Journal of Nuclear Science, Engineering and Technology (JONSAT)
In cooperation with the Iranian Nuclear Society

Study of Kinetic Parameters of Uranium (VI) Extraction and Stripping from Phosphoric Acid Medium by Bulk Liquid Membrane Containing Di-2-Ethylhexyl Phosphoric Acid

Document Type : Research Paper

Authors

R Davarkhah
M Asgari
B Salimi
P Ashtari
Abstract
Facilitated transport kinetics of uranium (VI) from a phosphoric acid medium into another phosphoric acid medium as a receiving phase through a bulk liquid membrane containing di-2-ethylhexyl phosphoric acid (HDEPA) as a carrier was studied. The influence of phosphoric acid concentration in source and receiving phases, carrier concentration, type of solvent, stirring speed and temperature were investigated. The kinetic parameters (ke,ks, tmax, Jmax) were calculated for the interfacial reactions, assuming two consecutive, irreversible first-order reactions. The activation energy values were calculated as 29.40 and 19.51 kJmol-1 for extraction and stripping, respectively. The values of the calculated activation energy indicated that the extraction process was controlled by the mixed regime (both kinetic and diffusion), and the stripping process was merely diffusionally controlled. In comparison with HDEPA optimized conditions, though with adding trioctyl-phosphine oxide into membrane phase as a synergic agent, the extraction rate remained approximately constant but the stripping rate diminished dramatically that led to the decrease of the transport kinetics.

Highlights

  1. F.J. Hurst, D.J. Crouse, K.B. Brown, US Atomic Energy Comm, Rep. ORNL-TM-2522, (1969).

 2.   W.J. Jia, Z.M. Zhou, A.D. He, Z.L. Wang, C.T. Chin, Kinetic studies on the solvent extraction of uranium(VI) from phosphoric acid solution with HDEHP using laser-induced optical fiber fluorimetry, J. Radioanal. Nucl. Chem. 130 (1989) 187-194.

  1.  3.   Y. Jian-Zhang, Z. Zuming, Q. Qizong, Kinetic studies on the extraction of U(VI) from phosphoric acid medium with HDEHP, Chinese J. Nucl. Radiochem. 10 (1988) 25-29.

 4.   F.J. Hurst, Interphase transfer kinetics of uranium between phosphoric acid and DEPA-TOPO extractant using Lewis cell techniques, Hydrometallurgy, 16 (1986) 197-208.

 5.   S. Girgin, N. Acarkan, A.A. Sirkeci, The uranium (VI) extraction mechanism of D2EHPA-TOPO from a wet process phosphoric acid, J. Radioanal. Nucl. Chem., 251 (2002) 263-271.

 6.   S.K. Singh, S.K. Misra, M. Sudersanan, A. Dakshinamoorthy, S.K. Munshi, P.K. Dey, Carrier-mediated transport of uranium from phosphoric acid medium across TOPO/n-dodecane-supported liquid membrane, Hydrometallurgy, 87 (2007) 190-196.

 7.   S.K. Singh, S.K. Misra, M. Sudersanan, A. Dakshinamoorthy, Studies on the recovery of uranium from phosphoric acid medium by D2EHPA/n-dodecane-supported liquid membrane, Sep. Sci. Technol. 44 (2009) 169-189.

 8.   S. Sifniades, T. Largman, A.A. Tunick, F.W. Koff, Recovery of uranium from phosphoric acid by means of supported liquid membrane, Hydrometallurgy, 7 (1981) 201-212.

 9.   J. Bock, P.L. Valint Jr, Uranium extraction from wet process phosphoric acid.A liquid membrane approach, Ind. Eng. Chem. Fundam. 21 (1982) 417-422.

 10.H.C. Hayworth, W.S. Ho, W.A. Burns Jr, N.N. Li, Extraction of uranium from wet process          phosphoric acid by liquid membranes, Sep. Sci. Technol. 18 (1983) 493-521.

11.W. Davies, W. Gray, A rapid and specific titrimetric method for the precise determination of uranium using iron(II) sulphate as reductant, Talanta, 11 (1964) 1203-1211.

 12.H. Gorecka, H. Gorecki, Determination of  uranium in wet phosphoric acid, Talanta, 31 (1984) 459-462.

 13.M. Ma, D. He, Q. Wang, Q. Xie, Kinetics of europium (III) transport through a liquid membrane containing HEH(EHP) in kerosene, Talanta, 55 (2001) 1109-1117.

 14.D. He, M. Ma, Kinetics of cadmium (II) transport through a liquid membrane         containing tricapryl amine in xylene, Sep. Sci. Technol. 35 (2000) 1573-1585.

