CAJ | 학술논문

为了精确预测非理想条件下稀土金属溶剂萃取的平衡分配比,研究了溶于Shellsol D70中的P507溶剂对盐酸液中钇(Ⅲ)和铕(Ⅲ)的萃取平衡,建立化学基模型,并通过非线性最小二乘法确定萃取平衡常数.所建模型涉及了在低酸度区的离子交换反应和高酸度区的溶剂化萃取反应；模型还考虑了稀土金属与Cl-的配位反应,并用萃取剂的有效浓度代替[(HR)2],进而分别对水相和有机相(HR2)的非理想性加以修正.对稀土单元体系,在较宽的初始浓度范围内(稀土浓度最高至0.1 mol/L,盐酸浓度0.07-3.00 mol/L,萃取剂浓度0.25-1.00 mol/L),由模型计算的稀土分配比与实验测得的数据吻合良好,验证了模型的有效性.对于稀土二元体系,该模型能以良好的精度对平衡分配比进行工程预测.
위료정학예측비이상조건하희토금속용제췌취적평형분배비,연구료용우Shellsol D70중적P507용제대염산액중을(Ⅲ)화유(Ⅲ)적췌취평형,건립화학기모형,병통과비선성최소이승법학정췌취평형상수.소건모형섭급료재저산도구적리자교환반응화고산도구적용제화췌취반응；모형환고필료희토금속여Cl-적배위반응,병용췌취제적유효농도대체[(HR)2],진이분별대수상화유궤상(HR2)적비이상성가이수정.대희토단원체계,재교관적초시농도범위내(희토농도최고지0.1 mol/L,염산농도0.07-3.00 mol/L,췌취제농도0.25-1.00 mol/L),유모형계산적희토분배비여실험측득적수거문합량호,험증료모형적유효성.대우희토이원체계,해모형능이량호적정도대평형분배비진행공정예측.
For the accurate prediction of equilibrium distribution ratios of rare earth metals during solvent extraction under non-ideal conditions,the extraction equilibria of yttrium(Ⅲ)and europium(Ⅲ)from the hydrochloric acid solutions with P507 in Shellsoi D70 were studied.A chemically-based model was established and the extraction equilibrium constants were determined by the nonlinear least squares method.The proposed model involves the cation exchange reaction and the solvation extraction in the low and high acidity regions,respectively.In the model,the nonideality of the aqueous phase and(HR)2 was corrected by considering the complexation of the metals with(Cl-)and by replacing[(HR)2]with its effective concentration,respectively.This model was verified by fair agreement between the calculated metal distribution ratios and those experimentally obtained in the single metal systems.The feed concentrations for the systems are in wide ranges of the metal(up to 0.1 mol/L),hydrochloric acid(0.07-3.00 mol/L)and the extractant(0.25-1.00 mol/L).The model enables the engineering prediction of the equilibrium distribution ratios with good accuracy in a binary metal system.