Precious Metals Recovery From Cyanide Solution Using EMEW Technology V3 ...
Precious Metals Recovery From Cyanide Solution Using EMEW Technology V3 ...
Precious Metals Recovery From Cyanide Solution Using EMEW Technology V3 ...
Abstract:
The recovery of gold and silver from cyanide bearing solutions using electrowinning
technology designed by Electrometals Technologies Ltd is reviewed. It has been
successfully implemented in copper electrowinning applications, silver refining and in
mining operations for recovery of gold and silver. The technology can be considered as
a complete or partial replacement for Merrill Crowe technology and offers several
advantages in the processing of high grade solutions The advantages of the EMEW
approach and actual plant applications and practices are evaluated and discussed.
1. Introduction
There are a number of approaches that have been proposed and used for the reduction
of silver and gold from cyanide solutions. The most common is the Merrill Crowe
approach which uses zinc cementation and the other is direct electrowinning of the
silver and gold cyanide from solution. The Merrill Crowe approach has found extensive
use as the process chemistry is simple and it can be applied directly to leach solutions
from mining operations as well as to concentrated solutions produced by the elution of
silver and gold absorbed onto activated carbon or ion exchange resins. It is also able to
reduce gold and silver in solution to very low levels, typically below 1 ppm or less.
However, since the advent of concentration technologies based on activated carbon,
electrowinning, using porous steel wool cathodes, has been extensively used to recover
gold and silver from the more concentrated solutions produced by the activated carbon
elution process. Electrowinning provides several advantages over the Merrill Crowe
process including the use of more compact equipment, fewer process steps, reduced
operating costs, the production of a higher grade dor and improved security of the high
value product.
Often the decision regarding the choice of Merrill Crowe or electrowinning for final
precious metals recovery is a critical part of the process flow sheet development. The
decision will depend on the nature of the ore and the choice of upstream processes,
1
such as flotation, leaching, pre-concentration via the use of activated carbon, and the
gold to silver ratios.
In fact, Merrill Crowe is often the recommended option for treating leach solutions with
high silver to gold ratios those exceeding 2:1 Ag:Au - due to the fact that large
amounts of silver reduce the absorption of gold onto activated carbon and, for effective
gold recovery, large amounts of activated carbon along with commensurately larger
processing plants need are required. 1, 2
Thus final reduction of precious metals from leach solutions leads to one of two
processing schemes. The first one shown in Figure 1, or some variant thereof, is usually
the one chosen for high gold ores.
Pretreatment
and/or Flotation
Cyanide Leach
Activated Carbon
Adsorption
Acitivated
Carbon Elution
Electrowinning
Figure 1: Activated carbon and electrowinning based flowsheet for the recovery
of precious metals from cyanide solutions.
The second, shown in Figure 2, is the one commonly considered for high silver
deposits.
Pretreatment
and/or Flotation
Cyanide Leach
Merrill Crowe
Figure 2: Merrill Crowe based flowsheet for the recovery of precious metals from
cyanide solutions.
However practical engineering considerations and the drive to increase recoveries can
result in a combination of these two flowsheets. In some operations, particularly silver
ones, the concentration of silver in the leach solution, say from a flotation concentrate,
is sufficiently high enough, >500 ppm, that an activated carbon concentration operation
is not needed. In these applications the precious metals can be recovered directly by
the Merrill Crowe approach. However, the tails from the pretreatment flotation operation
can contain recoverable amounts of precious metals that a leach followed by activated
carbon absorption and elution is warranted.
Cell design
As a result effective electrowinning of gold and silver from cyanide solutions requires a
complex interplay of operating parameters, equipment design and safety issues.
For the most part these conventional electrolytic cells perform well on the concentrated
leach solutions, but, over time, various other configurations have been proposed
including high flow, fluidized bed and porous cathodes of various configurations.5 Many
of these non-traditional designs have been focused on the recovery of precious metals
directly from dilute leach solutions but none have been a commercial success.
2.
The challenge associated with traditional electrowinning cell design with planar
electrode configurations is that current efficiencies plummet once the concentration of
the electrowon metal in solution decreases. Due to inadequate mixing, a zone of
depletion forms around the cathode and at low concentrations side reactions such as
hydrogen evolution occurs and other unwanted species are electrodeposited and the
morphology of the electrodeposited metal changes. This compromises both the
efficiency and selectivity of the electrowinning process.
In the 1990s a cylindrical electrowinning cell was designed and tested by Electrometals
Technologies Limited in Australia to overcome issues associated with poor solution
contact with the cathode and boundary layer effects. The cell design became known as
the EMEW cell, short for Electrometals Electrowinning, and involved an anode mounted
in the center of a cylindrical cathode and featured the tangential introduction and helical
flow of solution through and out of the electrowinning cell. Figure 1 shows the
comparison of the planar and EMEW anode and cathode configurations as well as the
solution flow through the EMEW cell.
The individual EMEW cells are constructed of 6 to 10 stainless steel cylinders with
plastic end caps to direct and collect the solution flow. The anodes, made of stainless
rods or dimensionally stable anode material are fitted through the center of the cell. The
cells are arranged in an array and solution flow is split between the cells through a
piping manifold. Figure 4 is a photograph of a bank of EMEW cells showing inlet and
outlet piping manifolds and electrical connections.
