YAN Dingliu,LI Xiangyang,et al.Application of thermodynamics on reaction of carbochlorination of titania rich slag in molten salt chlorination[J].Iron Steel Vanadium Titanium,2010,31(2):32-36.
[4]王亚锋,李俊峰,张兵兵,等.高钛渣沸腾氯化制备四氯化钛工艺研究[J].河南科技,2014,(2):36-37.WANG Yafeng,LI Junfeng,ZHANG Bingbing,et al.The technology research of producing titanium tetrachloride with high-grade titanium slag by fluid-bed chlorination[J].Journal of Henan Science and Technology,2014,(2):36-37.
[5]陈辉.沸腾氯化生产四氯化钛工艺技术[J].现代机械,2010,(5):68-70.CHEN Hui.The process technology of manufacturing titanium tetrachloride with boiling chlorination[J].Modern Machinery,2010,(5):68-70.
[6]张志铭,孟喜堂.沸腾氯化工艺在生产中的应用[J].钛工业进展,2002,(1):33-35.ZHANG Zhiming,MENG Xitang.Application of fluidized chlorination process in production[J].Titanium Industry Progress,2002,(1):33-35.
[7]王玉明,刘瑞丰,周荣会,等.制备四氯化钛过程中加碳氯化反应热力学[J].计算机与应用化学,2006,23(3):263-266.WANG Y M,LIU R F,ZHOU R H,et al.Thermodynamics on the reaction of carbochlorination of titania for getting titanium tetrachloride[J].Computers and Applied Chemistry,2006,23(3):263-266.
[8]黄润,吕学伟,张凯,等.攀枝花钛精矿碳热还原-真空冶炼工艺[J].中南大学学报(自然科学版),2014,45(3):684-689.HUANG Run,LV Xuewei,ZHANG Kai,et al.Carbothermic reduction and vacuum smelting of Panzhihua ilmenite concentrate[J].Journal of Central South University(Science and Technology),2014,45(3):684-689.
[9]崔帅,唐晓宁,张彬,等.煤气化和燃烧过程中砷元素迁移热力学分析[J].计算机与应用化学,2015,32(8):921-925.CUI Shuai,TANG Xiaoning,ZHANG Bin,et al.Thermodynamics analysis of migration of arsenic during coal gasification and combustion[J].Computers and Applied Chemistry,2015,32(8):921-925.
[10]代正华,胡敏,李超,等.气流床煤气化过程中氯元素的迁移特性[J].煤炭学报,2013,38(11):2048-2053.DAI Zhenghua,HU Min,LI Chao,et al.Chlorine migration in entrained-flow coal gasification process[J].Journal of China Coal Society,2013,38(11):2048-2053.
[11]唐晓宁.稀土热力学数据库计算体系研究[D].昆明:昆明理工大学,2011.TANG Xiaoning.Study on calculation system of rare earth thermodynamic database[D].Kunming:Kunming University of science and technology,2011.
[12]代正华,龚欣,王辅臣,等.气流床粉煤气化的Gibbs自由能最小化模拟[J].燃烧化学学报,2005,33(2):129-133.DAI Zhenghua,GONG Xin,WANG Fuchen,et al.Thermodynamic analysis of entrained-flow pulverized coal gasification by Gibbs free energy minimization[J].Journal of Fuel Chemistry and Technology,2005,33(2):129-133.
[13]胡元金.沸腾氯化原料特性分析[J].四川冶金,2014,36(2):45-47.HU Yuanjin.Characters of raw material on fluidized chlorination[J].Sichuan Metallurgy,2014,36(2):45-47.
[14]MORRIS A J,JENSEN R F.Fluidized-bed chlorination rates of Australian rutile[J].Metallurgical Transactions B,1975,7(2):76-82.
[15]侯丽平.四氯化钛的生产工艺改进[J].安徽化工,2012,38(4):51-52.HOU Liping.Improvement of production process of titanium tetrachloride[J].Anhui Chemical Industry,2012,38(4):51-52.
[16]令狐昌鸿.云南高钛渣沸腾氯化生产粗TiCl4可行性探讨[J].钛工业进展,2002(2):40-42.LINGHU Changhong.Discussion on feasibility of producing crude TiCl4 from Yunnan high titanium residue by boiling chlorination[J].Titanium Industry Progress,2002(2):40-42.
[17]黄权英,温旺光,钟法宝,等.攀矿高镁钙含钛物料的沸腾氯化问题[J].钢铁钒钛,1987(1):18-22.HUANG Quanying,WEN Wangguang,ZHONGFabao,et al.The problem of boiling chlorination of high-Mg-Ca-containing Ti-containing materials[J].Iron Steel Vanadium Titanium,1987(1):18-22.
[2]刘立文.四氯化钛生产工艺探讨[J].无机盐工业,2013,45(2):36-38.LIU Liwen.Research on manufacturing technology of titanium tetrachloride[J].Inorganic chemicals industry,2013,45(2):36-38.
