2nd ACE Workshop, Idaho University Consortia

Nuclear Materials Research, Issues, and Applications

May 8-9, 2007

ELECTROMETALLURGY REVIEW: How can pyroprocessing of

spent nuclear fuel benefit from the existing knowledge base, and
the need for future research
Batric Pesic
Materials Science and Engineering Department
pesic@uidaho.edu; Tel.: 208.885.6569

University of Idaho
ACKNOWLEDGMENT

Royce Smith - Phelps Dodge

Mike Simpson/Ken Marsden - INL

Fred Gunnerson UI/ACE

 OUTLINE

Objectives of the presentation

Brief review of the electrometallurgy principles

Commercial size plants and electrolytic cell design

Electrorefining of uranium- Need for further research

Movie: Molten salt electrometallurgy- electrowinning of aluminum

 OBJECTIVES

Define electrometallurgy

To demonstrate industrial scale electrometallurgy

To focus on electrolytic cell design in industrial practice

Review major present challenges during electrorefining of spent nuclear fuel

To point out that development of pyroprocessing of spent nuclear fuels

(electrometallurgy of uranium) technology should utilize the industrial
experience of base metals processing

Further research
 ELECTROMETALLURGY

Electrowinning Electrorefining Electroplating Electroforming

Insoluble anodes Soluble anodes

Electrolyte: Electrolyte: Bare metal Mundrel
- Aqueous - Aqueous cathode Thin film
- Molten salts - Molten salts metallization

Metal transfer Metal transfer Metal transfer Cathodic metal Cathodic metal
Molten salts Aqueous Me Me deposition deposition

Al, Mg, Li, Zn, Cd, Cu Pure metal: Cr plated bumpers Metallic masters
K, Na, etc. Ni, Co, etc. Cu, Pb, etc. Cu- interconnects, MEMS
Etc. Etching
Electropolishing
Etc.
 ELECTROLYTE CHOISE : Aqueous vs. Molten Salts
Determined by both, thermodynamics and kinetics. But, mainly by thermodynamics.

Standard reduction potential series: EMF of LiCl-KCl eutectic at 450 C

- Metal below reduces metal above Yamawaki et al. Pure Appl Chem vol 72, No 10, pp. 1839-1849
- Metals below hydrogen line cannot
be electrowon?
 INDUSTRIAL ELECTROMETALLURGY

Annual production = Annual usage of current amperage

Current amperage = Electrodeposition reaction rate

Faradays Law:
96500 C 1Eq.wt x10-6 tons
xAmp.31.5x10-6 sec/y X (tons)

High amperage however can result in high current density.

High current density will lead to electrodeposition of:
- Metal powders
- Dendrites

High current amperage (needed to meet the production rate) must be distributed
over large electrode area. Large electrode area achieved by using large
number of electrodes of flat plate geometry.

To deposit 1-ton/day Uranium: 14,084 Amps is needed.

At current density 100 A/m2, total cathode area needed is 140.84 m2.
 ELECTROLYSIS PLANT SCALE UP

Electrolytic cells utilizing flat plate electrodes can readily be wired for
proper distribution of CURRENT and POTENTIAL in order to ensure
plant production rate and good quality product (low current density)

Electrolytic cells are wired in series while the electrodes in a cell are wired
in parallel.
INDUSTRIAL ELECTROMETALLURGY EXAMPLES

Aqueous Electrolytes
- Electrowinning of copper
- Electrorefining of copper
- Electrowinning of zinc

Molten Salt Electrolytes

- Electrowinning of aluminum
 ELECTROMETALLURGY OF COPPER

Electrowinning: Electrorefining:
- Insoluble Anodes - Copper anodes
- Stainless steel cathodes - Copper cathodes
(thin starter sheets)
- SS cathodes (blanks)
CATHODE COPPER ON THE WAY TO STRIPPING
STRIPPING OF COPPER

Note perfect stripping (no adhesion problems)

of cathode copper.

Edges of stainless steel cathode are

protected with a plastic strip to prevent
encapsulation of electrode substrate.

SS cathode is undamaged, perfectly straight.

It will undergo waxing before its return to
electrolytic tank.
Zinc Tankhouse
Phelps Dodge
Morenci
Hydrometallurgical Division

Phelps Dodge Morenci

Hydrometallurgical Division Overview

May 9, 2007
Hydromet Processes
Leaching: process by which metals are removed
from ore using a percolating liquid

Solvent Extraction (SX): process by which leach

solution is concentrated and purified into an
electrolyte via a selective organic reagent

Electrowinning (EW): process by which metal is

electroplated from an electrolyte solution

May 9, 2007
Processing Material Flow
Morenci Hydrometallurgical Division
Run of Mine
(ROM) Leaching Solvent
Ore Extraction (SX)
from
Mine

Crush and
Convey
Mine for Leach Electrowinning
(MFL) (EW)

Morenci
Concentrator

Copper Copper
Concentrate Cathode
May 9, 2007
Hydromet Material Flow

RAFFINATE BARREN ORGANIC LEAN ELECTROLYTE

TANKHOUSE
TANKHOUSE
LEACHING
LEACHING EXTRACTIONSTAGE
EXTRACTION STAGE STRIPSTAGE
STRIP STAGE ELECTROWINNING
ELECTROWINNING
STOCKPILES
STOCKPILES 99.999% PURE CATHODE
99.9% PURE CATHODE

