稀土熔盐渣碳酸钠焙烧转型机理及浸出规律
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摘要
借助反应热力学计算和动力学分析,研究碳酸钠焙烧稀土熔盐的转型机理和焙烧条件对稀土浸出的影响。研究结果表明:碳酸钠焙烧稀土熔盐渣反应的活化能(E_a)约为174.31k J/mol,受化学界面反应控制,温度升高可促进氟化稀土向氧化稀土转变;提高焙烧温度,延长焙烧时间,增加碳酸钠添加量均有利于提高稀土浸出率。稀土熔盐渣焙烧转化的优选条件如下:焙烧温度为700℃,反应时间为60 min,碳酸钠添加量为原料质量的30%。碳酸钠焙烧—水洗除氟—盐酸优溶可使熔盐渣中含稀土物在较低温度下发生物相转化,进而实现稀土的高效回收。
The transformation mechanism of rare earth fluoride molten salt slag(REFMSS) mixed with Na_2CO_3 in the roasting process and the effects of roasting conditions on rare earth(RE) leaching efficiency were investigated through thermodynamic calculations of reactions and the kinetic analysis. The results show that the activation energy(E_a) is about174.31 kJ/mol, and the roasting process is controlled by interface chemical reaction. The transformation of rare earth fluoride to rare earth oxide(REO) is promoted at elevated temperature. Moreover, the increase of temperature, reaction time and Na_2CO_3 dosage is beneficial to RE leaching efficiency. The optimum roasting conditions for REFMSS are determined at 700 ℃, 60 min, and Na_2CO_3 dosage with 30% mass fraction of raw material. Through the processes of Na_2CO_3 roasting, defluorination by washing and leaching by hydrochloric acid, the transformation of rare earth phases in REFMSS is achieved at lower temperature, which realizes the efficient recycle of RE.
The transformation mechanism of rare earth fluoride molten salt slag(REFMSS) mixed with Na_2CO_3 in the roasting process and the effects of roasting conditions on rare earth(RE) leaching efficiency were investigated through thermodynamic calculations of reactions and the kinetic analysis. The results show that the activation energy(E_a) is about174.31 kJ/mol, and the roasting process is controlled by interface chemical reaction. The transformation of rare earth fluoride to rare earth oxide(REO) is promoted at elevated temperature. Moreover, the increase of temperature, reaction time and Na_2CO_3 dosage is beneficial to RE leaching efficiency. The optimum roasting conditions for REFMSS are determined at 700 ℃, 60 min, and Na_2CO_3 dosage with 30% mass fraction of raw material. Through the processes of Na_2CO_3 roasting, defluorination by washing and leaching by hydrochloric acid, the transformation of rare earth phases in REFMSS is achieved at lower temperature, which realizes the efficient recycle of RE.
引文
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[23]李歌,李增和,马鸿文,等.热重分析法研究氢氧化镁纳米粉体的非等温分解动力学[J].化工学报,2014,65(2):576-582.LI Ge,LI Zenghe,MA Hongwen,et al.Non-isothermal decomposition kinetics of nano-Mg(OH)2 using thermal gravimetric analysis[J].CIESC Journal,2014,65(2):576-582.
[24]KISSINGER H E.Reaction kinetics in differential thermal analysis[J].Analytical Chemistry,1957,29(11):1702-1706.
[25]周秋生,齐天贵,彭志宏,等.熟料烧结过程中氧化铁反应行为的热力学分析[J].中国有色金属学报,2007,17(6):973-978.ZHOU Qiusheng,QI Tiangui,PENG Zhihong,et al.Thermodynamics of reaction behavior of ferric oxide during sinter-preparing process[J].The Chinese Journal of Nonferrous Metals,2007,17(6):973-978.
[26]BARIN I.Thermochemical data of pure substances[M].New York,USA:Wiley-VCH Publishers,1995:404,754,758,931,936,1117,1122,1186,1190,1323,1327.
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[2]RAO Jinsong,LI Huaji,XUE Hansong.Ignition-proof mechanism of ZM5 magnesium alloy added with rare earth[J].Journal of Central South University,2010,17(1):28-33.
