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Electrowinning Cu/EW
P
more appreciative knowledge of the ‘simple’ a
electrowinning reactor.
p
Synopsis The first part of the paper goes through the
fundamentals and culminates in an example e
An engineering house’s perspective of required inputs in designing reactor being developed. Note that not all r
a copper electrowinning tank house and ancillary equipment calls
design procedures are named as this would
for both understanding of the key fundamental controlling
compromise TMP’s intellectual property.
mechanisms and the practical requirements to optimize cost,
However, the reader will be able to get a very
schedule and product quality. For direct or post solvent extraction
good understanding of what is required to
copper electrowinning design, key theoretical considerations include
current density and efficiency, electrolyte ion concentrations, cell
design and build a copper electrowinning
voltages and electrode overpotentials, physical cell dimensions, cell plant.
flow rates and electrode face velocities, and electrolyte temperature.
Part 1: Copper electrolysis theoretical
Practical considerations for optimal project goals are location of
plant, layout of tank house and ancillary equipment, elevations,
considerations
type of cell furniture, required cathode quality, number and type of Faraday’s law
cells, material of construction of cells, structure and interconnecting
equipment, production cycles, anode and cathode material of
For the winning of copper by the addition of
construction and dimensions, cathode stripping philosophy, plating electrons
aids, acid mist management, piping layouts, standard electrical [1]
equipment sizes, electrolyte filtration, impurity concentrations, bus
bar and rectifier/transformer design, electrical isolation protection, Cations go towards the cathode, and
crane management, sampling and quality control management, anions go to the anode. The working electrode
staffing skills and client expectations. All of the above are required is where reduction takes place and the counter
to produce an engineered product that can be designed easily, electrode is where oxidation occurs. The
constructed quickly and operated with flexibility. working electrode is the cathode and the
counter electrode the anode. For the general
oxidation/reduction reaction:
[2]
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[30]
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[45]
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Table I
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Table II
the DLCs calculated this does not mean that the plant is For copper reduction on an electrode the last term of the
incapable of adequate production but only means that the B-V equation can be neglected to give:
correlation may not be representative of the exact conditions
in that plant. [61]
The correlations do not take into account gas evolving
electrodes of which all copper electrowining anodes are. this
omission in the correlations may underestimate the DLC Taking the log of both sides of the equation and
significantly. This gas evolution can have a strong influence separating for overpotential gives:
on the mass transfer of ions due to the forced convection
effects inside the parallel plate arrangement. [62]
Overall electrode process
The earlier sections dealt with the two mechanisms of Substituting for the concentration ratio gives:
electron transfer for an electrode. This section deals with an
overall process of both heterogeneous electron transfer and [63]
mass transfer that is relevant to copper electrowinning in
practice. This equation describes overpotential, applied current and
The B-V equation that describes the heterogeneous DLC in a single equation.
electron transfer in terms of current and overpotential is:
Example of a fictional cell reactor
A fictional cell reactor is developed to show the relationship
[26] of overpotential to current for varying conditions of concen-
tration and flow in the cell. High level differences between the
scenarios are:
➤ Cell 1, low flow rate
➤ Cell 2, high flow rate
The current density described by Fick’s and Faraday’s law ➤ Cell 3, low flow rate, high copper concentration
for mass transfer is: ➤ Cell 4, high flow rate, high copper concentration.
Each cell has the same physical characteristics and
[44]
features a cathode plating area of 1 m x 1 m. The physical
properties of the electrolyte are kept constant except for the
and
concentrations and flow rates in the cells. Table III also gives
[45] the DLC results for various correlations.
➤ The forced convection correlation of Equation [53] and
Substituting and resolving for concentrations gives: Equation [54] described by the hydrodynamic charac-
teristics of the cell are strongly influenced by the
[60] change in flow rate. Compared to the natural convection
correlations of Equation [55] and Equation [59] that,
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Overpotential volts
as expected, are not influenced by the changing flow This graph shows the following conclusions to be drawn:
rate as these correlations do not take into account the ➤ Increasing the flow rate at the same copper production
flow system but only density difference along the plate rate results in an increase of DLC from 190 A/m2 to
surface 300 A/m2, ‘Cu Lo MT’ to ‘Cu Hi MT’
➤ The graph of overpotential versus current is called a ➤ Increasing the copper concentration and flow rate
voltammogram. For the development of the voltam- slightly results in increasing the DLC from 190 A/m2 to
mogram the correlation from Equation [53] is used as 230 A/m2, ‘Cu Lo MT’ to ‘Cu Lo MT Hi Conc’
this DLC changes with concentration and flow rate
➤ Increasing the copper concentration and flow rate
which is phenomenologically correct. Although it may
significantly has the largest effect of increasing the
not fully account for all mass transfer driving forces
DLC, from 190 A/m2 to 310 A/m2, ‘Cu Lo MT’ to ‘Cu Hi
such as the gas evolution at the anode, this correlation
MT Hi Conc’.
