RENOVARE INTERNATIONAL, INC.

REVIEWING THE OPERATION

OF GOLD ELECTROWINNING
CELLS
RenoCell® Technical Bulletin

June 28, 2011

NOTICE

Renovare International, Inc. believes the information and recommendations herein to be

accurate and reliable as the date of this document and that Renovare's products mentioned
herein are reasonably fit for the recommended purposes. However, as use conditions are
not within its control, Renovare does not guarantee results from use of such products or
other information herein; no warranties, expressed or implied, are given. As governmental
regulations and application or use conditions may change, it is the User's responsibility to
determine the appropriateness of Renovare's products for User's specific end uses.
Freedom from patents or trade secrets of Renovare or others is not to be inferred. For any
information that may have been published subsequent to the document’s date, contact
Renovare International, Inc.

The footnotes (1-4) provide the result of an analysis that is associated with Equation 5 in
Tables A through D. The Au concentration with Table A, with Au concentration over the
range 0.2 incrementally to 2G/M3(footnote 1); Table B the range 2 to20 in increments of 2
G/M3; Table C the range 20 to 200 increments of 20G/M3;Table D from 200 to 2000. The
corresponding equilibrium potential is provided with each Au concentration.
REVIEWING THE OPERATION OF GOLD
ELECTROWINNING CELLS
RENOCELL® TECHNOLOGY

The RenoCell® is an advanced, patented electrolytic cell design that is being used today for
electrowinning (EW) metal recovery from process and waste water streams of a variety of
precious and heavy metals. The RenoCell® consistently and efficiently reduces dissolved
heavy (and all precious) metal to the sub-mg/L (ppm) concentration levels in a wide range
of applications. The revolutionary performance of the RenoCell® is the result of a patented
EW cell design that, for the first time, effectively utilizes a three-dimensional (3-D) cathode
incorporating a porous carbon fiber plating element. The key to performance in any EW
cell design is effective use of the surface area of the cathode available for electrodeposition
of the dissolved metal ions. Since the porous carbon felt has at least a 500 times greater
effective surface area than an equivalent 2-D planar cathode, and the RenoCell® design
provides effective current and fluid flow distribution to this surface area, RenoCell®
performance is greatly enhanced when compared to existing electrolytic cell designs.

The net result is that the RenoCell® can achieve much lower final metal ion concentrations
using far less energy. This results in more metal removal in less time, and lower metal
concentrations than has ever been achieved by EW technology to remove a given amount of
metal from a metal-bearing solution. In general, RenoCell® is capable of a factor of 100 or
lower final concentration of metal ions and three to ten or more times higher current
efficiency than other electrolytic cells. RenoCell® is being used to achieve metal discharge
effluent limits without further treatment; collects metals as elements ready for reuse or
sale; use removable cartridges for ease of operations and maintenance; and improve cost
effectiveness and reduce life cycle costs. RenoCell®’s enclosed cell design and small
“footprint” allow the user substantial flexibility in placing a unit in a tight space.

A RenoCell® metal recovery system consists of the world’s most efficient and highest
performance electrowinning (EW) cell, a direct current (DC) power supply, and auxiliary
equipment. Metal-bearing waste water or a process stream is electrolytically stripped of
dissolved heavy metal ions as it passes through the RenoCell®. The metal ions are
deposited as solid metal onto a specialized high surface area, carbon cathode. When the
cathode is fully loaded, it is easily removed from the cell and replaced with a fresh one. The
loaded carbon cathode can then be burned in a furnace or sold for its metal value.

RRII-110010-0 1 Renovare International, Inc.

1. INTRODUCTION

As mining operations strive to increase ore throughput and grade, it is becoming

increasingly common for plant personnel to find plant solution tails rising. Often, this is a
result of not moving the carbon through the adsorption circuit quickly enough. Inadequate
stripping capacity, particularly in circuits using the Zadra elution process, is sometimes the
limiting step. Within the stripping process it is often electrowinning (EW) performance that
is determining maximum stripping frequency. With this in mind, it may be useful to review
gold electrowinning and explore if and how electrowinning efficiency may be improved.

This technical paper will:

• Present some EW theory,

• Discuss the factors that can effect EW efficiency, and
• Discuss the EW RenoCell® technology and experience, as related to the more
common EW cells.

To a great extent, the calculations made to size a standard gold electrowinning cells are
based on data and models reported by Roger Paul of Mintek in SA. Extensive plant data
collected and interpreted by Mike Costello (Australia) has been used to further enhance the
methodology used to size common gold EW cells. Discussion presented is based on the
“Mintek”-type cell and compared to the RenoCell® and others as available. Most comments,
except for RenoCell®’s efficiencies and potential for Direct electrowinning (DEW) are
relevant to other cell types.

