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A Molecular Dynamics Study on the liquid-liquid extraction of Uranyl ions with Tri-Butyl-Phosphate

Mark Thomas

Figure 1: Structure of TBP molecule.

1. Introduction

 

Nuclear reprocessing is becoming an increasingly important process in a time where there is a large focus on the sustainability of power generation. Not only can it reduce the high-level waste volume, but can improve the efficiency of the cycle, by recycling unreacted fuel. The PUREX process is the most widely used method.

 

1)The fuel rods are dissolved in nitric acid; 2)This is then contacted with an organic phase containing 30% v/v tri-butyl-phosphate (TBP) (as seen in figure 1) in dodecane;

3)The TBP selectively binds to uranyl nitrate; 4)These neutral complexes readily migrate into the organic phase.

(UO 2 2+ ) aq +2(NO 3 - ) aq +2(TBP) org → ??? → (UO 2 (NO 3 ) 2 Ÿ 2TBP) org

Although widely used since the 1950’s , there are many aspects of the process that are not understood on a molecular level. The TBP tends to form structures called reverse micelles around polar molecules such as water and acids due to its hydrophilic and hydrophobic properties, aggregating at the interface [1] . The particular mechanism of the extraction around the interface is unknown. Moreover, there have been continuous improvements in the force field models used for Molecular Dynamics (MD) simulations, meaning that the validity of earlier results are now bought into question. The drivers for third phase formation are still unknown, an occurrence that can seriously impair the liquid-liquid extraction.

2. Motivations & Objectives

 

Motivations Increase efficiency of process by gaining further understanding on rate of mass transfer and partitioning coefficients

 

To further understand the driving forces of third phase so it can be avoided Objectives

Systematically and rigorously test the force field models for TBP, water and dodecane Gain further insight into the kinetics, complexation and extraction mechanisms

4. Binary System New TBP partial charges optimised for the description of a TBP/dodecane system, were
4. Binary System
New TBP partial charges optimised for the description of a TBP/dodecane system, were
found to lead to TBP/water immiscibility, counter to experimental observation. It is known
that saturation point TBP:H 2 O is 1:1 [6] .
•  Changing Lennard-Jones (LJ) potentials had little effect on structure
•  Scaling partial charges on TBP resulted in homogenous mixture and better
thermodynamic properties of system (reasonable description of TBP/dodecane also)
•  0.9 best match with free energy of solvation, 0.8 best match with excess enthalpy of
mixing. 0.84 OPLS-MNDO compromise was taken
Figure 3: 0.84 MNDO TBP (PINK) & TIP3P H 2 O (PURPLE).
Figure 4: TBP (RIGHT) & H 2 O (LEFT) dimer formed in system.
Figure 2: 0.6 MNDO TBP (PINK) & TIP3P H 2 O (PURPLE).
2
Table 2: Effect of charge of free
0.60
MNDO
energy of solvation.
0.84
MNDO
Simulation
Systems
1
Experimental
Free energy of
solvation of H 2 O
in TBP (kJ mol -1 )
Experimental
-19.58112
0.60
MNDO
-6.12 ± 0.29
0.9 MNDO
LJ – 1.25
LJ – 1.75
LJ – 2
LJ - 5
0
0.70
MNDO
-10.14 ± 0.79
0.80
MNDO
-15.47 ± 0.57
-1
0.81
MNDO
-15.18 ± 0.25
0.82
MNDO
-16.66 ± 0.39
0.83
MNDO
-14.38 ± 0.52
-2
0.84
MNDO
-17.05 ± 0.96
0.85
MNDO
-14.54 ± 0.15
0.86
MNDO
-17.71 ± 0.81
-3
0.87
MNDO
-18.99 ± 0.61
0.88
MNDO
-20.93 ± 1.04
0.89
MNDO
-19.29 ± 1.50
-4
0.6
0.7
0.8
0.9
1
0.90
MNDO
-19.75 ± 0.41
Scaling factor for MNDO charge
1.00
MNDO
-22.84 ± 0.92
Figure 5: Effect of partial charges on enthalpy of system.
Figure 6: RDF of OW-OW interactions. Effect of partial charges & LJ scaling.
Excess enthaly of mixing (kJ/mol)
 

7. Umbrella Sampling

 

Uranyl nitrate ion was pulled across interface, expected to lose 2 (H 2 O ) a n d f o r m (UO 2 (NO 3 ) 2 Ÿ2TBP). Uranyl nitrate in fact pulled water across interface and did not bind with TBP. Gibbs free energy profile indicates that extrachon process is unfavourable, with an achvahon energy of 60 kJ mol -1 . This result can not be true otherwise the PUREX process wouldn't work, and we believe we have seriously undereshmated the anrachons between TBP and uranyl. “Double Pull” simulahon, showed that organic phase is more favourable than

kJ mol -1

Gibbs Free Energy Profile “Double Pull”
Gibbs Free Energy Profile
“Double Pull”

Figure 12: Gibbs free energy curve for pulling & “double” pulling simulation.