demonstrates that reactor design is strongly influenced
by flow rate and concentrations. Although the DLC equations used to determine this
voltammogram are based on literature work, the functionality
The DLC3for each cell is used to plot the voltammogram
remains correct. In order to optimize the cell design in terms
on overpotential versus current density graph. The exchange
of capital cost for the same production rate, the DLC must be
current density io is taken from17 as
as high as possible so that the Faradaic current density is as
[64] high as possible (limited to producing a good product). These
conditions will allow for the same transformer/rectifier
Figure 1 compares the voltammograms for the four arrangement to:
fictional cells. ➤ Minimize installed electrowinning total plating area
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Traditional cell3,6,10,15,16 110 350 The solution and contact resistance can be taken as
EMEW cell12,13 250 600 <0.6 V combined6.
CSS cell11 430 1000
Air sparging10 1000 3000
Then the required cell voltage to obtain a current flow to
Ultrasonic agitation10 3300 10500 produce copper cathode from solution is
Periodic current reversal10 430 ---
[76]
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Current density
[77] P
Depending on the type of operation, current densities can a
vary between 200 and up to about 375 A/m2. Operations
where solvent extraction precedes electrowinning normally p
The efficiency is strongly dependent on additional side produce cathodes with a good surface quality at higher e
reactions that occur; for the electrowinning of copper the current densities than direct electrowinning operations. r
decomposition of water lowers the current efficiency. Furthermore, the clarity of the feed solution needs to be
However, the single greatest effect is the presence of iron in taken into account. The Ruashi design includes multimedia
the solution. The cyclic oxidation and reduction of dissolved coalescing filters for the removal of both solids as well as
iron can significantly reduce the efficiency of an operation. organics from the Cu feed solution before the solution reports
Iron can be removed by a number of methods that include. to the cellhouse. Process engineers are in general quite
comfortable operating in the region of 250 to 300 A/m2 when
➤ Solution precipitation
SX and multimedia filters are employed.
➤ Prior reduction of iron (III) by SO2 or copper metal
It is also advisable to consult the vendors of the
➤ Increasing the bleed stream volume
rectiformers. There are standard designs for the transformer-
➤ Use of a diaphragm cell.
rectifier pairs, ranging in size from small up to 30 kA. For the
Current efficiencies for direct electrowinning operations Ruashi design, two sets of 30 kA were purchased to satisfy
can be as low as 65% whereas efficiencies for post SX the design requirement of 60 kA total DC supply to the
electrowinning can be as high as 95%. electrowinning cells. Depending on the rectiformer supply,
the cell design can be modified to suit.
Part 2: Practical considerations
The following is based on a case study of the Ruashi BMR Cathode centre to centre spacing
designed by TWP Matomo Process Plant. Design current density is also dependent on electrode
Production rates spacing. The minimum spacing recommended for Cu
electrowinning operations for cathode centre to cathode
Production rates are usually specified by the client, centre is 95 mm. Below this the risk of shorts due to
depending on the mass balance and the environment for electrode alignment and nodular growths is considered to be
which the electrowinning is to be designed. Design conditions unacceptably high.
will normally be in the region of specified rate plus 10%; this
excludes availability. Cathode quality
Availability This is normally specified by the client. Within the cellhouse,
there are very few variables that influence cathode quality; it
Mechanical availability depends on the following factors:
is normally a function of the preceding purification steps.
➤ Site conditions and location. The Ruashi BMR is
located in Lubumbashi, DRC, and as such, consid- Sampling specification and procedure
eration was given to have stand-by units for all key
mechanical equipment. Operation within South Africa Sampling on site is normally done on site for in-house
would not necessarily require the same design. Dual quality control purposes only. The client usually sells his
availability design was included for cellhouse product through a third party, who will be responsible for
circulation pumps, feed to and return from pumps sample analysis. Some mining houses have accredited
servicing the cellhouse, overhead cranes, stripping laboratories; in this case, the laboratory analyses samples
machines (for which an additional allowance was made received from the plant. Two commonly used methods to
to allow manual stripping of cathodes in a specifically obtain a sample are either to drill holes in randomly selected
designated area in case of equipment breakdown). samples on randomly selected locations of the cathode. The
Both the loaded electrolyte pond feeding the cellhouse drillings are then sent for analysis in the accredited
as well as the spent electrolyte pond returning spent laboratory. The second method follows the same procedure;
electrolyte solution to the solvent extraction circuit is of however, instead of drillings, a manually operated punching
split design, providing for maintenance on the pond machine is used. It has to be taken into consideration that
linings without having to shut down the plant normal drill bits are not used for drilling samples, since iron
➤ Maintenance programmes proposed or in place at the contamination of the samples frequently occurs. Regarding
operation depend on site management in terms of pro- the selection of cathodes in a group to be analysed and the
active maintenance, service schedules, etc. This cannot location on each cathode, a standard procedure was
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Figure 2—Cellhouse layouts showing access platform, feed pipes Figure 5—Showing cathode bail removing four cathodes
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Cell elevation
In order to facilitate the gravity overflow of cells to the
circulation tank, cells need to be elevated of the ground.