 15.D. He, M. Ma, Z. Zhao, Transport of cadmium ions through a liquid membrane containing amine extractants as carriers, J. Membr. Sci. 169 (2000) 53-59.

 16.W. Zhang, J. Liu, Z. Ren, S. Wang, C. Du, J. Ma, Kinetic study of chromium (VI) facilitated transport through a bulk liquid membrane using tri-n-butyl phosphate as carrier, Chem. Eng. J. 150 (2009) 83-89.

 17.A. Yilmaz, A. Kaya, H.K. Alpoguz, M. Ersoz, M. Yilmaz, Kinetic analysis of chromium(VI) ions transport through a bulk liquid membrane containing p-tert-butyl calix[4] arene dioxaoctylamide derivative, Sep. Purif. Technol., 59 (2008) 1-8.

 18.A.O. Saf, S. Alpaydin, A. Sirit, Transport kinetics of chromium (VI) ions through a bulk liquid membrane containing p-tert-butyl calix[4] arene 3-morpholino propyl diamide derivative, J. Membr. Sci. 283 (2006) 448-455.

 19.H.K. Alpoguz, S. Memon, M. Ersoz, M. Yilmaz, Transport kinetics of Hg2+ through bulk liquid membrane using calix[4] arene ketone derivative as carrier, Sep. Sci. Technol., 39 (2005) 799-810.

 20.C.F. Baes Jr, The extraction of metallic species by dialkylphosphoric acids, J. Inorg. Nucl. Chem. 24 (1962) 707-720.

  21.B.J. Thamer, Spectrophotometric and solvent-extraction studies of uranyl phosphate complexes, J. Amer. Chem. Soc., 79 (1957) 4298-4305.

 22.G. Charlot, Les Réactions Chimiques en Solution Aqueuse, Paris: Masson et Cie, (1983).

 23.M. Shamsipur, R. Davarkhah, Y. Yamini, R. Hassani, A.R. Khanchi, Selective facilitated transport of uranium (VI) across a bulk liquid membrane containing benzoyltrifluoroacetone as extractant carrier, Sep. Sci. Technol., 44 (2009) 2645-2660.

 24.T. Sato, The extraction of uranium (VI) from hydrochloric acid solutions by di-(2-ethylhexyl)-phosphoric acid, J. Inorg. Nucl. Chem., 27 (1965) 1853-1860.

 25.J. Rydberg, C. Musikas, G.R. Choppin (Eds), Principles and Practice of Solvent Extraction; Marcel Dekker: New York (1992).

 26.Z. Lazarova, L. Boyadzhiev, Kinetic aspects of copper (II) transport across liquid membrane containing LIX-860 as a carrier, J. Membr. Sci., 78 (1993) 239-245.

 27.S. Khorfan, J. Stas, M. Kassem, Stripping of uranium from Dehpa/kerosene solvents by different aqueous media, J. Radioanal. Nucl. Chem., 238 (1998) 145-148.

Keywords

Extraction
Stripping
Uranium (VI)
Phosphoric Acid
HDEPA
  1. F.J. Hurst, D.J. Crouse, K.B. Brown, US Atomic Energy Comm, Rep. ORNL-TM-2522, (1969).

 2.   W.J. Jia, Z.M. Zhou, A.D. He, Z.L. Wang, C.T. Chin, Kinetic studies on the solvent extraction of uranium(VI) from phosphoric acid solution with HDEHP using laser-induced optical fiber fluorimetry, J. Radioanal. Nucl. Chem. 130 (1989) 187-194.

  1.  3.   Y. Jian-Zhang, Z. Zuming, Q. Qizong, Kinetic studies on the extraction of U(VI) from phosphoric acid medium with HDEHP, Chinese J. Nucl. Radiochem. 10 (1988) 25-29.

 4.   F.J. Hurst, Interphase transfer kinetics of uranium between phosphoric acid and DEPA-TOPO extractant using Lewis cell techniques, Hydrometallurgy, 16 (1986) 197-208.

 5.   S. Girgin, N. Acarkan, A.A. Sirkeci, The uranium (VI) extraction mechanism of D2EHPA-TOPO from a wet process phosphoric acid, J. Radioanal. Nucl. Chem., 251 (2002) 263-271.

 6.   S.K. Singh, S.K. Misra, M. Sudersanan, A. Dakshinamoorthy, S.K. Munshi, P.K. Dey, Carrier-mediated transport of uranium from phosphoric acid medium across TOPO/n-dodecane-supported liquid membrane, Hydrometallurgy, 87 (2007) 190-196.

