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采用恒界面池法研究了N263-HSCN体系萃取锆和铪的动力学,考察界面积、萃取槽搅拌速度、温度对萃取锆和铪的影响,从而确定萃取动力学类型。结果表明,当搅拌速度小于130 r/min时,萃取过程由扩散反应控制,锆铪的萃取速率常数随搅拌速度的增加而增大;当搅拌速度在130~170 r/min时,萃取过程由化学反应控制,锆和铪的萃取速率常数随搅拌速度的增加基本保持不变。随着界面积的增加和温度的提高,锆和铪的萃取速率常数均增加,其表观活化能分别为42.06 kJ/mol和31.77 kJ/mol,说明该萃取过程为相界面处的化学反应控制过程。计算出锆和铪萃取的焓变分别为39.59 kJ/mol和29.30 kJ/mol,熵变分别为-147.53 J/(mol·K)和-174.38 J/(mol·K),在298.15 K时吉布斯自由能变分别为83.57 kJ/mol和81.29 kJ/mol。
Abstract:Extraction kinetics of zirconium and hafnium extracted by N263-HSCN system was studied by constant Lewis cell technique.Effects of stirring speed, interfacial area and temperature of extraction tank on extraction of zirconium and hafnium were explored to determine the type of extraction kinetics.The results show that when stirring speed is less than 130 r/min, the extraction rate constant of zirconium and hafnium rises with the increase of stirring speed, and the extraction process is controlled by diffusion reaction; When stirring speed is within 130-170 r/min, the extraction rate constants of zirconium and hafnium remains basically stable with the increase of stirring speed, and the extraction process is controlled by chemical reaction.With the increase of interfacial area and temperature, the extraction rate constants of zirconium and hafnium rise, the apparent activation energies of zirconium and hafnium extraction are 42.06 kJ/mol and 31.77 kJ/mol respectively, indicating that the extraction process is controlled by chemical reaction process at the phase interface.The enthalpy changes of zirconium and hafnium extraction are 39.59 kJ/mol and 29.30 kJ/mol respectively.The entropy changes are-147.53 J/(mol·K) and-174.38 J/(mol·K) respectively, and the Gibbs free energy changes are 83.57 kJ/mol and 81.29 kJ/mol respectively at 298.15 K.
[1] 熊炳昆,罗方,田振业,等.我国锆铪矿产资源利用可持续发展研究[J].稀有金属快报,2004,23(5):2-7.XIONG B K,LUO F,TIAN Z Y,et al.Study on sustainable development of zirconium and hafnium mineral resources utilization in China[J].Rare Metals Letters,2004,23(5):2-7.
[2] BANDA R,LEE M S.Solvent extraction for the separation of Zr and Hf from aqueous solutions[J].Separation & Purification Reviews,2014,44(3):199-215.
[3] AMARAL J C B S,SOUZA A L,MORAIS C A.Liquid-liquid separation of zirconium and hafnium from nitric liquor in order to obtain nuclear zirconium oxide using TBP as extractant[J].Chemical Engineering Communications,2019,207(1):73-83.
[4] TAGHIZADEH M,GHASEMZADEH R,ASHRAFIZADEH S N,et al.Determination of optimum process conditions for the extraction and separation of zirconium and hafnium by solvent extraction[J].Hydrometallurgy,2008,90(2/3/4):115-120.
[5] LARSSON K,BINNEMANS K.Separation of rare earths by split-anion extraction[J].Hydrometallurgy,2015,156:206-214.
[6] 徐志高,吴明,池汝安,等.DIBK-TBP体系萃取铪和锆的动力学研究[J].有色金属(冶炼部分),2014(2):35-38.XU Z G,WU M,CHI R A,et al.Extraction kinetics of hafnium and zirconium in DIBK-TBP system[J].NonferrousMetals (Extractive Metallurgy),2014(2):35-38.
[7] 赵骏,徐志高,张文杰,等.DIBK-TOPO体系萃取锆和铪的动力学研究[J].稀有金属,2017,41(1):108-112.ZHAO J,XU Z G,ZHANG W J,et al.Extration kinetics of zirconium and hafnium in DIBK-TOPO system[J].Chinese Journal of Rare Metals,2017,41(1):108-112.
