Aqueous Processing
A Bright Future for Copper
Electrowinning
Michael Moats and Michael Free
Over the past 40 years, the copper
mining industry has undergone a dra-
matic shift toward hydrometallurgical
extraction of copper at the mine site.
This has increased the importance of
recovering high-purity copper by electro-
winning. High-purity cathode production
was achieved by implementing numer-
ous technologies including superior
lead-alloy anodes, improved cathode
handling and/or stainless steel blanks,
better electrolyte control, and advanced
tankhouse automation. In the future, it is
projected that tankhouses will produce
high-quality copper at lower costs using
technologies that could include dimen-
sionally stable anodes, alternative anode
reactions, innovative cell designs, novel
electrolyte circulation systems, and more.
This paper reviews existing commercial
copper electrowinning technologies and
discusses advances that need to be made
to implement future technologies.
INTRODUCTION
Electrowinning has a relatively unique
position among processing technologies
due to its ability to produce high-purity
metal on large scales at reasonable
cost. It can be used to produce bright,
34
shiny, nanoscale copper coatings for the
microelectronics industry or bulk cath-
ode copper in the raw metal production
industry. The process of electrowinning
involves the input of electrical energy to
reverse the process of metal dissolution.
Its chemistry, which is discussed in more
detail elsewhere,1,2 is essentially the same
as the recharging of a battery. It is an
important method of metal production.
The production of copper by electro-
winning has increased in importance
since the commercial implementation of
solvent extraction at the Bluebird mine
in Arizona in 1968.3 Since that time, the
combination of solvent extraction and
electrowinning has been implemented
at many facilities throughout the world.
Overall worldwide copper production
levels are compared to electrowinning
copper production levels in Figure 1. The
data trend in Figure 1 shows clearly that
the fraction of world copper produced
by the combination of solvent extrac-
tion and electrowinning has increased
rapidly in the last 15 years; electrowin-
ning contributed less than 3% of the total
in 1980 in contrast to approximately
20% of the world copper production in
2005.4–6 Although the growth rate for
Figure 1. A comparison of
worldwide copper production by
combined methods (total) and
solvent extraction/electrowin-
ning (SX/EW) between 1980
and 2005.4–6
Overview
electrowinning production in the near
future is not likely to sustain the growth
rate observed in the last 15 years, it is
likely to be greater than the total rate of
copper production.
Reasons for the rapid growth rate
of electrowinning production include
simplified flow sheets, diverse process
integration options, lower costs, and
more size flexibility than general copper
production. Production by electrowin-
ning involves leaching, solvent extrac-
tion, and electrowinning. In contrast,
most commercial copper is produced
by grinding, concentrating (flotation),
smelting (combined with converting,
fire refining, and acid production), and
electrorefining. This more common
processing sequence generally requires
large-scale production to justify the nec-
essary capital-intensive infrastructure.
Recent advances in integrating
electrowinning with chalcopyrite con-
centrate leaching are likely to drive
continued growth of copper production
by electrowinning. These advances
include enhanced bioleaching and pres-
sure leaching technologies as well as
performance enhancing electrowinning
technologies. Such advances are neces-
sary to sustain electrowinning produc-
tion growth because chalcopyrite is the
dominant mineral for copper production,
and the use of electrowinning has been
generally confined to production from
other copper minerals.
RECENT TRENDS IN
ELECTROWINNING
TECHNOLOGY
During the production increase shown
in Figure 1, electrowinning technology
has improved and matured through
incremental changes. Presented in Table
I are some areas that highlight the extent
to which certain copper tankhouse
JOM • October 2007
technologies have been implemented.
The data presented were compiled
from two operation surveys presented
by Davenport and others at the Copper
1999 and Copper 2007 meetings.7,8
From these surveys, the data collected
in 1996–1998 were compared to data
collected in 2006–2007. While different
plants are represented in the surveys and
thus some sampling error and bias may
exist, it is felt by the authors that the
information in Table I represents trends
that have occurred over the past decade
in copper electrowinning.
In copper electrowinning, there con-
tinues to be an increase in the use of
stainless-steel cathodes as the substrate
for copper deposition (63% of plants in
1999 vs. 74% of plants in 2007). Essen-
tially, all new plants are designed using
stainless-steel cathode and automated
stripping technology. Additionally,
almost all plants now use rolled Pb-Ca-Sn
anodes (83% in 1999 vs. 94% in 2007).
