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2 nd ACE Workshop, Idaho University Consortia Nuclear Materials Research, Issues, and Applications May 8-9,
2 nd 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
UniversityUniversityUniversity ofofof IdahoIdahoIdaho
ACKNOWLEDGMENT Royce Smith - Phelps Dodge Mike Simpson/Ken Marsden - INL Fred Gunnerson – UI/ACE

ACKNOWLEDGMENT

ACKNOWLEDGMENT Royce Smith - Phelps Dodge Mike Simpson/Ken Marsden - INL Fred Gunnerson – UI/ACE

Royce Smith - Phelps Dodge

Mike Simpson/Ken Marsden - INL

Fred Gunnerson – UI/ACE

OUTLINE

OUTLINE Objectives of the presentation Brief review of the electrometallurgy principles Commercial size plants and

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

OBJECTIVES • Define electrometallurgy • To demonstrate industrial scale electrometallurgy • To focus on electrolytic

• 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

ELECTROMETALLURGYELECTROMETALLURGY

ELECTROMETALLURGY ELECTROMETALLURGY Electroplating Bare metal cathode Cathodic metal deposition Cr plated bumpers
Electroplating Bare metal cathode Cathodic metal deposition Cr plated bumpers Cu- interconnects, Etc.
Electroplating
Bare metal
cathode
Cathodic metal
deposition
Cr plated bumpers
Cu- interconnects,
Etc.
Electrowinning Electrorefining Insoluble anodes Electrolyte: Soluble anodes Electrolyte: - Aqueous - Aqueous -
Electrowinning
Electrorefining
Insoluble anodes
Electrolyte:
Soluble anodes
Electrolyte:
- Aqueous
- Aqueous
- Molten salts
- Molten salts
Metal transfer
Molten salts
Metal transfer
Aqueous
Metal transfer
Me Me
Al, Mg, Li,
K, Na, etc.
Zn, Cd, Cu
Ni, Co, etc.
Pure metal:
Cu, Pb, etc.

Electroforming

Mundrel

Thin film metallization

Cathodic metal deposition

Metallic masters MEMS Etching Electropolishing Etc.

ELECTROLYTE CHOISE : Aqueous vs. Molten Salts

ELECTROLYTE CHOISE : Aqueous vs. Molten Salts Determined by both, thermodynamics and kinetics. But, mainly by

Determined by both, thermodynamics and kinetics. But, mainly by thermodynamics.

thermodynamics and kinetics. But, mainly by thermodynamics. Standard reduction potential series: - Metal below redu ces
thermodynamics and kinetics. But, mainly by thermodynamics. Standard reduction potential series: - Metal below redu ces

Standard reduction potential series:

- Metal below reduces metal above

- Metals below hydrogen line cannot be electrowon?

EMF of LiCl-KCl eutectic at 450 C

Yamawaki et al. Pure Appl Chem vol 72, No 10, pp. 1839-1849

INDUSTRIAL ELECTROMETALLURGY

INDUSTRIAL ELECTROMETALLURGY Annual production = Annual usage of current amperage Current amperage = Electrodeposition

Annual production = Annual usage of current amperage

Current amperage

= Electrodeposition reaction rate

Faraday’s Law:

96500 C xAmp.31.5x10 -6 sec/y

1Eq.wt x10 -6 tons 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/m 2 , total cathode area needed is 140.84 m 2 .

ELECTROLYSIS PLANT SCALE UP

ELECTROLYSIS PLANT SCALE UP Electrolytic cells utilizing flat plate electrodes can readily be “wired” for proper

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

INDUSTRIAL ELECTROMETALLURGY EXAMPLES Aqueous Electrolytes - Electrowinning of copper - Electrorefining of copper -

Aqueous Electrolytes

- Electrowinning of copper

- Electrorefining of copper

- Electrowinning of zinc

Molten Salt Electrolytes

- Electrowinning of aluminum

ELECTROMETALLURGY OF COPPER

ELECTROMETALLURGY OF COPPER Electrowinning: - Insoluble Anodes - Stainless steel cathodes Electrorefining: - Copper anodes

Electrowinning:

- Insoluble Anodes

- Stainless steel cathodes

Electrorefining:

- Copper anodes

- Copper cathodes (thin starter sheets)

- SS cathodes (blanks)

Stainless steel cathodes Electrorefining: - Copper anodes - Copper cathodes (thin starter sheets) - SS cathodes

CATHODE COPPER ON THE WAY TO STRIPPING

CATHODE COPPER ON THE WAY TO STRIPPING

STRIPPING OF COPPER

STRIPPING OF COPPER Note perfect stripping (no adhesion problems) of cathode copper. Edges of stainless steel
STRIPPING OF COPPER Note perfect stripping (no adhesion problems) of cathode copper. Edges of stainless steel