When elevation is already a necessity, it is then useful to
elevate the cells high enough to accommodate access for
personnel to inspect the civil structures from time to time,
especially since the cellhouse is such a corrosive
environment. Additionally, floor space underneath the cells
can then also be used as storage space for cell furniture. The
Ruashi Cells were lifted approximately 1.6 m of the ground.
Even so, the terrace level of the tankfarm had to be lowered
to allow overflow into the circulation tank. Additionally, the
circulation tank was designed low with a high floor space
(3.5 m high by 12.5 m diameter) to further accommodate
Figure 6—Overflow launders between cells
gravity feed into the tank.
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ia Current density of anodic reaction A/m2 7. WANG, J. Analytical Electrochemistry, John Wiley and Sons, Inc., 2001,
krev Rate constant of reverse reaction 1/s (2nd Edition).
Cred Concentration of reduced species gmol/m3 8. ZANELLO, P. Inorganic Electrochemistry: Theory, Practice and Application,
ko Rate constant at equilibrium 1/s The Royal Society of Chemistry, 2003.
α Separation factor Dimensionless 9. BRETT, C.M.A. and BRETT, A.M.O. Electrochemistry Principles, Methods,
Eo’ Formal electrode potential Volts and Applications, Oxford University Press, 1993.
Eo Standard electrode potential Volts 10. MACKINNON, D.J. and LAKSHMANAN, V.I. Recent Advances in Copper
γ Activity coefficient Dimensionless Electrowinning, Mineral Research Program, Mineral Research
Laboratories, CANMET Report 76–10, 1976.
io Exchange current density A/m2
Eeq Equilibrium potential Volts 11. ANDERSEN, A.K. and BALBERYSZSKI, T. Electrowinning of Copper at High
Current Densities with the CCS Cell, The Metallurgical Society of AIME,
η Overpotential (overvoltage) Volts
TMS Paper Selection, Paper A68-17, 1968.
Nox” Mass flux of oxidized species gmol/(m2.s)
D Diffusion coefficient of species m2/s 12. ESCOBAR, V., TREASURE, T., and DIXON, R.E. High Current Density EMEW®
Copper Electrowinning, Electrometals Technologies Ltd. Official Website.
(x,t) Species vector at time t and position x -------
http://www.electrometals.co.au.
v Velocity of species m/s
13. ROUX, E., GNOINSKI, J., EWART, I., AND DREISINGER, D. Cu-Removal From the
dΦ/dx Potential gradient across electrolyte Volts/m
Skorpion Circuit Using EMEW® Technology, The South African Institute
∇ Laplace operator -------
• of Mining and Metallurgy, The Fourth Southern African Conference on
ra Reaction rate for species a gmol/(m3.s) Base Metals, 2007.
•
rox Reaction rate for oxidized species gmol/(m3.s)
• 14. Short course on Electrochemistry, Electrochemical Engineering and
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Electrometallurgy: Module on Thermodaynamics and Kinetics, University
dx,dy,dz Distance in x, y and z directions m of the Witwatersrand, Johannesburg, 2005.
δ Boundary layer thickness m
15. SANDENBERGH, R. University of Pretoria Electrochemistry class notes, 2007.
iL Diffusion limited current A/m2
16. HOULACHI, G.E., EDWARDS, J.D., and ROBINSON, T.G. Cu 2007, vol. V, Copper
Re Reynolds number Dimensionless Electrowinning and Elecrorefining, Toronto, Metsoc Publication, August
L Characteristic length m 2007.
ρ Density kg/m3 17. Short course on Electrochemistry, Electrochemical Engineering and
μ Viscosity kg/(m.s) Electrometallurgy: Module on Applications of Fundamentals to
Sc Schmidt number Dimensionless Electrowinning and Electrorefining of Metals. University of the
Sh Sherwood number Dimensionless Witwatersrand, Johannesburg, 2005. ◆
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