1.1 LEACH CHEMICAL PROCESS

The hydrometallurgical leaching of gold from gold-bearing ores or the dissolution of gold
metal during the recycling of electronic and precious metal scrap is performed every day
using hazardous chemicals. These chemicals represent risks for workers and threat for the
environment. However, several other reagents are known to dissolve gold at the laboratory
scale, none of these are used industrially. All of the hydrometallurgical gold extraction
routes utilize a leaching step to produce a gold-bearing solution as an intermediate product
while the recycling of secondary gold from the recycling of secondary gold from electronic
and precious metal scrap using selective and fast dissolution of the precious metal
constituents. Therefore, either leaching or dissolution operations require highly corrosive
media due to the well-known chemical inertness of the noble metal toward most acids and
bases.

RRII-110010-0 2 Renovare International, Inc.

Several reagents are known to leach gold from gold-bearing ores. It has been known for
more than a century that alkaline solutions of alkali-metal cyanides (e.g., NaCN, KCN)
dissolve gold under aerated conditions. The dissolution of metallic gold is due to the strong
complexing capabilities of cyanide anions combined with the oxidizing properties of the
dissolved molecular oxygen. Upon dissolution, gold forms the stable dicyanoaurate (III)
complex anion [Au(CN) –], as follows:

4 Au + 8 CN- + O2 + 2 H2O = 4 Au(CN)2- + 4 OH-

Other oxidizing compounds like cyanogen bromide (CNBr) can also be used to replace
dissolved oxygen. Gold metal is also leached by aerated aqueous solutions of ammonium
thiosulfate according to the overall reaction scheme given in the following formula:

4 Au + 8 (NH4)2S2O3 + O2 + 2 H2O = 4 (NH4)2Au(S2O3)2 + 4 (NH4)OH

Finally, gold metal is dissolved by an aerated solution containing thiourea according to the
following overall reaction:

4 Au + 8 NH3CSNH2 + O2 + 2 H2O = 4 Au[CSNH2)2 + 4 OH-

However, only the cyanidation process is used industrially in hydrometallurgical processes.

The optimized leaching conditions are usually a concentration of lixiviant of 0.1 - 0.2
mol·dm– NaCN. Enough NaOH must be present as neutralizer to maintain alkaline
3

conditions at a constant pH of 11.

Several reagents can be used in the dissolution of gold metal from electronic and precious
metal scrap. Among them, hot aqua regia is extensively used in small- and medium-scale
operations. It is obtained by mixing three parts of concentrated hydrochloric acid (HCl)
with one part of concentrated nitric acid (HNO3). Moreover, it usually contains a halogen or
even a certain amount of hydrogen peroxide to increase the dissolution rate. Upon
dissolution in this media, gold forms the stable tetrachloroaurate (III) complexing anion
(AuCl4-), in the following formula:

Au + 8 HCl + HNO3 = HAuCl4 + NO + 2 H2O

The main drawback of the treatment with aqua regia is the nitric oxide (NO) gas that
evolves when the metal is digested. This noxious gas represents a major threat for the
health and safety of the workplace. Apart from aqua regia, other corrosive reagents have
been used or tested. For example, gold was dissolved into chlorine water (i.e., water
saturated by chlorine gas) while bromine water has also been mentioned. It was the first
metallurgical process to recover gold. Others studying the action of chlorine water onto
gold, suggested that the dissolution mechanism is based on the reaction of molecular
chlorine in water followed by a decomposition of a fraction of the hydrochloric acid,

RRII-110010-0 3 Renovare International, Inc.

yielding nascent chlorine. On the other hand, strong halohydric acids HX (e.g., HCl, HBr) in
which the corresponding halogen X (e.g., Cl , Br ) is dissolved have been known and used
from several in the presence of both a strong oxidant and a halide anion under highly acidic
solutions. Moreover, a hot solution of hydrochloric acid mixed with a hydrogen peroxide
also dissolves gold by the following:

2 Au + 8 HCl + 3 H2O2 = HAuCl4 + 6 H2O

It has been shown that the dissolution of gold is facilitated by formation of the highly
reactive nascent chlorine. However both the hydrometallurgical leaching of gold ores by
cyanidation and the aqua regia process used for the secondary gold from waste electronics
and precious metal scrap recovery are processes where both the lixiviant and reagent are
hazardous chemicals that have serious health, safety, and environmental concerns but are
widely used commercially because they are proven and have lower capital and, often, lower
operating costs than competing techniques.

The hydrometallurgical leaching of gold from gold-bearing ores or the dissolution of gold
metal during the recycling of electronic and precious metal scrap is performed every day
using hazardous chemicals. These chemicals represent risks for workers and threat for the
environment. However, several other reagents are known to dissolve gold at the laboratory
scale, none of these are used industrially. All the hydrometallurgical gold extraction routes
utilize a leaching step to produce a gold-bearing solution as an intermediate product while
the recycling of secondary gold from the recycling of secondary gold from electronic and
precious metal scrap using selective and fast dissolution of the precious metal constituents.
Therefore, either leaching or dissolution operations require highly corrosive media due to
the well-known chemical inertness of the noble metal toward most acids and bases.

