In Situ Monitoring and Kinetic Analysis of the Extraction of Nitric Acid by Tributyl Phosphate in N-Dodecane Using Raman Spectroscopy

被引:9
作者
Asmussen, Susan E. [1 ]
Lines, Amanda M. [1 ]
Bottenus, Danny [1 ]
Heller, Forrest [1 ]
Bryan, Samuel A. [1 ]
Delegard, Calvin [2 ]
Louie, Christina [1 ,3 ]
Lumetta, Gregg [1 ]
Pellegrini, Kristi [1 ]
Pitts, W. Karl [1 ]
Clark, Sue [1 ,4 ]
Casella, Amanda [1 ]
机构
[1] Pacific Northwest Natl Lab, Richland, DC USA
[2] TradeWind Serv LLC, Richland, DC USA
[3] Washington State Univ, Dept Engn & Bioengn, Pullman, WA 99164 USA
[4] Washington State Univ, Dept Chem, Pullman, WA 99164 USA
关键词
Raman spectroscopy; PUREX; TBP; interfacial transfer; NORMAL-BUTYL PHOSPHATE; SOLVENT-EXTRACTION; MULTIVARIATE-ANALYSIS; WATER; SYSTEM; TBP; EQUILIBRIUM; MECHANISM; MODEL;
D O I
10.1080/07366299.2019.1630071
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Understanding the fundamental rates of transfer and complex formation is crucial in maintaining optimal efficiency and effectivity in solvent extraction. Methodologies to analyze solvent extraction systems are lacking in that they are commonly performed off-line in subsequent experiments. Thus, a method to proficiently investigate solvent extraction systems in a Lewis cell using in situ Raman spectroscopy paired with chemometric modeling has been developed to allow for on-line analysis and monitoring. Forward and reverse interfacial transfer coefficients for the extraction of nitric acid by tributyl phosphate, a process crucial to used nuclear fuel reprocessing, were measured by spectroscopic monitoring of both phases simultaneously in a two-phase solvent extraction system. Concentration data was derived from the chemometric modeling using Raman spectra. The concentration data was fit to a nonlinear least squares regression model to allow for the calculation of the transfer coefficients in the system. The reverse interfacial transfer coefficient, k(r), was determined along with the parameter 95% confidence intervals and 95% prediction intervals. The forward interfacial transfer coefficient, k(f), was then back calculated from k(r) and the aqueous phase and organic phase equilibrium concentrations. The average calculated values of k(r) and k(f) were 2.56 (+/- 0.50) x 10(-5) m s(-1) and 4.75 (+/- 1.13) x 10(-6) m s(-1), respectively. The information obtained regarding solvent extraction parameters and transfer can be applied in the study of systems of higher complexity, involving complex formation and their transfer across a liquid:liquid interface.
引用
收藏
页码:157 / 172
页数:16
相关论文
共 57 条
[41]   Calculation of the equilibrium in the extraction of nitric acid with 30 and 12% Tri-n-butylphosphate solutions in dodecane [J].
Ochkin, A. V. ;
Nekhaevskii, S. Yu. .
THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING, 2015, 49 (05) :649-655
[42]   MECHANISM OF EXTRACTION BY TRIBUTYL PHOSPHATE-N-HEXANE SOLVENTS .2. [J].
OLANDER, DR ;
BENEDICT, M .
NUCLEAR SCIENCE AND ENGINEERING, 1963, 15 (04) :354-&
[43]  
Orth D. A., 1984, SCI TECHNOLOGY TRIBU, P161
[44]   Kinetics of extraction of nitric acid into binary mixture of tri-n-butyl phosphate and normal paraffin hydrocarbon [J].
Pandey, N. K. ;
Augustine, Elizabeth ;
Murali, Rernya ;
Desigan, N. ;
Mudali, U. Kamachi ;
Joshi, J. B. .
CHEMICAL ENGINEERING RESEARCH & DESIGN, 2016, 111 :492-503
[45]   Nitric acid: modeling osmotic coefficients and acid-base dissociation using the BIMSA theory [J].
Ruas, Alexandre ;
Pochon, Patrick ;
Simonin, Jean-Pierre ;
Moisy, Philippe .
DALTON TRANSACTIONS, 2010, 39 (42) :10148-10153
[46]  
Ryan T. P., 2008, MODERN REGRESSION ME, P642
[47]  
Schulz W., 1984, SCI TECHNOLOGY TRIBU, VI.
[48]  
Sharaf M.A., 1986, CHEMOMETRICS
[49]   Rotating membrane cell technique for the study of liquid/liquid extraction kinetics. [J].
Simonin, JP ;
Weill, J .
SOLVENT EXTRACTION AND ION EXCHANGE, 1998, 16 (06) :1493-1514
[50]   EXTRACTION OF NITRIC-ACID BY TBP SOLUTIONS IN KEROSENE [J].
SOVILJ, M ;
LUKESOVA, S ;
ROD, V .
COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, 1985, 50 (03) :738-744