 7.   S.K. Singh, S.K. Misra, M. Sudersanan, A. Dakshinamoorthy, Studies on the recovery of uranium from phosphoric acid medium by D2EHPA/n-dodecane-supported liquid membrane, Sep. Sci. Technol. 44 (2009) 169-189.

 8.   S. Sifniades, T. Largman, A.A. Tunick, F.W. Koff, Recovery of uranium from phosphoric acid by means of supported liquid membrane, Hydrometallurgy, 7 (1981) 201-212.

 9.   J. Bock, P.L. Valint Jr, Uranium extraction from wet process phosphoric acid.A liquid membrane approach, Ind. Eng. Chem. Fundam. 21 (1982) 417-422.

 10.H.C. Hayworth, W.S. Ho, W.A. Burns Jr, N.N. Li, Extraction of uranium from wet process          phosphoric acid by liquid membranes, Sep. Sci. Technol. 18 (1983) 493-521.

11.W. Davies, W. Gray, A rapid and specific titrimetric method for the precise determination of uranium using iron(II) sulphate as reductant, Talanta, 11 (1964) 1203-1211.

 12.H. Gorecka, H. Gorecki, Determination of  uranium in wet phosphoric acid, Talanta, 31 (1984) 459-462.

 13.M. Ma, D. He, Q. Wang, Q. Xie, Kinetics of europium (III) transport through a liquid membrane containing HEH(EHP) in kerosene, Talanta, 55 (2001) 1109-1117.

 14.D. He, M. Ma, Kinetics of cadmium (II) transport through a liquid membrane         containing tricapryl amine in xylene, Sep. Sci. Technol. 35 (2000) 1573-1585.

 15.D. He, M. Ma, Z. Zhao, Transport of cadmium ions through a liquid membrane containing amine extractants as carriers, J. Membr. Sci. 169 (2000) 53-59.

 16.W. Zhang, J. Liu, Z. Ren, S. Wang, C. Du, J. Ma, Kinetic study of chromium (VI) facilitated transport through a bulk liquid membrane using tri-n-butyl phosphate as carrier, Chem. Eng. J. 150 (2009) 83-89.

 17.A. Yilmaz, A. Kaya, H.K. Alpoguz, M. Ersoz, M. Yilmaz, Kinetic analysis of chromium(VI) ions transport through a bulk liquid membrane containing p-tert-butyl calix[4] arene dioxaoctylamide derivative, Sep. Purif. Technol., 59 (2008) 1-8.

 18.A.O. Saf, S. Alpaydin, A. Sirit, Transport kinetics of chromium (VI) ions through a bulk liquid membrane containing p-tert-butyl calix[4] arene 3-morpholino propyl diamide derivative, J. Membr. Sci. 283 (2006) 448-455.

 19.H.K. Alpoguz, S. Memon, M. Ersoz, M. Yilmaz, Transport kinetics of Hg2+ through bulk liquid membrane using calix[4] arene ketone derivative as carrier, Sep. Sci. Technol., 39 (2005) 799-810.

 20.C.F. Baes Jr, The extraction of metallic species by dialkylphosphoric acids, J. Inorg. Nucl. Chem. 24 (1962) 707-720.

  21.B.J. Thamer, Spectrophotometric and solvent-extraction studies of uranyl phosphate complexes, J. Amer. Chem. Soc., 79 (1957) 4298-4305.

 22.G. Charlot, Les Réactions Chimiques en Solution Aqueuse, Paris: Masson et Cie, (1983).

 23.M. Shamsipur, R. Davarkhah, Y. Yamini, R. Hassani, A.R. Khanchi, Selective facilitated transport of uranium (VI) across a bulk liquid membrane containing benzoyltrifluoroacetone as extractant carrier, Sep. Sci. Technol., 44 (2009) 2645-2660.

 24.T. Sato, The extraction of uranium (VI) from hydrochloric acid solutions by di-(2-ethylhexyl)-phosphoric acid, J. Inorg. Nucl. Chem., 27 (1965) 1853-1860.

 25.J. Rydberg, C. Musikas, G.R. Choppin (Eds), Principles and Practice of Solvent Extraction; Marcel Dekker: New York (1992).

 26.Z. Lazarova, L. Boyadzhiev, Kinetic aspects of copper (II) transport across liquid membrane containing LIX-860 as a carrier, J. Membr. Sci., 78 (1993) 239-245.

 27.S. Khorfan, J. Stas, M. Kassem, Stripping of uranium from Dehpa/kerosene solvents by different aqueous media, J. Radioanal. Nucl. Chem., 238 (1998) 145-148.

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