[3]曹祖军,孔纲,车淳山.稀土Nd对Zn-5%Al合金显微组织和耐蚀性的影响[J].中国有色金属学报,2017,27(1):24-31.CAO Zunjun,KONG Gang,CHE Chunshan.Effect of Nd addition on microstructure and corrosion resistance of Zn-5%Al alloy[J].The Chinese Journal of Nonferrous Metals,2017,27(1):24-31.
[4]李庆林,李斌强,李进宝,等.混合稀土对过共晶Al-20Si合金显微组织与力学性能的影响[J].中国有色金属学报,2017,27(12):2443-2450.LI Qinglin,LI Binqiang,LI Jinbao,et al.Effect of mischmetal on microstructure and mechanical properties of hypereutectic Al-20Si alloy[J].The Chinese Journal of Nonferrous Metals,2017,27(12):2443-2450.
[5]刘余九.中国稀土产业现状及发展的主要任务[J].中国稀土学报,2007,25(3):257-263.LIU Yujiu.Present state and main task of development of rare earth industry in China[J].Journal of the Chinese Rare Earth Society,2007,25(3):257-263.
[6]何捍卫,孟佳.采用P507(HEH/EHP)从废FCC催化剂中回收稀土[J].中南大学学报(自然科学版),2011,42(9):2651-2657.HE Hanwei,MENG Jia.Recycling rare earth from spent FCCcatalyst using P507(HEH/EHP)as extractant[J].Journal of Central South University(Science and Technology),2011,42(9):2651-2657.
[7]YANG Yongxiang,WALTON A,SHERIDAN R,et al.REErecovery from end-of-Life NdFeB permanent magnet scrap:a critical review[J].Journal of Sustainable Metallurgy,2017,3(1):122-149.
[8]BINNEMANS K,JONES P T,BLANPAIN B,et al.Recycling of rare earths:a critical review[J].Journal of Cleaner Production,2013,51:1-22.
[9]RADEMAKER J H,KLEIJN R,YANG Yongxiang.Recycling as a strategy against rare earth element criticality:A systemic evaluation of the potential yield of NdFeB magnet recycling[J].Environmental Science&Technology,2013,47(18):10129-10136.
[10]BINNEMANS K,JONES P T.Perspectives for the recovery of rare earths from end-of-life fluorescent lamps[J].Journal of Rare Earths,2014,32(3):195-200.
[11]KUMARI A,JHA M K,PATHAK D D.Review on the processes for the recovery of rare earth metals(REMs)from secondary resources[C]//TMS Meeting&Exhibition.Cham:Springer,2018:53-65.
[12]邓庚凤,吴继平,邓亮亮,等.自然氧化预处理钕铁硼废料浸出过程[J].有色金属科学与工程,2017,8(2):119-123.DENG Gengfeng,WU Jiping,DENG Liangliang,et al.NdFeBmagnet scrap pretreated by air oxidation and its leaching process[J].Nonferrous Metals Science and Engineering,2017,8(2):119-123.
[13]庞思明,颜世宏,李宗安,等.我国熔盐电解法制备稀土金属及其合金工艺技术进展[J].稀有金属,2011,35(3):440-450.PANG Siming,YAN Shihong,LI Zongan,et al.Development on molten salt electrolytic methods and technology for preparing rare earth metals and alloys in China[J].Chinese Journal of Rare Metals,2011,35(3):440-450.
[14]陈占恒.我国稀土行业2017年回顾及未来展望[J].新材料产业,2018(6):31-34.CHEN Zhanheng.Review and prospects of China's rare earth industry in 2017[J].Advanced Materials Industry,2018(6):31-34.
[15]肖勇,陈月华,许鸽鸣,等.稀土镨钕熔盐电解废料中有价成分的分离及回收方法:中国,CN 104805292A[P].2015-07-29.XIAO Yong,CHEN Yuehua,XU Geming,et al.Separation and recovery method of valuable components of rare earth praseodymium neodymium electrolysis in molten salt waste:China,CN 104805292A[P].2015-07-29.