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

Zinc Tankhouse
Zinc Tankhouse
Zinc Tankhouse
Zinc Tankhouse

Phelps Dodge

Morenci

Hydrometallurgical Division

Phelps Dodge Morenci Hydrometallurgical Division Phelps Dodge Morenci Hydrometallurgical Division Overview May 9, 2007

Phelps Dodge Morenci Hydrometallurgical Division Overview

May 9, 2007

Hydromet Processes

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

reagent • Electrowinning (EW): process by which metal is electroplated from an electrolyte solution May 9,
reagent • Electrowinning (EW): process by which metal is electroplated from an electrolyte solution May 9,
reagent • Electrowinning (EW): process by which metal is electroplated from an electrolyte solution May 9,

May 9, 2007

reagent • Electrowinning (EW): process by which metal is electroplated from an electrolyte solution May 9,

Processing Material Flow

Processing Material Flow

Morenci Hydrometallurgical Division

Solvent Extraction (SX)

Solvent Extraction (SX) Electrowinning (EW)

Electrowinning

(EW)

Solvent Extraction (SX) Electrowinning (EW)

Run of Mine (ROM) Leaching

(SX) Electrowinning (EW) Run of Mine (ROM) Leaching Ore from Mine Crush and Convey Mine for
Ore from Mine
Ore
from
Mine

Crush and

Convey

Run of Mine (ROM) Leaching Ore from Mine Crush and Convey Mine for Leach (MFL) Morenci
Run of Mine (ROM) Leaching Ore from Mine Crush and Convey Mine for Leach (MFL) Morenci
Run of Mine (ROM) Leaching Ore from Mine Crush and Convey Mine for Leach (MFL) Morenci
Run of Mine (ROM) Leaching Ore from Mine Crush and Convey Mine for Leach (MFL) Morenci

Mine for Leach (MFL)

Ore from Mine Crush and Convey Mine for Leach (MFL) Morenci Concentrator Copper Concentrate Copper Cathode

Morenci

Concentrator

from Mine Crush and Convey Mine for Leach (MFL) Morenci Concentrator Copper Concentrate Copper Cathode May
from Mine Crush and Convey Mine for Leach (MFL) Morenci Concentrator Copper Concentrate Copper Cathode May

Copper

Concentrate

Copper

Cathode

May 9, 2007

from Mine Crush and Convey Mine for Leach (MFL) Morenci Concentrator Copper Concentrate Copper Cathode May

Hydromet Material Flow

Hydromet Material Flow

RAFFINATE

BARREN ORGANIC

LEAN ELECTROLYTE

B A R R E N O R G A N I C LEAN ELECTROLYTE PREGNANT

PREGNANT LEACH SOLUTION

LOADED ORGANIC

RICH ELECTROLYTE

PREGNANT LEACH SOLUTION LOADED ORGANIC RICH ELECTROLYTE TANKHOUSE TANKHOUSE ELECTROWINNING 99.9% 99.999%

TANKHOUSE TANKHOUSE ELECTROWINNING 99.9% 99.999% ELECTROWINNING PURE PURE CATHODE CATHODE

ELECTROLYTE TANKHOUSE TANKHOUSE ELECTROWINNING 99.9% 99.999% ELECTROWINNING PURE PURE CATHODE CATHODE May 9, 2007
ELECTROLYTE TANKHOUSE TANKHOUSE ELECTROWINNING 99.9% 99.999% ELECTROWINNING PURE PURE CATHODE CATHODE May 9, 2007

May 9, 2007

ELECTROLYTE TANKHOUSE TANKHOUSE ELECTROWINNING 99.9% 99.999% ELECTROWINNING PURE PURE CATHODE CATHODE May 9, 2007

Hydromet Overview

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

2,000 MW per day to electroplate cathode • Harvest more than 2.2 million pounds of copper

Solution Extraction PFD: Straight Series Parallel

Solution Extraction PFD: Straight Series Parallel

Raffinate Pond

Raw Water LE LE W1 S1 E2S E1S E1P LO RE Wash Tank BO BO
Raw Water
LE
LE
W1
S1
E2S
E1S
E1P
LO
RE
Wash
Tank
BO
BO
Tank
PLS Pond
PLS
May 9, 2007

Metcalf SX

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

of 24,000 gpm PLS • Currently running 34,000 gpm of PLS • Organic reagent is LIX

May 9, 2007

of 24,000 gpm PLS • Currently running 34,000 gpm of PLS • Organic reagent is LIX

Modoc SX

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

gpm PLS • Currently running 36,500 gpm of PLS • Organic reagents are LIX 616 produced