The control of metallurgical processing
and composition of the anodes along with
better tankhouse control have led to an
increase in anode life. Since the anodes
are not corroding as fast, the quality of
cathode has improved based on the <3
ppm lead data. Interestingly, the plants
reporting <2 ppm lead and <5 ppm sulfur
in the cathode have decreased over the
past decade. The authors believe this
has resulted from most operations not
receiving an economic benefit from
producing greater cathode quality than
London Metals Exchange-grade copper
and thus not warranting additional
costs to improve cathode purity. The
utilization of the more dimensionally
stable electrodes and better electrolyte
control has led tankhouses to operate
at higher current densities and achieve
higher current efficiencies. Some of
the electrolyte control comes from the
increased usage of electrolyte manifold
distribution systems. Finally, the use of
polymer concrete cells continues to grow,
leading to reduced cell maintenance and
lower costs. Many of these recent trends
in the constantly evolving commercial
electrowinning practice are likely to
continue or undergo significant shifts as
future technologies are implemented.
FUTURE TECHNOLOGIES
Many new technologies have been
explored to enhance electrowinning per-
2007 October • JOM
Table I. Selected Summary of Electrowinning Plant Data Surveyed in 1996–1998
and 2006–20077,8
Categories
Number of Plants a
Using Stainless Steel Blanks
Cathode Quality
< 3 ppm Pb
< 2 ppm Pb
< 5 ppm S
Using Rolled Pb-Ca-Sn Anodes
Anode Lifetime <5 y
Cathode Current Density >300 A/m2
Current Efficiency >92%
Using Electrolyte Manifold
Polymer Concrete Cellsb
a
The actual plants surveyed were not exactly the same in each time period.
b
Plant included if some of the cells were manufactured from polymer concrete.
formance and production. Some provide
modest enhancements in performance
or production, while others offer incre-
mental increases in energy efficiency
and improvements in environmental
quality. A few new technologies offer
the potential to more rapidly change
processing methods, chemistries, or
equipment. Some new technologies
accomplish a combination of improved
energy, environmental, productivity, and
processing performance.
Reduced Energy Consumption
and Environmental Impact
Two of the largest concerns in the
future electrowinning technology are
energy consumption and the environ-
mental impact caused by operations.
This environmental impact relates to the
generation of hazardous and potentially
harmful by-products (e.g., lead and acid
mist). It is projected that electrowinning
facilities in the future will be moved to
lower energy consumption processes
that eliminate the generation of these
hazardous/harmful by-products.
To address these potential problems,
new technology related to anodes and
anodic reactions is being developed.
From an energy and environmental
standpoint, the use of lead alloy anodes
poses an area for future improvement.
Lead alloy anodes are relatively inex-
pensive, form a self-healing protective
oxide layer during service, and are robust
in industrial service. The downsides of
using these anodes are that the lead oxide
layer eventually spalls, creating a hazard-
ous by-product and contamination in the
cathode. In addition, the potential needed
1996–1998 2006–2007
35 34
63% 74%
67% 77%
61% 42%
48% 35%
83% 94%
62% 35%
18% 50%
23% 32%
60% 71%
51% 79%
to form the lead oxide layer combined
with the oxygen evolution results in an
extra 600 mV of potential at the anode.
This is approximately 30% of electrical
power consumed by an electrowinning
cell.
To reduce the environmental concerns
and energy consumption of copper
electrowinning, two technologies are
being developed: alternative anodes and
alternative anode reactions. The most
promising alternative anodes appear to be
coated titanium anodes. These anodes are
coated with a precious metal oxide coat-
ing based on RuO2 or IrO2. The advan-
tages of these anodes9–11 are lower power
consumption (10–17%), elimination of
lead sludge and lead contamination of the
product, and elimination of cobalt sulfate
addition. The main drawbacks for these
anodes have been cost versus lifetime.
Recently, coated titanium mesh attached
to lead anode substrates operated for 3.25
years in a commercial electrowinning
tankhouse.12 No published costs were
given for the demonstration anodes.
Another potential technology advance
that will reduce the environmental impact
and energy consumption of copper elec-
trowinning is the use of an alternative
anode reaction. Presently, water is
decomposed resulting in the generation
of acid and oxygen gas. It has been
proposed for some time that switching
the anodic reaction to ferrous ion oxida-
tion could be advantageous. Ferrous
reduction would lower the electrical
power consumption by potentially 50%.
The elimination of gas bubbles bursting
at the electrolyte surface would signifi-
cantly reduce the generation of acid mist,
35
which is a corrosion issue as well as a
worker safety issue. The drawbacks of
using ferrous oxidation are possible
current inefficiencies caused by high
levels of ferric iron in the electrolyte,
effective regeneration of the ferrous ion,
and the generation of acid needed in
solvent extraction and leaching. Sig-
nificantly, a flowsheet that uses ferrous
oxidation has been developed13 and is
highlighted in another article in this issue
of JOM.
Enhanced Productivity
Productivity can be enhanced by
increasing current density and decreas-
ing cell down times. Increasing current
density without producing adverse side
effects requires appropriate process
control through additives, cell monitor-
ing, and in many cases, the use of elec-
trolyte distribution manifolds. Modifica-
tions in these parameters result in modest
improvements in productivity.
The replacement of copper starter
sheets with stainless-steel blanks has
been an ongoing trend in copper elec-
trowinning. Regardless of the cathode
starting material, electrowinning has
been a batch harvesting system since its
inception. Starter sheets or blanks are
inserted into the system, copper is depos-
ited for 5–10 days, cathodes are har-
vested, and then the process is started
over again. Automation of the harvesting
process has led to improved electrode
alignment and decreased manpower, yet
harvesting remains a batch process.
In the future, a continuous process of
electrowinning copper and harvesting
looks likely. Several attempts have been
made recently at producing copper con-
tinuously. These include powder produc-
tion in a flow-through cell14,15 and copper
granules or beads in a fluidized bed
reactor.16–18 Additionally, the production
of copper foil using a rotating drum
maybe feasible. In all of these designs,
copper is harvested continuously and
can employ alternative anodes and anode
reactions as described previously.
Expanded Processing
Opportunities
Technologies that integrate with elec-
trowinning include a variety of pressure
oxidation, biooxidation, and atmospheric
pressure leaching processes that may
impact future production. These tech-
36
nologies are too numerous to discuss
adequately in this paper. Although many
of these processes have the potential for
future electrowinning impact, most have
not been demonstrated on a commercial
scale. Most of the improved technologies
in the area of biooxidation of chalcopy-
rite ores have been limited to pilot-scale
production levels. Biooxidation technol-
ogy has been demonstrated at the 20,000
t/y level, but there have been no firm
commitments for large-scale implemen-
tation.19 Similarly, atmospheric pressure
leaching and electrowinning operations
have not been demonstrated on a large
scale, despite abundant opportunities
and research.20 However, pressure oxida-
tion technologies have been demon-
strated with modest success. The most
notable pressure oxidation success at
this time is the pressure oxidation process
that is used at Bagdad, Arizona by Free-
port-McMoran /Phelps Dodge and will
soon be used in a new facility under
construction at Morenci, Arizona. In
addition, this process offers considerable
flexibility in acid production through
control of temperature and environment.
Pressure oxidation processing is par-
ticularly interesting because of the
potential opportunity to send the leach-
ing solution directly to electrowinning
without the use of solvent extraction.21
It is likely that improvements in hydro-
metallurgical extraction of copper from
chalcopyrite will drive much of the
copper electrowinning production
growth in the future.
CONCLUSIONS
Electrowinning has become for many
projects the preferred method for primary
copper recovery. During the growth of
electrowinning processing over the past
20 years, improved technologies have
led to lower costs, higher productivity,
and high-purity cathodes. The capabili-
ties of electrowinning to produce high-
volume, high-purity copper in increas-
ingly efficient and environmentally
responsible ways, combined with oppor-
tunities to integrate it with a wide variety
of processing methods at reasonable cost
will ensure a bright future for copper
electrowinning.
References
1. M.L. Free, Chemical Processing and Utilization of
Metals in Aqueous Media, 2nd Edition (Ann Arbor, MI:
XanEdu Original Works, 2004).
2. M.L. Free, “Fundamentals of Electrometallurgy in
Aqueous Media,” JOM, 59 (5) (2007), pp. 28–33.