Figure 4: A bank of EMEW cells showing the piping manifold and electrical
connections.
The electrodeposited metal is plated out on the inside of the cylinder and Figure 5
shows the powdery deposit that is characteristic of silver. The nature of the silver
deposit makes harvesting of the silver fairly easy. A short pulse of very high solution
flow is effective at stripping most of the silver off the inside of the cylinder. The silver
can then be recovered as a powder from solution in a simple filter. In contrast, for a
metal like copper, which produces a solid coherent deposit, the top cap of the cylinder
needs to be removed in order extract an inner cylinder of copper. See Figure 6 which
shows the removal of a typical copper deposit.
Array of cells
Piping manifold
Pump
Rectifier
Electrolyte tank
PLC controller
The basic component configuration is shown in Figure 7. The regular mode of operation
during electrolysis involves circulating the solution from the electrolyte tank through the
7
cells. The system is fully automated and controlled by a PLC. Periodically the solution
flow through the cells is reversed and significantly increased to strip off the
electrodeposited silver which is then separated from the electrolyte on a fine screen or
some other filtration device. After the short strip cycle, the solution flow returns to its
normal mode of circulation from the electrolyte tank through the cells.
Figure 7: Key Components and solution flows through an EMEW silver electrowinning
operation
The EMEW design has been successfully applied to the electrolytic recovery of copper
from sulfate solutions, silver from nitrate and cyanide solutions, nickel from sulfate
solutions, and tin from hydroxide solutions. There are over 15 commercially operating
EMEW plants around the world and many more are presently under consideration.
Development work for the commercial application of the technology to lead, cadmium
and other metals is underway.
10
Figure 8: Depletion curves for silver, gold and copper in an EMEW circuit treating
cyanide solutions
The silver deposits as a fine crystalline powder on the inside of the cathode similar to
that shown in Figure 5. Solution flows are typically of the order of 2 m3/h/cell and every
15 minutes or so the solution flow is reversed and substantially increased to 10 m3/h/cell
for about 10 seconds in the flush cycle. This high flow flushes the fine powdery silver
out of the cell into a tank which is then pumped through a filter press to recover the
precious metals.
Current efficiencies vary considerably over the depletion profile for the solution.
Typically the overall current efficiency is of the order of 10 to 15% over the 1000 to 100
ppm concentration range which is low compared to conventional electrowinning circuits
involving metal recovery from high concentrations of metal but better than the
electrolytic recovery of solutions from low concentrations using conventional
electrowinning cells.
As expected current efficiencies are highly dependent on solution concentrations and
Figure 9 shows current efficiencies for silver recovery from multiple depletion runs
plotted on the same chart. It can be observed at higher solution concentrations, current
11
efficiencies are of the order of 30-40% but then rapidly decrease to 5-10% at lower
concentrations. This data is crucial to developing optimizing the performance of the
EMEW operation and for developing the best operating regime for the EMEW process.
50%
40%
30%
20%
10%
0%
-
250
500
750
1,000
1,250
Figure 9: Current densities for silver recovery from cyanide solution in an EMEW circuit.
In practice the EMEW operation has worked well and has produced a lot of silver and
gold. Challenges associated with the EMEW operation have included leaks, corrosion of
cathode contacts, lack of maintenance and the absence of automated voltage
monitoring on the individual cells plus the fact the EMEW operation is a more highly
automated operation than the Merrill Crowe process and a higher level of operator
training is required.
3.2 Electrowinning Versus Merrill Crowe Complimentary Rather than Competing
Technologies
Based on recent plant experience as well as the elevated precious metals prices over
the past few years, the original concept for the EMEW technology as a direct and
complete replacement for the Merrill Crowe process for the recovery of silver and god
from cyanide solution has been reconsidered. Initially it was proposed that direct
electrowinning would be sufficient to recover all the precious metals and to produce
spent solutions with 50 ppm levels of silver. However, plant practice has demonstrated,
that for some operations, the EMEW process works better in conjunction with, rather
than as a replacement, of the Merrill Crowe operation. The Palmarejo operation now
incorporates both processes. EMEW is used for the recovery of the bulk of the silver
and gold and the Merrill Crowe process is used as a polishing operation to achieve very
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low concentration of precious metals in the spent solution. Or, if conditions require the
treatment of large volumes of solution, the EMEW and Merrill Crowe processes can be
operated in parallel resulting in a substantial increase in capacity. A simplified version of
the Palmarejo flowsheet is shown in Figure 10
The EMEW approach works very well for the recovery of silver from higher
concentrations, >100 ppm Ag, and, even though low silver concentrations can be
achieved in the EMEW process, lengthy residence times and low current efficiency
result. On the other hand, the Merrill Crowe process is well suited for rapid recovery of
low concentration of residual precious metals. In cases where the spent electrolyte is
not recycled to the leach or elution circuits, mine operators may require a Merrill Crowe
process onsite to polish silver to low concentrations before spent solutions are sent to
tailings.