[3]居殿春,严定鎏,李向阳,等.高钛渣加碳氯化反应热力学在熔盐氯化中的应用[J].钢铁钒钛,2010,31(2):32-36.JU Dianchun,YAN Dingliu,LI Xiangyang,et al.Application of thermodynamics on reaction of carbochlorination of titania rich slag in molten salt chlorination[J].Iron Steel Vanadium Titanium,2010,31(2):32-36.
[4]王亚锋,李俊峰,张兵兵,等.高钛渣沸腾氯化制备四氯化钛工艺研究[J].河南科技,2014,(2):36-37.WANG Yafeng,LI Junfeng,ZHANG Bingbing,et al.The technology research of producing titanium tetrachloride with high-grade titanium slag by fluid-bed chlorination[J].Journal of Henan Science and Technology,2014,(2):36-37.
[5]陈辉.沸腾氯化生产四氯化钛工艺技术[J].现代机械,2010,(5):68-70.CHEN Hui.The process technology of manufacturing titanium tetrachloride with boiling chlorination[J].Modern Machinery,2010,(5):68-70.
[6]张志铭,孟喜堂.沸腾氯化工艺在生产中的应用[J].钛工业进展,2002,(1):33-35.ZHANG Zhiming,MENG Xitang.Application of fluidized chlorination process in production[J].Titanium Industry Progress,2002,(1):33-35.
[7]王玉明,刘瑞丰,周荣会,等.制备四氯化钛过程中加碳氯化反应热力学[J].计算机与应用化学,2006,23(3):263-266.WANG Y M,LIU R F,ZHOU R H,et al.Thermodynamics on the reaction of carbochlorination of titania for getting titanium tetrachloride[J].Computers and Applied Chemistry,2006,23(3):263-266.
[8]黄润,吕学伟,张凯,等.攀枝花钛精矿碳热还原-真空冶炼工艺[J].中南大学学报(自然科学版),2014,45(3):684-689.HUANG Run,LV Xuewei,ZHANG Kai,et al.Carbothermic reduction and vacuum smelting of Panzhihua ilmenite concentrate[J].Journal of Central South University(Science and Technology),2014,45(3):684-689.
[9]崔帅,唐晓宁,张彬,等.煤气化和燃烧过程中砷元素迁移热力学分析[J].计算机与应用化学,2015,32(8):921-925.CUI Shuai,TANG Xiaoning,ZHANG Bin,et al.Thermodynamics analysis of migration of arsenic during coal gasification and combustion[J].Computers and Applied Chemistry,2015,32(8):921-925.
[10]代正华,胡敏,李超,等.气流床煤气化过程中氯元素的迁移特性[J].煤炭学报,2013,38(11):2048-2053.DAI Zhenghua,HU Min,LI Chao,et al.Chlorine migration in entrained-flow coal gasification process[J].Journal of China Coal Society,2013,38(11):2048-2053.
[11]唐晓宁.稀土热力学数据库计算体系研究[D].昆明:昆明理工大学,2011.TANG Xiaoning.Study on calculation system of rare earth thermodynamic database[D].Kunming:Kunming University of science and technology,2011.
[12]代正华,龚欣,王辅臣,等.气流床粉煤气化的Gibbs自由能最小化模拟[J].燃烧化学学报,2005,33(2):129-133.DAI Zhenghua,GONG Xin,WANG Fuchen,et al.Thermodynamic analysis of entrained-flow pulverized coal gasification by Gibbs free energy minimization[J].Journal of Fuel Chemistry and Technology,2005,33(2):129-133.
[13]胡元金.沸腾氯化原料特性分析[J].四川冶金,2014,36(2):45-47.HU Yuanjin.Characters of raw material on fluidized chlorination[J].Sichuan Metallurgy,2014,36(2):45-47.
[14]MORRIS A J,JENSEN R F.Fluidized-bed chlorination rates of Australian rutile[J].Metallurgical Transactions B,1975,7(2):76-82.
[15]侯丽平.四氯化钛的生产工艺改进[J].安徽化工,2012,38(4):51-52.HOU Liping.Improvement of production process of titanium tetrachloride[J].Anhui Chemical Industry,2012,38(4):51-52.
[16]令狐昌鸿.云南高钛渣沸腾氯化生产粗TiCl4可行性探讨[J].钛工业进展,2002(2):40-42.LINGHU Changhong.Discussion on feasibility of producing crude TiCl4 from Yunnan high titanium residue by boiling chlorination[J].Titanium Industry Progress,2002(2):40-42.
[17]黄权英,温旺光,钟法宝,等.攀矿高镁钙含钛物料的沸腾氯化问题[J].钢铁钒钛,1987(1):18-22.HUANG Quanying,WEN Wangguang,ZHONGFabao,et al.The problem of boiling chlorination of high-Mg-Ca-containing Ti-containing materials[J].Iron Steel Vanadium Titanium,1987(1):18-22.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |