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RSR

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

Refined Lead output: 1,200,000 tonnes per annum


Anodes output:
100,000 anodes per annum
THE WORLDS LARGEST LEAD COMPANY
CONFIDENTIAL

Eco-Bat Technologies Limited


Worlds largest recycler of lead
Metals and materials recycling operations in Europe,

South Africa, and the US

11 battery recycling plants in UK, France, Germany,


Austria and Italy

3 battery recycling plants in USA

1 battery recycling plant in South Africa

Main products refined lead, sheet lead, lead anodes,

recycled polypropylene, sulphuric acid, sodium


sulfate and gypsum
CONFIDENTIAL

RSR Anodes Group


Worlds largest rolled anodes manufacturer: 4

plants

Le Plomb Franais in France to service Europe Russia


India

Castle Lead Works in South Africa to service Africa Australia

Castle Lead Works in Zambia to service Africa Australia

Quemetco Metals Inc. in AZ to service N. and S.


America China

Main products: Rolled and Cast Lead Anode


Recycling Facilities: Europe, USA & South Africa
Sheet Lead Plants
in UK, France & South Africa
CONFIDENTIAL

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

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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

E (Cu 2+ /Cu) = 0.337 + .059 log(aCu2+)


2

Anode:2H2O O2 + 4H+ + 4eE (O2/H2O) = 1.229 .059 (4 pH log (pO2))


4
Cell Voltage:
Eqbrm potentials + Overpotentials + Solution IR + Contact Potential
~ 2.0 V
Current Density: ~ 300 Amps/m2
Energy Reqmnt: ~ 2.0 kWh/kg
Overpotentials: Anodic + Cathodic

CONFIDENTIAL

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)

Contact Potential Drops


Contact Potentials

Anode to Bus Bar; Cathode to Bus Bar


Salt deposition in contacts area
Significant differences within a cell
Typically ~ 20-50 mV
Bad contacts ~ as high as 200 mV
Current distribution issues; Short
circuits

CONFIDENTIAL

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

CONFIDENTIAL

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

CONFIDENTIAL

Why Lead Anodes?


Lead anodes are the preferred material for
EW Anodes from Acidic Sulfate Solution
Insoluble
Ability to form a protective PbO2 layer
Corrosion resistant
Economical
Acceptable Operating Voltage
Robust in a tankhouse environment

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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

Uses: Copper, Nickel, Cobalt and Zinc EW


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Lead-Calcium Phase Diagram

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Mechanical Properties of Pb-Ca-Sn Anodes

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Effect of Tin in Anodes for Electrowinning


Imparts Strength to the Lead Alloy and Reduces Creep
Reduces Corrosion by Segregation into Interdentritic
Eutectic Phase Forming Layers of Tin-Rich Material;
Parallel to Surface for Rolled Anodes
Improves Conductivity
Prevents Formation of Tetragonal PbO
Produces Conducting Paths through Corrosion Layer
Uses: Copper, Nickel and Cobalt Electrowinning

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Mechanical Properties of Pb-Ca-Sn Anodes

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Cast vs. Rolled Anode


Sheets

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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
CONFIDENTIAL

Deformation During Rolling


As the billet is rolled, the cast grains are
elongated and stretched in the rolling
direction.
The cast in tin segregation within the
material is maintained as the grains bend.
Once the grains are bent to the rolling
direction further rolling elongates the
grains.
CONFIDENTIAL

Cast Lead Calcium Tin

CONFIDENTIAL

Rolled 100mm to 50mm 2:1

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Rolled 100mm to 25mm 4:1

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Rolled 25mm to 15mm 7:1

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Rolled 25mm to 6mm 16:1

CONFIDENTIAL

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
CONFIDENTIAL

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

CONFIDENTIAL

Rolled Pb-Ca-Sn Anodes

CONFIDENTIAL

Anode Corrosion Products


Cast Anode

Rolled Anode
CONFIDENTIAL

Mechanical Properties of Typical


Pb-alloys for Electrowinning
Alloy

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

Pb-(0.75%)Ag Alloy Rolled

18.8

9.0

54

-26

CONFIDENTIAL

Advances in Anode Manufacturing

U.S. Patents: 6,131,798 and 5,172,850


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Advanced in Anode Manufacturing

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EFFECTS OF OXYGEN
EVOLUTION IN COPPER
ELECTROWINNING

CONFIDENTIAL

Effects of Oxygen Evolution


Creation of Acid Mist

Control methods = plastic ball or beads


coverage, foam mist suppressants,
mechanical shields, cell hoods & ventilation

Increased Mass Transport and Reduced


Concentration Gradients
Electrolyte Stirring

May cause variations in the concentration


layer at the surface of the cathode impacting
quality of Cu-deposit
Stir up PbO2 flakes from cell bottom; lead
contamination
CONFIDENTIAL

Effects of Oxygen Evolution


Transfer to Cathode and Oxidation of
Copper

Reduction in current efficiency

Oxidation of Iron

Oxidation of Ferrous (Fe2+) at anode and


reduction of Ferric (Fe3+) at cathode reduces
current efficiency

Oxidation of Manganese

MnO2 reacts with corrosion product PbO2


Light PbO2-MnO2 layer may shed and can cause
severe cathode contamination
CONFIDENTIAL

MATERIAL OXIDATION IN
SOLUTION
Degradation of Organic Additives
Controlling Cu-deposit
Oxidation of Organics from SX-Circuit /
Additive

Formation of reactive radicals attacking the


anode at electrolyte surface
O2 + 2RH 2 R+ + H2O
R+ + PbO2 PbO + R=O
PbO + H2SO4

PbSO4 + H2O

Start of fires when sparks ignite flammable


organic on surface
May soften flakes,
which spall off easier
CONFIDENTIAL

Organic Burn at Pb-Ca-Sn Anode

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Anode Corrosion

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Anode Corrosion

CONFIDENTIAL

Effect of Anode Oxidation


Major Consequence is Corrosion of Lead
Anode at the surface

PbO2 (rhombic, large closely packed


crystals, dense, hard, brownish color =
metastable)
PbO2 (tetragonal, fine needle-shaped
crystals, black color)

Main Mechanism
Formation of PbSO4
Oxidation to PbO2
Oxygen diffusion through PbO2 and
formation of PbO2
CONFIDENTIAL

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

Corrosion at and along grain boundaries

CONFIDENTIAL

Anode Corrosion

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Protective -PbO2

Brownish, Hard, Dense, Adherent


CONFIDENTIAL

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

increases corrosion rate; MnCl2, PbCl2 formation;

10 - 20 ppm desired to prevent dendrite formation at


cathode;
100 ppm dangerous

Cobalt Concentration

reduces oxygen evolution potential; promotes


oxygen evolution instead of anode corrosion
amount between 100 - 200 mg/l mainly depending
on current density and manganese concentration
CONFIDENTIAL

Lead Corrosion Films

Adapted from Burbank, J., Anodization of Lead in Sulfuric


Acid, J. Electrochemical Society, Volume 103, Issue 2, 87-91,
1956.

CONFIDENTIAL

Unconventional Penetrating Corrosion

Characteristic of Unstable PbO2 Layer

CONFIDENTIAL

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 Disruption of PbO2

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MnO2 Corrosion

Formation of large, soft, loosely adherent layers of PbO2


CONFIDENTIAL

Effect of Cobalt Addition


Reduces new PbO2 formation
Prevents deterioration of anode corrosion layer by depositing
cobalt oxide on the PbO2 layer effectively doping it.
Reduces Oxygen Evolution Potential
150 mV at 200 mg/l

Oxidizes preferentially to Manganese


Hardens flakes making them difficult to spall
Reduces Pb Contamination at Cathode
Co-content
f (i, Mn-concentration)
No economical benefit above 200 mg/l

CONFIDENTIAL

Effect of Cobalt Addition

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Lead Contamination
in Copper Deposits

CONFIDENTIAL

Lead Contamination in Copper Deposit


Reduction Potential Electrodeposition
Cu2+ +2e- Cu
E0 = 0.34 V
PbSO4 + 2e- Pb + SO42E0 = -0.36 V
Pb2+ +2e- Pb
E0 = -0.13 V
No co-reduction of Pb ions
Only physical occlusion of particulate Pb species
PbO2 reduction to PbSO4 or PbO possible

PbO2 + SO42- + 4H+ 2e- PbSO4 + 2H2O


PbO2 + H2O + 2e- PbO + 2OH-

E0 = 1.69 V

E0 = 0.25 V

No further reduction of PbO


PbO + H2O + 2e- PbO + 2OH-

CONFIDENTIAL

E0 = -0.58 V

Lead in Copper Deposit


High Electrolyte Temperature and Variations
Elevated Manganese or Chloride Levels
Increased Current Density
Mass Transport though Oxygen Evolution

CONFIDENTIAL

Lead in Copper Deposit, cont.


Electrolyte Distribution by Manifold
Hole size and velocity of electrolyte injection
Angle and angle direction
Clearance between manifold - cell bottom &
manifold - electrodes

Infrequent anode washing


No sludge removal
Short circuits

CONFIDENTIAL

Power Loss

CONFIDENTIAL

Power Loss
SULFATION REACTIONS OF ANODE
WHEN POWER IS LOST:
Cu + PbO2 + 2H2SO4 CuSO4 + PbSO4
+ 2H2O
Cu+ MnO2 + 2H2SO4 CuSO4 + MnSO4
+ 2H2O
CONFIDENTIAL

Lead Corrosion Films

Adapted from Burbank, J., Anodization of Lead in Sulfuric


Acid, J. Electrochemical Society, Volume 103, Issue 2, 87-91,
1956.

CONFIDENTIAL

TIN SEGREGATION IN PbO2


LEAD- CALCIUM-TIN-ALLOY

CONFIDENTIAL

Anode

Discharge Product on Rolled Pb-Ca-Sn-Anode

CONFIDENTIAL

Re-Start after Power Loss


Proposed Ramping up of Power to
avoid
overheating of conductive SnO2
tubes and subsequent spalling at
metal
corrosion product
interface
Initial Current
50 A/m2 or 5 (A/ft2)
After 5 Minutes
After 15 Minutes
After 25 Minutes

100 A/m2 or 10 (A/ft2)


150 A/m2 or 15 (A/ft2)
200 A/m2 or 20 (A/ft2)

Then raise 5 A/m2/minute


CONFIDENTIAL

Anode Warping

CONFIDENTIAL

Possible Reasons for Anode Warping


Ca-content above 0.08%
Improper Rolling of Anode Sheet
Assembling of Sheet to Hanger Bar
Transportation
Storage
Tankhouse Operation
Anode Cleaning
Spacers
CONFIDENTIAL

Possible Reasons for Anode Warping


Non-uniform grain structure of sheet
large, equal-sized grains on one side
directionally oriented grains on other side

Differential corrosion on each side of the

sheet
CONFIDENTIAL

Anode Maintenance

CONFIDENTIAL

Maintenance of Pb-Ca-Sn Anodes


Build up of thick corrosion layers
Anode cleaning with pressurized water to
remove adherent flakes

Anodes have to be frequently checked for


warpage and straightened, if necessary
Before anode straightening remove corrosion
product to bare metal

CONFIDENTIAL

Summary

CONFIDENTIAL

Anode Current Status


Lead Alloys are Preferred Material for EW Anodes
from Acidic Sulfate Solution

Insoluble
Ability to form protective PbO2 layer
Corrosion resistant
Economical
Acceptable Operating Voltage
Robust in a Tankhouse Environment

CONFIDENTIAL

Copper EW: Best Available Anode


Rolled PbCaSn Anode
Microstructure has an important effect on anode

corrosion rate

Chemical Composition for Cu-EW


Lead alloy containing 0.07% Ca and 1.35% Sn
Impurity levels in electrolyte affect anode corrosion

Good Mechanical Properties and Form


Stability
Excellent Corrosion Resistance

CONFIDENTIAL

Best Available Anode


Resists Passivation
Independent of raw material source
Primary or Secondary Lead

Conducting Current
Low potential drop between sheet and hanger bar

( 1 mV) due to complete metallurgical bond at


soldered joint
Low potential drop is maintained throughout
anode life

CONFIDENTIAL

THANK YOU!