Beruflich Dokumente
Kultur Dokumente
David DePaoli
Oak Ridge National Laboratory
Managed by UT-Battelle
for the Department of Energy
Presented at:
Introduction to Nuclear Chemistry and Fuel Cycle
Separations
North Las Vegas, Nevada
July 20, 2011
Outline
Introduction
Some applications to date
Solvent extraction
Plant-level modeling
Agent design
Products
varied composition
meeting stringent
specifications
shearing
solidification
dissolution
Fuel
voloxidation
feed & accountability
solvent extraction
cycles
off-gas treatment
waste treatment
recovery systems
Waste forms
TBP
TBP
M ( NO3 ) ai bi TBP
A. D. Ryon,
ORNL-3045,
1961
NO
ai
NO3 M
a
M ( aqi ) ai NO3 ( aq) bi TBP( org)
Ki
ai
M ( NO )
bi TBP(org)
3 ai
M ( NO ) b TBP
M NO TBP
3 ai
ai
aq
org
ai
3 aq
bi
org
Original predictions:
Graphical stage
calculations using
experimental equilibrium
data and operating lines
KU'
UO NO TBP
2
'
KTh
aq
org
Th NO TBP
4
aq
K H'
2
3 aq
4
3 aq
3
org
HNO3 3 TBPorg
H NO TBP
aq
3 aq
org
KU' C1 C2 C3 2 C2 3
'
KTh
C5 C6 C7 2 C8 3
H 3 UO22 10 Th 4
Rainey and Watson, 1975
Feed
Compositions
D value
100
SASPE
Activities
1000
Distribution
Ratio
Calculation
10
1
D( M )
Organic
Phase
Speciation
0.1
TBP , NO
, H
, H
OK 0 , K1 ,...K n ,
1 ,... n
0.01
0.001
0.1
10
100
[HNO3 ], M
Input
Mass
Balance
SASSE
Process
Parameters
Flowsheet
Module
y1i
Mass
Balance
y1o
y2i y2o
y3i
y3o
yi
Org.
Org.
Org.
yo
xo
Aq
Aq
Aq
xi
x1i
x1o
x2i x2o
x3i
x3o
Calculated
Flowsheet
Strip
b
Scru
n
4.50E-02-5.00E-02
o
acti
E x tr
1.00E+00
1.00E-02
1.00E-04
3.50E-02-4.00E-02
0.050
2.50E-02-3.00E-02
0.045
2.00E-02-2.50E-02
1.50E-02-2.00E-02
0.040
1.00E-02-1.50E-02
0.035
Conc., M
4.00E-02-4.50E-02
3.00E-02-3.50E-02
Output
1.00E-06
1.00E-08
1.00E-10
Org
1.00E-12
Aq
1.00E-14
5.00E-03-1.00E-02
0.00E+00-5.00E-03
0.030
1.00E-16
1.00E-18
0.025
Stage
0.020
0.015
0.010
0.005
Stage
0.000
Dec. Scrub
Concentration
Product
Raffinate
-1-0
-2--1
-3--2
-4--3
-5--4
-6--5
-7--6
-8--7
-9--8
-10--9
-11--10
-12--11
Stage
Scrub conc.
-1-0
-2--1
-3--2
-4--3
-5--4
-6--5
-7--6
-8--7
-9--8
-10--9
-11--10
-12--11
-13--12
-14--13
Stage\
HNO3, feed
broken down into three segments that were executed separately to achieve a steadystate material balance for the complete plant.
R. T. Jubin, ORNL
B. B. Cipiti, SNL
O
O
O
O
O
O O
O O
O
O
O
O O
106
1010
O
O O
105
103
N
N
Hg2+/Cu2+ = 5
N
N
N
N
Cu2+/Hg2+ = 104
HO2C
HO2C
CO2H
HO2C
CO2H
HO2C
Eu3+/Al3+ = 13
CO2H
CO2H
Al3+/Eu 3+ = 500
B.Hay, ORNL
Optimize:
binding affinity
selectivity
solubility
stability
cost
Design
criteria
Computational
screening
Molecular
modeling
Ligand synthesis
Structural characterization
including X-ray analysis
Thermodynamic studies,
Binding constant measurement
B.Hay, ORNL
140 g
360 g
500 g
Experimental validation
3.90
3.30
N
O
Extraction into t-butylbenzene from Oaqueous
solution
containing 1 M NaNO3, 1.5 mM HNO13, 0.1 mM
Eu(N03)3, and 1-L of 15 5Eu tracer solution.
Horwit z, E.P.; Diet z, M.L.; Fisher, D.E. Solvent Ext r. Ion Exch.
O 1991, 9, 1.