1.1.1 CYANIDE LEACH CHEMISTRY

Cyanide leaching of gold (Au) is an electrochemical procedure that can be described by the
following reactions:

Anodic:

4 Au = 4 Au+ + 4e-

4 Au+ + 4 CN- = 4 AuCN

4 AuCN + 4 CN- = 4 Au(CN)2-

Cathodic:

O2 + 2 H2O + 2 e- = H2O2+ 2 OH-

RRII-110010-0 4 Renovare International, Inc.

H2O2- +2 e- = 2 OH-

that yields:

4 Au + 8 CN- + O2 + 2 H2O = 4 Au(CN)2- + 4 OH-

In aqueous, alkaline cyanide leaches, Au oxidizes and dissolves forming Au (I) cyanide
complexes in three stages where the species causes temporary passivation of the Au
surface leading to a complex with free cyanide to form a Au(CN)2- ion and finally a
passivating Au (III) oxide layer that only is available at a high positive potential that is not
common.

2. MORE ELECTROWINNING THEORY

EW involves the exchange of electrons between a solid electrode and ions or molecules
dissolved in solution. The rate of the reactions involved depends on the electrode potential,
the electrode area and the rate of mass transport of the electroactive species to the
electrode surface of interest.

If the cathode potential is sufficiently negative, all of the electroactive species undergo
reduction to metal as soon as they reach its surface. The current at which this point is
reached is known as the limiting current. Further increasing the cathode potential only
results in the depletion, at the cathode surface, of the metal salt (ion) being reduced. At this
point the transport of the ionic species through the Nernst boundary layer to the cathode
surface becomes the rate-determining step. That is, the rate of metal reduction at the
cathode has moved from electrochemical (kinetic) control to mass transport control. To
increase the rate of the EW process under these conditions, it is necessary to increase
either the electrode area (RenoCell®) or the rate at which the electroactive species are
delivered (RenoCell®) to the cathode.

For the conditions noted, Tables A through F present the equilibrium electrode potential
(Eeq)SHE for a number of reactions of the general form:

M(CN)xy-x + ye- = M + xCN-

Table A: Equilibrium Potential for the Reduction of Metal-Cyanide Ions*

REACTION METAL VALENCE METAL CONC. (G/M3) EEQ (VSHE)

(1) 2H2O + O2 + 4e- = 4OH- pH = 13 - +0.45

(2) Hg(CN) 4 2- + 2e- = Hg + 4CN- 2 0.2 -0.448

(3) Pb(CN)4 2- + 2e- = Pb + 4CN- 2 0.2 -0.498

(4) Ag(CN) 2- + e- = Ag + 2CN- 1 0.1 -0.568

RRII-110010-0 5 Renovare International, Inc.

 (5) Au(CN) 2- + e- = Au + 2CN- 1 1 0.2 -0.514

(6) Cu(CN)32- +e- = Cu + 3CN- 1 0.06 -0.868

(7) 2H2O + 2e- = H2 (g) + 2OH- pH = 13 - -0.78

(8) Fe(CN)64- + 2e- = Fe + 6CN- 2 0.06 -1.108

(9) Ni(CN) 42- + 2e- = Ni + 4CN- 2 0.06 -1.188

(10) Zn(CN) 42- + 2e- = Zn + 4CN- 2 0.07 -1.338

* Metal ion concentration = 10-6 mol/liter; Free cyanide concentration = 0.2%

Table A has been carefully prepared to serve as a model for Tables B through F, with the
only real difference being metal ion concentrations and their ion equilibrium potential
reduction of metal-cyanide ions, focusing upon the Au ions in a variety of analyses, as
follows:

Table B: Equilibrium Potential for the Reduction of Metal-Cyanide Ions*

REACTION METAL VALENCE METAL CONC. (G/M3) EEQ (VSHE)

(1) 2H2O + O2 + 4e- = 4OH- pH = 13 - +0.45

(2) Hg(CN) 4 2- + 2e- = Hg + 4CN- 2 2.0 -0.389

(3) Pb(CN)4 2- + 2e- = Pb + 4CN- 2 2.1 -0.439

(4) Ag(CN) 2- + e- = Ag + 2CN- 1 1.1 -0.509

-0.572
(5) Au(CN) 2- + e- = Au + 2CN- 2 1 2.0

(6) Cu(CN)32- +e- = Cu + 3CN- 1 0.6 -0.809

(7) 2H2O + 2e- = H2 (g) + 2OH- pH = 13 - -0.78

(8) Fe(CN)64- + 2e- = Fe + 6CN- 2 0.6 -1.049

(9) Ni(CN) 42- + 2e- = Ni + 4CN- 2 0.6 -1.129

(10) Zn(CN) 42- + 2e- = Zn + 4CN- 2 0.7 -1.279

1 Au conc. G/M3: 0.02, 0.04,0.06; 0.08, 0.1, 0.12, 0.14, 0.16, 0.18, 0.2

EEQ: -0.456;0.4783 -0.483, -0.491, -0.496, -0.500, -0.505, -0.5.8, -0.511, -0.517

2 Au conc. G/M3: 0.2, 0.4, 0.59, 0.79, 0.99, 1.18, 1.29, 1.57, 1.77, 2.0

EEQ: -0.517, -0.513, -0.,541 -0.548, -0.554, -0.559, -0.563, -0.566, -0.569, -0.572

RRII-110010-0 6 Renovare International, Inc.