The bulk of the precious metals are recovered in a easy to manage form that yields
a higher grade dor material than that would be possible from the Merrill Crowe
alone
13
Processing material through the EMEW process results in the removal of a good
deal of the particulate content and clarification of solution which is often required
before treating solutions in the Merrill Crowe process.
The Merrill Crowe process at the end is an effective, rapid and efficient polishing
step and produces spent solutions with low concentrations of precious metals.
It allows operations personnel to make operating decisions based on the relative
costs of the two process and in particular the costs of zinc vs. electricity.
14
ln Ct/Co
0
-
2.00
4.00
6.00
8.00
10.00
-0.5
-1
-1.5
-2
y = -0.2437x
R = 0.9966
-2.5
Figure 11: Natural log plot vs. time for the electrolytic recovery of silver from cyanide
solution.
The circuit constant for this run is determined from the slope to be 0.247h-1. This circuit
constant serves as a useful design and operations tool. It can be readily determined for
each electrolysis run and serves as a useful confirmation that the circuit is operating
close to design conditions. A large deviation from the design value would serve as an
indicator of a short coming (or perhaps a short circuit!) in the operation
Table 1 shows the variability and correlation coefficients for a series of runs for the
same circuit running under similar conditions over a 10 day period.
Table 1: Circuit constants for the recovery of silver from cyanide solution in and EMEW
circuit determined using first order kinetics for a series of runs
Run
1
2
Circuit
Constant
-0.316
-0.375
15
4
5
3
-0.290
-0.244
-0.291
It is noted that these depletion curves are similar to those observed for packed bed
precious metal electrowinning units where the same first order relationship has been
proposed.13 In these systems the kinetics are mass transfer controlled which leads to
the first order relationship. On reflection an EMEW system with solution passing
through hundreds of individual cells could be viewed as an approximation of a packed
bed unit where the solution is passing through multiple openings in the packed bed. The
key difference being that packed bed units show a voltage profile through the packed
bed cathode, whereas, in each of the EMEW cells, the voltage profile is less
pronounced and is close to identical in each individual cell.
3.4 Operating Cost Assessments
Our update of published costs projections for the EMEW and Merrill Crowe processes
are shown in Table 2. It must be noted that these are our estimates only based on
generic high silver operation and do not reflect the costs at the Palmarejo operations.
Table 2: Comparison of operating costs for the EMEW and Merrill Crowe process for the
recovery of silver from cyanide solutions.
Labor
Zinc
Electricity
Reagents
General Consumables
Filter aid & cloths
Maintenance
Crucible & Refract
Fluxes
Diesel
Total/kg Ag
Total/troy oz Ag
EMEW
$
7.46
$
$
5.18
$
$
0.11
$
0.13
$
0.74
$
0.13
$
0.01
$
$
13.75
0.43
Merrill
Crowe
$ 10.67
$
4.00
$
3.11
$
0.23
$
0.33
$
0.75
$
1.59
$
0.90
$
0.13
$
0.46
$ 22.16
$
0.69
Earlier analysis10 indicated operating cost of the EMEW operation were ~50% of the
Merrill Crowe cost, however, with increased fossil fuel costs and commodity cost,
adjustments and corrections were necessary. Our updates, shown in Table 2, indicate
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that the difference has shrunk somewhat and the EMEW costs are ~60% of Merrill
Crowe costs. In both operations, the labor costs are estimated to be the most
significant. For the EMEW operation electricity costs are about $5.18/kg Ag whereas in
the Merrill Crowe operation zinc and electricity cost are $7.11/kg Ag. For these cost
estimates, highly conservative projections were used. High electricity and fuel costs,
$0.50/kWh and $6/gal of diesel, as well as very low current efficiencies, 10%, were
assumed. Lower electricity costs and improved current efficiencies would serve to
further improve the price differential between the EMEW and Merrill Crowe options.
4. Conclusions
The cylindrical EMEW electrowinning cell - designed, developed and implemented by
Electrometals - has been successfully implemented for the electrolytic recovery of a
variety of base and precious metals. Notably the electrowinning of silver and gold from
cyanide solution has been successfully implemented on a plant scale and as a result
millions of troy oz of silver (along with some gold) are recovered every year using
EMEW technology.
The EMEW operation results in substantial reductions in operating costs, it produces a
cleaner precious metals dor, and it permits automatic harvesting of the silver product.
In some cases, the EMEW process can be viewed a replacement for the Merrill Crowe
zinc cementation process but plant experience has demonstrated that some
circumstances might require both the implementation of the electrowinning and Merrill
Crowe process to operate in a complimentary manner. The bulk of the precious metals
recovery is done electrolytically to produce a low cost, higher precious metals content
dor and the Merrill Crowe process is used to recover the residual amounts of precious
metals in solution and to act, when necessary, as a second process to increase overall
precious metals throughput.
Even though implementation has been successful there remain many opportunities for
process improvement and optimization. These include voltage monitoring of individual
cells, increases in current densities and the determination of first order circuit constants
that can be used to monitor the performance of an EMEW circuit.
17
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2
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3
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4
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5
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6
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8
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