3. G. Kordosky and M. Virnig, “Equilibrium Modifiers in
Copper Solvent Extraction Reagents—Friend or Foe,”
Hydrometallurgy 2003, Vol. 1, ed. C.A. Young et al.
(Warrendale, PA: TMS, 2003), pp. 905–916.
4. International Copper Study Group (Lisbon, Portugal),
www.icsg.org/Factbook/copper_world/produc39.gif.
5. S. Mella, R. Villarroel, and A. Lillo, Copper
Electrowinning in the Absence of Acid Mist: Six Years
of Industrial Application (Madrid, Spain: Ingenieria
Industrial Same Ltda., 2004), pp. 1–13.
6. Metal Bulletin Monthly-Copper Supplement (March
1998).
7. J. Jenkins et al., “Electrolytic Copper—Leach,
Solvent Extraction and Electrowinning World Operating
Data,” Copper 99–Cobre 99—Fourth International
Conference, Volume 4, Hydrometallurgy of Copper, ed.
S.K. Young et al. (Warrendale, PA: TMS, 1999), pp.
493–566.
8. T. Robinson et al., “Electrolytic Copper
Electrowinning—2007 World Tankhouse Operating
Data,” Copper–Cobre 2007, ed. G.E. Houlachi, J.D.
Edwards, and T.G. Robinson (Montreal, Canada:CIM,
2007), pp. 375–424.
9. M. Moats, K. Hardee, and C. Brown, Jr., “Copper
Electrowinning in Cobalt-Free Electrolyte using Mesh
on Lead Anodes,” Proceedings of the Copper–Cobre
2003 International Conference, Volume V, ed. J.E.
Dutrizac and C. Clement (Warrendale, PA: TMS, 2003),
pp. 543–553.
10. M. Moats, K. Hardee, and C. Brown, Jr., “Mesh-on-
Lead Anodes for Copper Electrowinning,” JOM, 55 (7)
(2003), pp. 46–48.
11. K. Hardee and M. Moats, “Application of Titanium
Mesh-on-Lead Technology to Metal Electrowinning
Systems,” Electrochemistry in Mineral and Metal
Processing V, ed. R. Woods and F.M. Doyle (Pennington,
NJ: The Electrochemical Society, 2000), pp. 294–302.
12. M. Moats, C. Brown, and K. Hardee, “Nanocrystalline
Coatings for Composite Copper Electrowinning
Anodes,” Functional Fillers and Nanoscale Minerals II,
ed. Jon Kellar (Littleton, CO: SME, 2006), pp. 267–
273.
13. S.P. Sandoval et al., U.S. patent application
2005/025228 (3 February 2005).
14. J.O. Marsden et al., U.S. patent application
US2005/025086 (23 February 2006).
15. A.C. Stevens et al., U.S. patent application
US2005/025158 (23 February 2006).
16. R.M. Nadkarni et al., U.S. patent 5,695,629 (9
December 1997).
17. D.J. Robinson et al., U.S. patent application
US2007/0102302 (10 May 2007).
18. V. Jiricny, A. Roy, and J.W. Evans, “Copper
Electrowinning using Spouted-Bed Electrodes: Part I.
Experiments with Oxygen Evolution or Matte Oxidation
at the Anode,” Met. & Mat. Trans. B, 33B (2002), pp.
669–676.
19. Minerals Engineering International (Falmouth, U.
K.), www.min-eng.com/hydrometallurgy/134.html.
20. M.L. Free, “Electrochemical Coupling of Metal
Extraction and Electrowinning,” Electrometallurgy
2001, ed. J.A. Gonzales and J. Dutrizac (Montreal,
Canada: CIM, 2001), pp. 235–260.
21. R.G. MacDonald and D.M. Muir, “Pressure
Oxidation Leaching of Chalcopyrite. Part I. Comparison
of High and Low Temperature Reaction Kinetics and
Products,” Hydrometallurgy, 86 (3-4) (2007), pp. 191–
205.
Michael Moats and Michael Free are with the
Metallurgical Engineering Department at the
University of Utah, 135 S 1460 E, Salt Lake City, UT
84112. Dr. Moats can be reached at (801) 581-4013;
fax (801) 581-4937; michael.moats@mines.utah.
edu.
JOM • October 2007