* Metal ion concentration = 10-5 mol/liter; Free cyanide concentration = 0.2%

Table C: Equilibrium Potential for the Reduction of Metal-Cyanide Ions*

REACTION METAL VALENCE METAL CONC. (G/M3) EEQ (VSHE)

(1) 2H2O + O2 + 4e- = 4OH- pH = 13 - +0.45

(2) Hg(CN) 4 2- + 2e- = Hg + 4CN- 2 20 -0.33

(3) Pb(CN)4 2- + 2e- = Pb + 4CN- 2 20.7 -0.38

(4) Ag(CN) 2- + e- = Ag + 2CN- 1 10.7 -0.45

(5) Au(CN) 2- + e- = Au + 2CN- 3 1 19.7 -0.63

(6) Cu(CN)32- +e- = Cu + 3CN- 1 6.3 -0.75

(7) 2H2O + 2e- = H2 (g) + 2OH- pH = 13 - -0.78

(8) Fe(CN)64- + 2e- = Fe + 6CN- 2 5.5 -0.99

(9) Ni(CN) 42- + 2e- = Ni + 4CN- 2 5.9 -1.07

(10) Zn(CN) 42- + 2e- = Zn + 4CN- 2 6.5 -1.22

* Metal ion concentration = 10-4 mol/liter; Free cyanide concentration = 0.2%

Table D: Equilibrium Potential for the Reduction of Metal-Cyanide Ions*

REACTION METAL VALENCE METAL CONC. (G/M3) EEQ (VSHE)

(1) 2H2O + O2 + 4e- = 4OH- pH = 13 - +0.45

(2) Hg(CN) 4 2- + 2e- = Hg + 4CN- 2 200 -0.271

(3) Pb(CN)4 2- + 2e- = Pb + 4CN- 2 207 -0.321

(4) Ag(CN) 2- + e- = Ag + 2CN- 1 107 -0.391

(5) Au(CN) 2- + e- = Au + 2CN- 4 1 197 -0.736

(6) Cu(CN)32- +e- = Cu + 3CN- 1 63 -0.691

(7) 2H2O + 2e- = H2 (g) + 2OH- pH = 13 - -0.78

(8) Fe(CN)64- + 2e- = Fe + 6CN- 2 55 -0.99

3 Au conc. G/M3: 2.0, 3.94, 5.91, 7.85, 9.85, 11.52, 12.50, 14.78, 16.85, 18.81, 19.7

EEQ: -.0.572, -0.589, -0.600, -0.607; -0.612; -0.617; -0.621; -0.624; -0.627;-0.633

4 Au conc. G/M3: 20;39.4;59.1, 78.5, 98.5, 115.2, 135.0; 158.5, 178.1, 197

EEQ: -.0.63;-0.648;-0.658;-.0665;-0.671;-0.675;-0.679;-0.682;-0.685;-0.688

RRII-110010-0 7 Renovare International, Inc.

 (9) Ni(CN) 42- + 2e- = Ni + 4CN- 2 59 -1.011

(10) Zn(CN) 42- + 2e- = Zn + 4CN- 2 65 -1.161

* Metal ion concentration = 10-3 mol/liter; Free cyanide concentration = 0.2%

Table E: Equilibrium Potential for the Reduction of Metal-Cyanide Ions*

REACTION METAL VALENCE METAL CONC. (G/M3) EEQ (VSHE)

(1) 2H2O + O2 + 4e- = 4OH- pH = 13 - +0.45

(2) Hg(CN) 4 2- + 2e- = Hg + 4CN- 2 2000 -0.212

(3) Pb(CN)4 2- + 2e- = Pb + 4CN- 2 2070 -0.262

(4) Ag(CN) 2- + e- = Ag + 2CN- 1 1070 -0.332

(5) Au(CN) 2- + e- = Au + 2CN- 1 19.7 -0.63

(6) Cu(CN)32- +e- = Cu + 3CN- 1 630 -0.632

(7) 2H2O + 2e- = H2 (g) + 2OH- pH = 13 - -0.78

(8) Fe(CN)64- + 2e- = Fe + 6CN- 2 550 -0.872

(9) Ni(CN) 42- + 2e- = Ni + 4CN- 2 590 -0.952

(10) Zn(CN) 42- + 2e- = Zn + 4CN- 2 650 -1.102

*Metal ion concentration = 10-2 mol/liter; Free cyanide concentration = 0.2%

Table F: Equilibrium Potential for the Reduction of Metal-Cyanide Ions*

REACTION METAL VALENCE METAL CONC. (G/M3) EEQ (VSHE)

