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RSRAnodes
Anodesfor
for
Copper
CopperElectrowinning
Electrowinning
Dr. Abbas Mirza, Senior Product Engineer, RSR Technologies, Dallas, TX
Dr. Abbas Mirza, Senior Product Engineer, RSR Technologies, Dallas, TX
Mr. Larry Webb, President, Quemetco Metals Limited, Casa Grande, AZ
Mr. Larry Webb, President, Quemetco Metals Limited, Casa Grande, AZ
Mr. Jerry Gagnon, Senior International Sales Manager, QML
Mr. Jerry Gagnon, Senior International Sales Manager, QML
ECO-BAT TECHNOLOGIES
Organization
E C O -B A T T E C H N O L O G IE S L td .
UK
H . J . E n th o v e n L td .
H J ENTHOVEN
se c o n d a ry
FRA N CE
L e P L O M B F R A N C A IS
BLM
L ead S heet
STCM
L ead S heet
TO U LO U SE
s e c o n d a ry
BAZOCHE
s e c o n d a ry
A PSM
s e c o n d a ry
STOLBERG
p r im a ry
GERM ANY
IT A L Y
A U S T R IA
B E R Z E L IU S
M E T A L L H O L D IN G S
E C O B A T SpA
BM G
se c o n d a ry
F R E IB E R G
s e c o n d a ry
ZIMCO GROUP
SOUTH AFRICA
BRAUBACH
s e c o n d a ry
M A R C IA N IS E
s e c o n d a ry
PAD ERNO
s e c o n d a ry
RSR GROUP
USA
plants
Presentation Overview
Introduction
Anode Requirements
Anode Alloys
Effect of Alloying Elements (Calcium, Tin, etc.)
Cast vs. Rolled Anodes
Anode Manufacture
Effect of Oxygen during Electrowinning
Mechanism of Anode Corrosion
CONFIDENTIAL
Presentation Overview
Pb-Contamination in Cu-Deposit
Power Loss
Anode Warping
Anode Maintenance
Summary
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Anode Systems
and Requirements
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Copper Electrowinning
Cathode: Cu2+ + 2e- Cu
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Cell Voltage
Cathode OP
Contact Potential
Solution IR Drop
Anode OP
Anode OP
EE0 0
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Cell Voltage
Cell Voltage = Thermodynamic Potential
+ Anode Overpotential + Cathode Overpotential
+ Solution IR Drop + Contact Potential
Overpotential = Potential above what is theoretically
required
(Related to kinetics of reaction)
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Standard Requirements
High Mechanical Strength against Warpage and Creep
(Form Stability)
Low Overpotential for Oxygen Evolution
Quick and Stable Formation of Hard, Dense and Adherent
Protective Corrosion Layer (Conditioning)
High Corrosion Resistance
Long Service Life
Low Production Cost
Design and Material Integral Part of Tankhouse Concept
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Anode Development
Efficiency of electrowinning step is strongly
governed by anode performance
Advances characterized by and resulted in:
Substitution of Lead Alloys by other Lead Alloys
Structural Evolution of Anode Microstructure
Standard Cu-EW Anode:
Pb-(0.07-0.08%)Ca-(1.35%)Sn
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Effect of
Alloying Elements
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Effect of Calcium
Increases Mechanical Properties of Anode
Decreases the Anode Potential
Increases Rate of Anode Corrosion
Particularly above 0.08% Ca because of Pb3Ca
formation
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Cast Anodes
Randomly oriented, dendritic
grain structure
Many grain boundaries
Low creep resistance
Tin segregates to interdentritic regions and GBs
Casting Defects
Porosity
Considerable creep
Concentric cracking of
corrosion layer
Non-uniform Electrochemistry
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Rolled Anodes
Breaks up original Cast
Structure
As the billet is rolled, the
cast grains are elongated
and stretched in the rolling
direction.
Once the grains are bent to
the rolling direction further
rolling only elongates the
grains.
Elongated and Highly
Oriented Grains
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Rolled Anodes
Tin Segregation Remains
Homogeneous Grain Size
No Casting Defects and
Porosity
High Creep Resistance
Excellent Corrosion
Resistance
Higher Resistance to Initial
Conditioning
Cast Anodes
Cobalt Absorption at Anode
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Rolled Anode
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UTS
(MPa)
0.2% YS
(MPa)
Elongation
(%)
Hardness
(RR30)
Pb-(3%)Sb Cast
65.5
55.2
10
85
Pb-(3%)Sb Rolled
24.6
16.3
40
64
Pb-(6%)Sb Cast
73.8
71.0
87
Pb-(6%)Sb Rolled
30.6
19.5
35
65
Pb-(0.07%)Ca-(1.35%) Sn Cast
46.4
35.3
29
71
Pb-(0.07%)Ca-(1.35%) Sn Rolled
71.0
65.3
14
85
Pb-(0.07%)Ca-(1.35%)Sn-(0.05%)Ag Rolled
80.0
76.8
10
88
Pb-(0.07%)Ca-(0.35%)Ag Rolled
37.8
35.5
42
68
18.8
9.0
54
-26
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EFFECTS OF OXYGEN
EVOLUTION IN COPPER
ELECTROWINNING
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Oxidation of Iron
Oxidation of Manganese
MATERIAL OXIDATION IN
SOLUTION
Degradation of Organic Additives
Controlling Cu-deposit
Oxidation of Organics from SX-Circuit /
Additive
PbSO4 + H2O
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Anode Corrosion
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Anode Corrosion
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Main Mechanism
Formation of PbSO4
Oxidation to PbO2
Oxygen diffusion through PbO2 and
formation of PbO2
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Anode Corrosion
Secondary Corrosion
Occurs through periodic failure and re-growth
of oxide layer
Corrosion behavior of lead is dependent both
on microstructure and chemical composition
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Anode Corrosion
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Protective -PbO2
Anode Corrosion
FORMATION RATE AND STABILITY OF PbO2
FILM MAINLY DEPENDS ON:
Current Density
almost linear increase in corrosion rate with increasing
current density
Electrolyte Temperature
Temperature increase of 100 C doubles corrosion rate
Manganese Content
Chemical attack of MnO4- ions forms voluminous nonprotective PbO & Pb(OH)2
Forms MnO2/PbO2 flakes; larger, softer, lighter; tend to
spall; <40 ppm desirable CONFIDENTIAL
Anode Corrosion
FORMATION RATE AND STABILITY OF PbO2
FILM MAINLY DEPENDS ON:
Chloride Concentration
Cobalt Concentration
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Manganese Problem
The manganese attacks the PbO2 layer and
causes MnO2 to build up in the layer.
MnSO4 + PbO2 -> PbSO4 +MnO2
The PbSO4 is converted back to PbO2, but it is
now deposited in loose layers.
These layers are easily spalled off causing
contamination of the copper cathode.
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MnO2 Corrosion
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Lead Contamination
in Copper Deposits
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E0 = 1.69 V
E0 = 0.25 V
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E0 = -0.58 V
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Power Loss
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Power Loss
SULFATION REACTIONS OF ANODE
WHEN POWER IS LOST:
Cu + PbO2 + 2H2SO4 CuSO4 + PbSO4
+ 2H2O
Cu+ MnO2 + 2H2SO4 CuSO4 + MnSO4
+ 2H2O
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Anode
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Anode Warping
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sheet
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Anode Maintenance
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Summary
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Insoluble
Ability to form protective PbO2 layer
Corrosion resistant
Economical
Acceptable Operating Voltage
Robust in a Tankhouse Environment
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corrosion rate
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Conducting Current
Low potential drop between sheet and hanger bar
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THANK YOU!