May 9, 2007

gpm PLS • Currently running 36,500 gpm of PLS • Organic reagents are LIX 616 produced

Central SX

Central SX

One train running 1P x 2E x 1S

Design flow of 19,000 gpm PLS

Reagent is LIX 616 produced by Cognis

One train running 1P x 2E x 1S • Design flow of 19,000 gpm PLS •

May 9, 2007

One train running 1P x 2E x 1S • Design flow of 19,000 gpm PLS •

Stargo SX

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

flow of 17,500 gpm PLS • Currently running 26,500 gpm of PLS • Reagent is LIX

May 9, 2007

flow of 17,500 gpm PLS • Currently running 26,500 gpm of PLS • Reagent is LIX

Electrowinning PFD

Electrowinning PFD
AC Cobalt FC-1100 S. A. Rectifiers DC LE RE from SX ER Filters HX HX
AC
Cobalt
FC-1100
S. A.
Rectifiers
DC
LE
RE from
SX
ER
Filters
HX
HX
Tankhouse
Tank
CE
LE to SX
Cathode
Boilers
Recalculating Boiler
Water

May 9, 2007

RE from SX ER Filters HX HX Tankhouse Tank CE LE to SX Cathode Boilers Recalculating

Central EW

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

cathode technology using stainles s steel blanks with a bottom edge strip • Two stripping machines

May 9, 2007

cathode technology using stainles s steel blanks with a bottom edge strip • Two stripping machines

Southside EW

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

Permanent cathode technology using stainless steel blanks with a waxed bottom • Single stripping machine May

May 9, 2007

Permanent cathode technology using stainless steel blanks with a waxed bottom • Single stripping machine May

Stargo EW

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

capacity of 135,000 amps • Permanent cathode technology using ISO 2000 process • Two stripping machines

May 9, 2007

capacity of 135,000 amps • Permanent cathode technology using ISO 2000 process • Two stripping machines

ELECTROWINNING OF METALS FROM MOLTEN SALT ELECTROLYTES

ELECTROWINNING OF METALS FROM MOLTEN SALT ELECTROLYTES
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

PYROPROCESSING OF SPENT NUCLEAR FUEL ELECTROREFINING OF URANIUM
PYROPROCESSING OF SPENT NUCLEAR FUEL ELECTROREFINING OF URANIUM
Mark-IV electrorefiner for processing driver fuel Mark-V electrorefiner for processing blanket fuel Two technical

Mark-IV electrorefiner for processing driver fuel

Mark-IV electrorefiner for processing driver fuel Mark-V electrorefiner for processing blanket fuel Two technical

Mark-V electrorefiner for processing blanket fuel

Two technical problems:

for processing blanket fuel Two technical problems: 1. Dendritic growth of uranium 2. Cylindrical geometry of

1. Dendritic growth of uranium

2. Cylindrical geometry of electrodes is difficult to scale-up

Two technical problems: 1. Dendritic growth of uranium 2. Cylindrical geometry of electrodes is difficult to
Two technical problems: 1. Dendritic growth of uranium 2. Cylindrical geometry of electrodes is difficult to

ONGOING RESEARCH EFFORTS

ONGOING RESEARCH EFFORTS … are directed toward developing the methods for electrodeposition of compact uranium! Compact

… 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

RESEARCH CONCEPTS Fundamental understanding of the mechanisms for growth of dendritic uranium. Focus on the

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

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:

are more strongly bound to each other than to substrate: Layer-by-layer growth (Frank-van der Merwe) produces

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:

and are characterized with fast solid-state diffusion: Mixed growth (Stranski-Krastanov) initiates in a layer by

Mixed growth (Stranski-Krastanov) initiates in a layer by layer mechanism and then forms three dimensional islands due to energetic changes:

initiates in a layer by layer mechanism and then forms three dimensional islands due to energetic

Effect of Electrokinetic Parameters

Electrodeposition occurs in three distinct steps:

Mass transport:

U 3+ (solution) <=> U 3+ (interface) Charge-transfer:

(1)

U 3+ (interface) <=> U o (surface) Surface diffusion:

(2)

U o (surface) <=> U o (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.)

only if the reaction is In ACTIVE REGION. (Note: Active region is determined from Tafel Polarization

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

either: 1. Slow down the CHARGE TRANSFER REACTIONS or 2. To increase the rate DIFFUSION CONTROLLED
THANK YOU VERY MUCH FOR YOUR ATTENTION
THANK YOU VERY MUCH
FOR YOUR ATTENTION