(1) 2H2O + O2 + 4e- = 4OH- pH = 13 - +0.45

(2) Hg(CN) 4 2- + 2e- = Hg + 4CN- 2 20000 -0.153

(3) Pb(CN)4 2- + 2e- = Pb + 4CN- 2 20700 -0.203

(4) Ag(CN) 2- + e- = Ag + 2CN- 1 10700 -0.273

(5) Au(CN) 2- + e- = Au + 2CN- 5 1 197 -0.688

(6) Cu(CN)32- +e- = Cu + 3CN- 1 6300 -0.573

(7) 2H2O + 2e- = H2 (g) + 2OH- pH = 13 - -0.78

(8) Fe(CN)64- + 2e- = Fe + 6CN- 2 5500 -0.813

5 Au conc. G/M3: 197;394;591;758;986;1182

EEQ: -0.688;.0.705;-0.716;-0.723;-0.726;-0.733

RRII-110010-0 8 Renovare International, Inc.

 (9) Ni(CN) 42- + 2e- = Ni + 4CN- 2 5900 -0.893

(10) Zn(CN) 42- + 2e- = Zn + 4CN- 2 6500 -1.043

* Metal ion concentration = 10-1 mol/liter; Free cyanide concentration = 0.2%

Table G: Equilibrium Potential for the Reduction of Metal-Cyanide Ions with

Changing Temperatures*
Au
T Au EEQ EEQ Au EEQ
REACTION (G/M3
C (G/M3) (VSHE) (VSHE) (G/M3) (VSHE)
)
Au(CN) 2- + e- = Au + 2CN- 20 0.2 - 1.97 - 19.7 -

25 0.2 -0.54 1.97 -0.572 19.7 -0.63

30 0.2 -0.59 1.97 -0.570 19.7 -0.63

40 0.2 -0.506 1.97 -0.568 19.7 -0.63

50 0.2 -0.501 1.97 -0.566 19.7 -0.63

60 0.2 -0.497 1.97 -0.564 19.7 -0.63

70 0.2 -0.493 1.97 -0.562 19.7 -0.63

80 0.2 -0.490 1.97 -0.560 19.7 -0.63

90 0.2 -0.485 1.97 -0.558 19.7 -0.63

120 - - - - - -
* All other ions concentration = 10-4 mol/liter (each); Free cyanide concentration = 0.2%

Table H: Equilibrium Potential for the Reduction of Metal-Cyanide Ions with

Changing Temperatures*
T Au EEQ Au EEQ Au EEQ
REACTION
C (G/M3) (VSHE) (G/M3) (VSHE) (G/M3) (VSHE)
Au(CN) 2- + e- = Au + 2CN- 20 19.7 -0.63 197 -0..688 1970 -0.746

25 19.7 -0.63 197 -0.689 1970 -0.748

30 19.7 -0.63 197 -0.690 1970 -0.750

40 19.7 -0.63 197 -0.692 1970 -0.754

50 19.7 -0.63 197 -0.694 1970 -0.758

60 19.7 -0.63 197 -0.696 1970 -0.762

70 19.7 -0.63 197 -0.698 1970 -0.764

80 19.7 -0.63 197 -0.700 1970 -0.766

RRII-110010-0 9 Renovare International, Inc.

 90 19.7 -0.63 197 -0.702 1970 -0.700

120 19.7 -0.63 197 - 1970 -

* All other ions concentration = 10-4 mol/liter (each); Free cyanide concentration = 0.2%

Eeq is calculated using the Nernst equation:

Eeq = E0 + 0.059 log {M(CN)xy-x / [CN-]x}

The standard reduction potential E0 is calculated from the standard reduction potentials of
the reaction:

My+ + ye- = M

with the equilibrium constant for the reaction:

My+ + xCN- = M(CN)xy-x

As indicated in Tables A thru F above, cyanide complexes of mercury, lead, and silver will
be electrodeposited in preference to gold. This is a very important point to note if you are
electrowinning gold from an eluate with a high silver content since silver will be deposited
(and hence will consume current) in preference to gold.

The reduction potentials for copper, nickel, iron and zinc are more negative than gold in
cyanide chemistry. However, at the potential used in gold EW, the deposition of copper in
particular is problematic depending on the copper concentration in the eluate. It is noted
that every tenfold increase in copper concentration causes a positive shift of +0.059V in the
copper equilibrium potential. Consequently, the equilibrium potential for 630 ppm copper
in eluate will be approximately –0.63V, the same as gold at 20 ppm. As would be expected,
copper recovery increases as the voltage (and consequently the current) applied increases.

2.1 INFLUENCE OF BASE METALS

Conventional electrowinning is best suited to the partial recovery of gold from solutions
with high gold tenors. Furthermore, no foreign ions are introduced into the solution and it
can also be efficiently operated at higher temperatures. High-grade gold can be produced
that requires no further purification, provided that the solution to be treated does not
contain metal ions that will be plated during EW. Unfortunately, this is an idealized
assumption because base metals such as silver, copper, nickel, cobalt and iron typically
occur with gold in the electrolyte as cyanide complex ions and may be plated out during
EW. A major disadvantage of the conventional gold electrowinning process is its inability to
produce discardable tailings. This is mainly due to the cathodic shift in the reduction
potential of the Au(CN)₂ /Au half reaction when the gold in solution decreases, resulting in

RRII-110010-0 10 Renovare International, Inc.

preferential deposition of base metals, and also a decrease in the mass transfer rate of
aurodicyanide to the cathode surface, which may cause a significant decrease in the
efficiency of conventional EW process.

As stated previously, base metals may influence the gold electrowinning process when
present in high concentrations relative to that of gold or when too high overpotentials are
applied. Base metals can adversely affect the EW process in terms of decreased current
efficiencies, poor bullion fineness, and passivation of the cathode surface, and by
influencing the morphology of the plated gold.

Much of these issues and problems are overcome by the RenoCell® electrowinning
technology, either by producing discardable tailings and/or making direct electrowinning
(DEW) and its positive features and extensive benefits available to the end user and
operator.

The following electrochemical reactions are of relevance during the gold electrowinning
process (E values quoted for metal ion concentrations of 10-4 mol.dm-3, NaCN concentration
of 0.2% and NaOH concentrations of 2%).

The gold, which is present in the solution in the form of aurodicyanide (Au(CN)2 ), is
reduced to metallic gold, according to Reaction (5) at potentials more negative than the
reversible potential. Reaction (1), representing oxygen reduction in alkaline solutions, is
another cathodic reaction competing with gold deposition. This is primarily because the
electrolyte is typically saturated with oxygen due to the oxygen evolution occurring at the
anode. Reaction (7) represents the evolution of hydrogen, which occurs at a significant rate
at potentials more negative than -0.9VSHE when working at pH values above 10.1. The
evolution of hydrogen should be under kinetic control at a significant range of potentials
more negative than -0.96 VSHE, and therefore may consume a high proportion of the
cathodic current.

The major anodic reaction is the oxidation of water to oxygen, also indicated by Reaction
(1) of the above tables. The reduction reaction of cuprous cyanide (Cu(CN)3 ) to metallic
copper is indicated in Reaction (7). The more negative potential for the reduction of
cuprous cyanide to metallic copper than that for the reduction of aurodicyanide to metallic
gold signifies that gold should plate preferentially to copper at these conditions. However,
copper may co- deposit with gold if high overpotentials are applied, or when the copper
concentration is high relative to that of gold.

The kinetics of electrochemical reactions is typically studied by conducting polarization

experiments in which the current required to change the potential of the electrode is
determined. If the potential of the electrode is changed at a continuous rate, so-called
potentiodynamic polarization diagrams are obtained. While it is relatively easy to obtain

RRII-110010-0 11 Renovare International, Inc.

polarization data, the interpretation is often difficult, as more than one reaction may
contribute to the currents measured. Thus, it is preferable to first simplify the investigation
of industrial scale systems by characterizing a purer electrolyte and then sequentially
adding species that may contribute to further electrochemical reactions. In this way the
contributions of the individual reactions may be isolated, if it can be assumed that
interaction between the species will be minimal.

From an industrial point of view, it is typically essential with conventional EW to obtain

loosely adherent precipitates that can be easily removed with high pressure water. If this
cannot be achieved, some gold will get locked up inside the conventional electrowinning
cells, which can result in electrowinning being uneconomical. This is not the case with the
RenoCell® which allows all the captured value to be readily easily to be recovered by
simply furnace processing of the metal coated carbon cathode by simple burning at
~600οC. Unlike the stainless steel cathodes, the electrolyte temperature, current density,
and conductivity of the electrolyte have typically proved to be the main parameters that
influence the adhesion of gold precipitates; co-deposition of base metals, such as copper,
may also have an effect on the morphology and adhesion of the precipitate.

The electrodeposition of gold in industrial electrowinning cells is typically operated under

mass transfer control. Various testing protocols have been developed over the decades to
allow important operational parameters to be investigated and allow more effective cells to
be investigated and compared, and RenoCell® is the world’s premier example.

Synthetic solutions are prepared to simulate plant conditions. For example, the electrolyte
may be prepared by adding 2 % caustic soda together with 0.1 % CN, to simulate
conditions normally encountered in plant practice. Chemical compositions typically ranged
from low to high copper and gold concentrations in order to determine at which
concentrations the influence of copper became problematic. The influence of gold and
copper at various concentrations is typically studied as is the morphology of the deposited
metal with conventional EW.

The influence of the gold tenor on the polarization behavior of stainless steel electrodes is
well established. A positive shift in the potential, where the gold reduction could be
noticed, from -1.09 VSSE to -0.95 VSSE at a current density of 85 mA/m2 can be observed
when the gold in solution concentration is changed from 5 ppm to 1,000 ppm. This signifies
that, during the electrowinning process, the potential for gold reduction will also shift to
more negative potentials as the gold is removed from the solution. This may result in a
change in the rate-limiting step of the electrochemical reaction from diffusion control to
chemical control when a constant potential is applied

As mentioned, copper may co-deposit with gold when present in high concentrations
relative to the concentration of gold. It is evident that copper present in concentrations of

RRII-110010-0 12 Renovare International, Inc.

200 ppm and higher will plate preferentially to gold present at 5 ppm. At these
concentrations, the current density for the copper reduction reaction is higher than that for
the gold reduction reaction at an applied potential of -1.0 VSSE. Copper will therefore plate
at a faster rate than gold under these conditions. Although the current efficiency for gold
electrowinning is expected to decrease as copper co-deposits with gold, the rate of gold
electrowinning should remain the same, whether copper is present in the solution or not.
This is because, at a specific applied potential, the limiting current for gold reduction
should be independent of the copper concentration, assuming that the electrode potential
will be such that the rate-determining step for gold deposition will be the mass transfer of
aurodicyanide to the reaction interface. Very loosely adherent precipitates were obtained
when gold is plated from solutions containing only gold. On the other hand, copper plated
from pure copper containing solutions proved to be moderate to highly adherent. Further
discussion of gold and mixed Au-Cu for common EW used by the gold mining industry now
is found in A Study of the Influence of Copper on the Gold Electrowinning Process, by J. Steyn
and R.F . Sandenbergh.

Although copper will co-deposit with gold during the electrowinning process, relatively
high-grade gold can still be produced by controlling the potential of the cathode. While the
presence of copper will lead to a decrease in the current efficiency for gold recovery, the
rate at which gold is recovered should remain unaffected if a constant potential is applied.
Observations made indicated that the influence of copper on the adhesion of the obtained
precipitate is of greater importance than its influence on the electrowinning performance
in terms of the rate and current efficiency. Highly adherent precipitates were obtained
when copper and gold were plated from solutions containing high copper concentrations,
typically at concentrations higher than 500 ppm Cu. The level of adhesion of a gold
precipitate obtained from a solution containing 100 ppm Au increased significantly when
1000 ppm Cu was added to the solution. Adhesion is not a factor with RenoCell®’s carbon
cathodes, which are disposable and allow the lowest residual level of barren gold to be
reached consistently.

Base metals may influence the gold electrowinning process when present in high
concentrations relative to that of gold or when too high overpotentials are applied. Base
metals can adversely affect the EW process in terms of decreased current efficiencies, poor
bullion fineness, and passivation of the cathode surface, and by influencing the morphology
of the plated gold.

Much of these issues and problems are overcome by the RenoCell® electrowinning
technology, by producing discardable tailings and/or making direct electrowinning (DEW)
and its positive features and extensive benefits available to the end user and operator.

RRII-110010-0 13 Renovare International, Inc.

Reaction (3) represents the evolution of hydrogen, which occurs at a significant rate at
potentials more negative than -0.9VSHE when working at pH values above 10.1. The
evolution of hydrogen should be under kinetic control at a significant range of potentials
more negative than -0.96 VSHE and, therefore, may consume a high proportion of the
cathodic current.

The major anodic reaction is the oxidation of water to oxygen, also indicated by Reaction
(2). The reduction reaction of cuprous cyanide (Cu(CN)3 ) to metallic copper is indicated in
Reaction (4). The more negative potential for the reduction of cuprous cyanide to metallic
copper than that for the reduction of aurodicyanide to metallic gold signifies that gold
should plate preferentially to copper at these conditions. However, copper may co-deposit
with gold if high overpotentials are applied, or when the copper concentration is high
relative to that of gold.

2.2 POLARIZATION DIAGRAMS

The kinetics of electrochemical reactions is typically studied by conducting polarization

experiments in which the current required to change the potential of the electrode is
determined. If the potential of the electrode is changed at a continuous rate, so-called
potentiodynamic polarization diagrams are obtained. While it is relatively easy to obtain
polarization data, the interpretation is often difficult, as more than one reaction may
contribute to the currents measured. Thus, it is preferable to first simplify the investigation
of industrial scale systems by characterizing a purer electrolyte and then sequentially
adding species that may contribute to further electrochemical reactions. In this way the
contributions of the individual reactions may be isolated, if it can be assumed that
interaction between the species will be minimal.