Table 3: Composition of

 

interface.

pulling simulations.

 

O

Aq

Figure 13: Pulling of uranyl ion (RED) from the aqueous phase consisting of NO (GREEN), H

Figure 13: Pulling of uranyl ion (RED) from the aqueous phase consisting of NO 3 - (GREEN), H 3 O + (ORANGE) & H 2 O (BLUE).

 

nH 2 O

4

1247

nHNO 3

35

-

nTBP

38

-

nDDC

108

-

nH 3 O +

-

210

nNO 3 -

-

210

 

3. Methodology

GROMACS 4.6.7 NPT – 1 atm Berendsen barostat. 298.15 K v-rescale thermostat [2] Time step of 1 ps Energy minimisation followed by MD

•   GROMACS 4.6.7 •   NPT – 1 atm Berendsen barostat. 298.15 K v-rescale thermostat
 

Force Field

System

OPLS-2005 [3]

TBP

MNDO & ‘DL’

Water

TIP3P & SPC/E

Dodecane

OPLS-AA

HNO 3

ESP [4]

UO 2 +

QM [5]

Table 1: Force fields used for system and each molecule.

5. Ternary System A new charged dodecane model was developed to prevent liquid-gel phase transition. Dodecane
5. Ternary System
A new charged dodecane model was developed to prevent liquid-gel
phase transition. Dodecane was added into the system for 3 different
TBP:H 2 O ratios. Hydrophobic dodecane avoids contact with water.
Resulted in single phase with possible reverse micelles formed.
P-OW
H 2 O-ddc
Figure 8: RDF of ddc-H 2 O & P-OW for ternary system.
Figure 7: Uncharged and charged dodecane model (PURE).
Figure 9: TBP (GREEN) & H 2 O (BLUE) for ternary system.
   

6. Quaternary System

 

Nitric acid was added into the system. Emulsion like structure observed. No H 2 O- dcc interactions, but HNO 3 slightly more dispersed. Down to more negatively charged H atom. Reverse micelles formed protecting polar molecules from ddc.

Nitric acid was added into the system. Emulsion like structure observed. No H O- dcc interactions,
Figure 11: TBP (GREEN), HNO (RED) H O (BLUE).

Figure 11: TBP (GREEN), HNO 3 (RED) H 2 O (BLUE).

 

Figure 10: TBP (RIGHT) & HNO 3 (LEFT) dimer.

8. Conclusion

 

The TBP scaling factor 0.6 underestimated intermolecular forces. A factor of 0.84 or 0.9 OPLS-MNDO is recommended The unchanged OPLS-AA dodecane prevents liquid-gel phase transition

 

Current force field models do not favour uranyl extraction, despite formation of reverse micelles

Recommendations Add polarizabilities to force field models, in particular phosphate head Increase LJ potential between uranyl and TBP Carry out/compare results to additional experimental data (neutron scattering & x-ray diffraction)

9. Acknowledgements

The author would like to thank Junju Mu, Karl Fairhurst and Gareth Myers for their results and continuing cooperation, and Andrew Masters fo r his limi tless help and knowledge throughout.

 

10. Bibliography

 

1.

C. A. Hawkins, L. X. Dang, M. Nilsson, and H. D. Nguyen Q. N. Vo, The Journal of Physical

 

2.

Chemistry, vol. 119, no. 4, pp. 1588–1597, 2015. J. Postma H. Berendsen, The Journal of Chemical Physics, vol. 81, no. 8, pp. 3684-3690, 1984.

3.

H. Beard, Y. Cao J. Banks, J. Comput. Chem., vol. 26, pp. 1752–1780, 2005.

4.

M. Burgard, and G. Wipff M. Baaden, J. Phys. Chem., vol. 105, pp. 11131-11141, 2001.

5.

S. P. Tiwari, and E. J. Maginn N. Rai, The Journal of Physical Chemistry, vol. 116, p.

6.

1088510897, 2012. L. Donadieu, and M. Benedict D. R. Olander, A.1.Ch.E. Journal, vol. 7, no. 1, pp. 152-157, 1961.

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