[16]陈冬英,欧阳红,刘莲翠,等.稀土电解废熔盐的综合利用研究[J].江西冶金,2005,25(1):4-8.CHEN Dongying,OUYANG Hong,LIU Liancui,et al.Study on recovery of scrapped molten salt in RE electrolysis[J].Jiangxi Metallurgy,2005,25(1):4-8.
[17]孙东江.稀土金属冶炼渣环保处理工艺:中国,CN104818390A[P].2015-08-05.SUN Dongjiang.Environment friendly treatment process of rare earth metal smelting slag:China,CN 104818390A[P].2015-08-05.
[18]林剑,何清平,黎春祥.一种从稀土熔盐电解废料中分离回收稀土元素的方法:中国,CN 101956078A[P].2011-01-26.LIN Jian,HE Qingping,LI Chunxiang.A method for separating and recovering rare earth element from rare earth molten salt electrolysis waste:China,CN 101956078A[P].2011-01-26.
[19]卢莹冰,朱水东.一种分解含氟稀土熔盐废渣的工艺:中国,CN 105256156A[P].2016-01-20.LU Yingbing,ZHU Shuidong.A process for fluoride-containing rare earth molten salt slag treatment:China,CN 105256156A[P].2016-01-20.
[20]胡德远,李来超,张榕贵.一种环保低成本从稀土氟化物熔盐电解废料中回收稀土的方法:中国,CN 104843761A[P].2015-08-19.HU Deyuan,LI Laichao,ZHANG Ronggui.An environmentally friendly and low-cost method for recovering rare earth from rare earth fluoride molten salt electrolytic waste:China,CN 104843761A[P].2015-08-19.
[21]LIANG Yong,LI Yongkang,XUE Liyan,et al.Extraction of rare earth elements from fluoride molten salt electrolytic slag by mineral phase reconstruction[J].Journal of Cleaner Production,2018,177:567-572.
[22]梁勇,黎永康,刘玉城,等.一种从氟盐体系稀土熔盐电解渣中高效提取稀土的方法:中国,CN 105369042A[P].2016-03-02.LIANG Yong,LI Yongkang,LIU Yucheng,et al.A method for efficiently extracting rare earth from rare earth molten salt electrolytic slag in fluoride salt system:China,CN 105369042A[P].2016-03-02.
[23]李歌,李增和,马鸿文,等.热重分析法研究氢氧化镁纳米粉体的非等温分解动力学[J].化工学报,2014,65(2):576-582.LI Ge,LI Zenghe,MA Hongwen,et al.Non-isothermal decomposition kinetics of nano-Mg(OH)2 using thermal gravimetric analysis[J].CIESC Journal,2014,65(2):576-582.
[24]KISSINGER H E.Reaction kinetics in differential thermal analysis[J].Analytical Chemistry,1957,29(11):1702-1706.
[25]周秋生,齐天贵,彭志宏,等.熟料烧结过程中氧化铁反应行为的热力学分析[J].中国有色金属学报,2007,17(6):973-978.ZHOU Qiusheng,QI Tiangui,PENG Zhihong,et al.Thermodynamics of reaction behavior of ferric oxide during sinter-preparing process[J].The Chinese Journal of Nonferrous Metals,2007,17(6):973-978.
[26]BARIN I.Thermochemical data of pure substances[M].New York,USA:Wiley-VCH Publishers,1995:404,754,758,931,936,1117,1122,1186,1190,1323,1327.
[27]周毓萍,杨正银,于红娟,等.1-苯基-3-甲基-4-苯甲酰基吡唑酮-5缩氨基硫脲稀土配合物的合成、表征及抑菌活性[J].应用化学,1999,16(6):37-41.ZHOU Yuping,YANG Zhengyin,YU Hongjuan,et al.Syntheses,characterization and bacteriostatic activities of 1-phenyl-3-methyl-4-benzoylpyrazolone-5-thiosemicarbazone and its rare earth complexes[J].Chinese Journal of Applied Chemistry,1999,16(6):37-41.