[8] ALBERY W J,BURKE J F,LEFFLER E B,et al.Interfacial transfer studied with a rotating diffusion cell[J].Journal of the Chemical Society,Faraday Transactions 1,1976,72:1618-1626.
[9] 易筱筠,古国榜.研究萃取动力学的新方法-气搅法[J].华南理工大学学报(自然科学版),2001,29(1):40-42.YI X Y,GU G B.A new method to study extraction kinetics-gas stirring method[J].Journal of South China University of Technology (Natural Science Edition),2001,29(1):40-42.
[10] 王玉洁,张淑敏,李德谦.中空纤维膜萃取分离混合稀土中的钍[J].中国稀土学报,1998,16(3):193-198.WANG Y J,ZHANG S M,LI D Q.Separation of Th3+ from RE3+with hollow fiber membrane extraction[J].Journal of Chinese Rare Earths Society,1998,16(3):193-198.
[11] BISWAS R K,HAYAT M A.Kinetics of solvent extraction of zirconium (Ⅳ) from chloride medium by D2EHPA in kerosene using the single drop technique[J].Hydrometallurgy,2002,65(2/3):205-216.
[12] KASAIE M,BAHMANYAR H,MOOSAVIAN M A.A kinetic study on solvent extraction of copper from sulfate solution with Cupromex-3302 using Lewis cell[J].Journal of Environmental Chemical Engineering,2017,5(3):3044-3050.
[13] 邢鹏,王成彦.P204钠皂萃取Mn(Ⅱ)动力学[J].过程工程学报,2011,11(1):61-64.XING P,WANG C Y.Extraction kinetics of Mn(Ⅱ) with P204 sodium soap[J].Journal of Process Engineering,2011,11(1):61-64.
[14] PANDEY N K,MURALI R,AUGUSTINE E,et al.Kinetics of interphase transfer of zirconium between nitric acid and tributyl phosphate solutions[J].Journal of Radioanalytical and Nuclear Chemistry,2017,314(3):1991-2001.
[15] 董攀飞,徐志高,吴明,等.N236-HSCN体系萃取分离锆铪的盐效应研究[J].有色金属(冶炼部分),2021(12):63-68.DONG P F,XU Z G,WU M,et al.Study on salt effect of extraction and separation of zirconium and hafnium in N263-HSCN system[J].Nonferrous Metals (Extractive Metallurgy),2021(12):63-68.
[16] XU Z G,ZHAO J,WANG L J,et al.Kinetics for extraction of zirconium and hafnium in DIBK-P350 system[J].Journal of Radioanalytical & Nuclear Chemistry,2016,309(2):701-707.
[17] YANG X L,WANG X X,WEI C,et al.Extraction kinetics of tantalum by MIBK from pulp using Lewis cell[J].Hydrometallurgy,2013,131:34-39.
[18] ZHANG L C,LI L J,SHI D,et al.Kinetics and mechanism study of lithium extraction from alkaline solution by HFTA and TOPO and stripping process using Lewis cell technique[J].Separation and Purification Technology,2019,211:917-924.
[19] JAVANSHIR S,ABDOLLAHY M,ABOLGHASEMI H,et al.Kinetics of Au(Ⅲ) extraction by DBC from hydrochloric solution using Lewis cell[J].International Journal of Mineral Processing,2011,98(1/2):42-47.
[20] HUGHES M A,PRESTON J S,WHEWELL R J.The kinetics of the solvent extraction of copper(Ⅱ) with LIX 64N reagents Ⅱ:Activation energies[J].Journal of Inorganic and Nuclear Chemistry,1976,38(11):2067-2069.
基本信息:
中图分类号:TF841.4
引用信息:
[1]董攀飞,徐志高,吴明,等.N263-HSCN体系萃取锆铪的动力学[J].有色金属(冶炼部分),2022(04):67-72.
基金信息:
国家自然科学基金资助项目(51774344,52104289); 湖北省自然科学基金项目(2020CFB165); 武汉市应用基础前沿项目(2019020701011449)
2022-03-21
2022-03-21