1
N
1,6
7
2
E
u
Ext
con
Eu(
E
u
3ICJ
3IDJ
3IEJ
N
O
10
102
log
DEu
Sr
E
u
104
100
10-2
N
O
[ligand], mollit -1
[ligand], mollit -1
10-4
-1
10-6
0.0001
0.001
0.01
0.1
[ligand], M
10 million times more effective
-2
10
12
14
U,
kcal/mol
U,
kcal/mol
16
B.Hay, ORNL
http://www-fp.mcs.anl.gov/anes/SMANES
/gnep06-final.pdf
Data must be captured, managed, integrated, and mined from a wide range of
sources to enable the optimal design and operation of separation processes
Computer resources and access
Export control issues
http://www.sc.doe.gov/bes/reports/
abstracts.html#ANES
Fundamental Methods
and Models
Cross-cutting
Methods and
Tools
Waste Forms
Safeguards and
Separations
Reactors
Integrated
Performance
and Safety
Codes
Nuclear Fuels
Safeguards
Used
Fuel
Disassembly
Head-end operations
Voloxidation
Dynamic Inventory
Analysis
Dissolution
Separations
Aqueous Separation
Steps
Electrochemical
Separation
Alternative Separation
Conversion
To
Recycled
Fuel
Production
Solid Waste
to
Repository
Solidification and
packaging
Offgas
Treatment
Gaseous Emissions
Distributed computing
capabilities
Support verification, validation,
and uncertainty quantification
Documentation and materials
that facilitate usage of the toolkit
FY10 Results
Finite Element-based (unstructured) Lattice Boltzmann Method (FELBM)
Testing of modifications to codes solver and BC implementation
Verified excellent parallel scaling performance up to 2048 cores on Argonnes BlueGene/P
OpenFOAM
Demonstration of limits to approach for three phase liquid-liquid-air simulation
Coupled mixing/separation zone contactor models exploring BC and mesh dependence
K. E. Wardle, ANL
oil is red
water is
transparent
blue
Only large droplets are resolved (~1mm)
25
8-Vane
Curved
K. E. Wardle, ANL
reconstructed
phase fraction
maps
electrodes
K. E. Wardle, ANL
28
1 mm
Elapsed time: 37 ms
Spatial resolution: ~7 m
1 mm
1 mm
seeing is believing . . .
3.5 mm
Generate data
useful for model
development
bubbles
noise
bubbles
300 m
Area (pixels)
drops
drops
Current focus:
Chemical Transport
Important chemical reactions occur at the interface
Challenges
Lack of basic understanding of how species move
across interfacial region
Strongly coupled physical and chemical processes
H2O
H+
HNO3TBP
UO22+
An approach to understand
solvent extraction
NO3
UO2(NO3)2 2 TBP
HNO32TBP
C12H26
?
10 nm 1
T BP
t = 0 ns
Uranyl
Nitrate Ion
Water
TBP
Dodecane
V. de Almeida, ORNL
WaterTBP-NDD
WaterTBP-NDD
mixture
Front
3 mm
E-chem modeling
Goal: Predictive capability of electrorefiner
performance
Mark-IV
0.010
i(U)
i(Np)
i(Gd)
i(total)
Experimental Data
i(Np-ss)
i(total-ss)
0.006
Current (A)
0.008
0.004
0.002
FY15 Target:
Model that incorporates electrochemical kinetics,
phase morphology, and property data.
0.000
-1.1
-1.3
-1.5
-1.7
-1.9
-2.1
Methodology:
Isotopic composition estimates of fuel assemblies calculated using Monte Carlo burnup
Determine neutron source terms and use MCNP for transport and multiplication calculations
H. R. Trellue, LANL
M. Collins, LANL
K. Michel, LANL
12:05:40
12:05:36
12:05:34
Summary
Modeling and simulation have provided useful input
to the development of fuel cycle separations over the
past several decades.
With significant scientific advancements and vast
increases in computational power, modeling and
simulation can play an increasing role in solving the
complex challenges to be overcome in developing
advanced nuclear energy systems.
Acknowledgments
Ben Cipiti
Michael Collins
Valmor de Almeida
Ben Hay
Bob Jubin
Alex Larzelere
Kelly Michel
Candido Pereira
Monica Regalbuto
Pratap Sadasivan
Holly Trellue
Kent Wardle
Prepared by Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, Tennessee 378316285, managed by UT-Battelle, LLC, for the U.S. Department of Energy under contract DEAC05-00OR22725.
The submitted manuscript has been authored by a contractor of the U.S. Government under
contract DE-AC05-00OR22725. Accordingly, the U.S. Government retains a nonexclusive,
royalty-free license to publish or reproduce the published form of this contribution, or allow
others to do so, for U.S. Government purposes.
This report was prepared as an account of work sponsored by an agency of the United States
government. Neither the United States government nor any agency thereof, nor any of their
employees, makes any warranty, express or implied, or assumes any legal liability or
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