PREGNANT LEACH
LOADED ORGANIC RICH ELECTROLYTE
SOLUTION

May 9, 2007
Hydromet Overview
SX
Four SX plants spread over approximately eight miles
Process over 116,000 gpm of pregnant leach solution (PLS)
Total daily production of 2.3 million pounds of rich electrolyte (RE)

EW
Three EW plants spread over approximately five miles
Consume over 2,000 MW per day to electroplate cathode
Harvest more than 2.2 million pounds of copper cathode per day

May 9, 2007
Solution Extraction PFD: Straight Series Parallel
Raffinate Pond

Raw Water LE
LE

E1P E2S E1S W1 S1

LO

RE

Wash
Tank

BO BO
Tank

PLS PLS Pond

May 9, 2007
Metcalf SX
Two SX Trains one running 2P x 1W x 1S and the other running 2P x 1S.
Design flow of 24,000 gpm PLS
Currently running 34,000 gpm of PLS
Organic reagent is LIX 616 produced by Cognis

May 9, 2007
Modoc SX

Two SX Trains both

running 1P x 2E x
1W x 1S

Design flow of
24,000 gpm PLS

Currently running
36,500 gpm of PLS

Organic reagents
are LIX 616
produced by Cognis

May 9, 2007
Central SX
One train running 1P x 2E x 1S
Design flow of 19,000 gpm PLS
Reagent is LIX 616 produced by Cognis

May 9, 2007
Stargo SX
One train running 1P x 2E x 1W x 1S
Design flow of 17,500 gpm PLS
Currently running 26,500 gpm of PLS
Reagent is LIX 616 produced by Cognis

May 9, 2007
Electrowinning PFD

AC
Cobalt FC-1100 S. A.
Rectifiers

DC
LE
RE from
SX
Filters HX ER Tankhouse
HX
Tank

CE
LE to SX Cathode
Boilers

Recalculating Boiler
Water

May 9, 2007
Central EW
Five cell lines with a total of 548 cells
Daily production is around 1 million pounds
Maximum rectifier capacity of 190,000 amps
Permanent cathode technology using stainless steel blanks with a bottom edge strip
Two stripping machines

May 9, 2007
Southside EW
Two cell lines with 110 cells each
Daily production is slightly more than 500,000 pounds
Maximum rectifier capacity of 90,000 amps
Permanent cathode technology using stainless steel blanks with a waxed bottom
Single stripping machine

May 9, 2007
Stargo EW
Three cell lines with 108 cells each
Daily production is approximately 800,000 pounds
Maximum rectifier capacity of 135,000 amps
Permanent cathode technology using ISO 2000 process
Two stripping machines

May 9, 2007
ELECTROWINNING OF METALS FROM
MOLTEN SALT ELECTROLYTES
PYROPROCESSING OF SPENT NUCLEAR FUEL
*** Current problems and ongoing research ***
PYROPROCESSING OF SPENT NUCLEAR FUEL
ELECTROREFINING OF URANIUM
 Two technical problems:

1. Dendritic growth of uranium

2. Cylindrical geometry of electrodes

is difficult to scale-up

Mark-IV electrorefiner for processing driver fuel

Mark-V electrorefiner for processing blanket fuel

 ONGOING RESEARCH EFFORTS

are directed toward developing the methods for electrodeposition

of compact uranium!

Compact uranium electrodeposits will enable simplification and scale up

of electrolytic cells for processing of spent nuclear fuel.

Simplification of electrorefining will be based on the use of electrodes

with parallel plate geometry (as found in base metal electrometallurgy).
 RESEARCH CONCEPTS

Fundamental understanding of the mechanisms for growth of

dendritic uranium.

Focus on the THERMODYNAMIC and KINETIC conditions for nucleation

and growth of uranium nuclei:

THERMODYNAMIC CONDITIONS
. KINETIC CONDITIONS

Island growth (Volmer-Weber) forms three dimensional islands

because slow diffusing film atoms are more strongly bound to each other
than to substrate:

Layer-by-layer growth (Frank-van der Merwe) produces films of highest

crystalline quality. The film atoms are more strongly bound to the substrate
than to each other, and are characterized with fast solid-state diffusion:

Mixed growth (Stranski-Krastanov) initiates in a layer by layer mechanism

and then forms three dimensional islands due to energetic changes:
 Effect of Electrokinetic Parameters

Electrodeposition occurs in three distinct steps:

Mass transport:
U3+(solution) <=> U3+ (interface) (1)
Charge-transfer:
U3+(interface) <=> Uo (surface) (2)
Surface diffusion:
Uo(surface) <=> Uo (lattice) (3)
The fundamental problem of electrodepositing uranium on solid cathode
Is a very fast CHARGE TRANSFER REACTION, due to high processing
temperatures (about 450 C)

Dendrite (or powder) formation can be precluded only if the reaction is

In ACTIVE REGION. (Note: Active region is determined from Tafel
Polarization Plots, see below.)
Therefore, with respect to growth of compact uranium deposits, the research
efforts should be directed toward the development of methods to either:

1. Slow down the CHARGE TRANSFER REACTIONS

or
2. To increase the rate DIFFUSION CONTROLLED REACTIONS
 N T ION
TH A TTE
AN YO U
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KY FOR
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