2.3 MORPHOLOGY OF THE PLATED GOLD

From an industrial point of view, with conventional EW it is essential to obtain loosely

adherent precipitates that can be easily removed with high pressure water. If this cannot
be achieved, some gold will get locked up inside the conventional electrowinning cells,
which can result in electrowinning being uneconomical. The electrolyte temperature,
current density, and conductivity of the electrolyte have typically proved to be the main
parameters that influence the adhesion of gold precipitates. Co-deposition of base metals,
such as copper, may also have an effect on the morphology and adhesion of the precipitate.

The electrodeposition of gold in industrial electrowinning cells is typically operated under

mass transfer control. Various testing protocols have been developed over the decades to
allow important operational parameters to be investigated and allow more effective cells to
be investigated and compared.

RRII-110010-0 14 Renovare International, Inc.

Synthetic solutions are prepared to simulate plant conditions. For example, the electrolyte
may be prepared by adding 2 % caustic soda together with 0.1 % CN, to simulate
conditions normally encountered in plant practice. Chemical compositions typically ranged
from low to high copper and gold concentrations in order to determine at which
concentrations the influence of copper became problematic. The influence of gold and
copper at various concentrations is typically studied, as is the morphology of the deposited
metal.

A decrease in the rate of gold electrowinning occurs when too-high overpotentials are
applied. This is likely to be due to a decrease in the effective cathode area available for
electrowinning because of the enhanced hydrogen evolution, as well as dislodging of the
gold from the cathode surface due to the increased surface turbulence caused by the
evolution of hydrogen gas. The optimum applied potential in conventional EW proved to be
-1.2 VSSE, since the fastest electrowinning rate was obtained at this potential and a more
loosely adherent precipitate can be expected than for gold plated at an applied potential of
-1.0 VSSE.

2.4 OPERATIONS

Although copper will co-deposit with gold during the electrowinning process, relatively
high-grade gold can still be produced by controlling the potential of the cathode. While the
presence of copper will lead to a decrease in the current efficiency for gold recovery, the
rate at which gold is recovered should remain unaffected if a constant potential is applied.

During the EW of gold from an alkali cyanide electrolyte, the following reactions occur at
the cathode and anode:

Cathode:

a) Au(CN)2- + e- = Au + 2 CN-

b) 2 H2O + 2 e- = H2 + 2 OH-

c) O2 + 2 H2O + 4e- = 4OH-

Anode:

d) 2 H2O = O2 + 4 H+ + 4 e-

Oxygen solubility in a hot eluate (electrolyte) is very low. Consequently, cathodic reaction
(c) should not consume very much current. However, if the eluate linear flow rate is too
high, oxygen generated at the anode may be carried into the cathode. Marsden and House
report that the reduction of oxygen at the cathode can account for up to 50 % of the applied

RRII-110010-0 15 Renovare International, Inc.

current in some EW cells. Under conditions when gold EW from alkali cyanide electrolytes
is mass transport controlled (that is, when the cathode potential is sufficiently negative),
cathodic reaction (b) also occurs and hydrogen is evolved. It can be seen that both
reactions (b) and (c) can generate hydroxide ion resulting in a localized increase in
electrolyte pH at the cathode.

Gold deposition, reaction (a), is electrochemically controlled to a cathode potential of

approximately –1.0V. At more negative cathode potential, the rate of gold reduction is
typically mass transport controlled. Experience indicates that hydrogen evolution and gold
reduction occur together until the limiting current is reached and the rate of gold
deposition becomes mass transport controlled. Above the limiting current, the
predominant reaction at the cathode is the evolution of hydrogen. When electrical energy is
passed through a solution containing a metal salt, deposition of metal at an electrode will
occur. The mass of metal deposited is dependent on the quantity of electrical energy passed
through the solution. The quantity of electrical energy applied is measured in coulombs,
where one coulomb is equal to one amp flowing for one second.

Assuming perfect current efficiency, the mass of metal deposited can be calculated using:

M = (I x t x A) / (Z x F)

where M = mass of metal (grams)

I = current (amps)

t = time (seconds)

A = atomic mass of the metal

Z = metal valence in solution

F = Faraday’s constant (96,500 coulombs)

In the case of gold, this formula indicates that the passage of 96,500 ampere seconds of
electrical energy should result in the deposition of 197 g of gold. However, the generation
of hydroxide ions, evolution of hydrogen, and reduction of other metals (such as Ag and Cu)
that also occur at the cathode, consume most of the current applied. To take account of this
inefficiency of the system, the term current efficiency (CE) is introduced. Data reported by
Costello indicates that CE decreases as gold concentration in the eluate decreases. Based on
operating plant data, Costello estimates that CE in a typical gold conventional EW cell is
equal to approximately 15 % of the mean eluate gold grade. However, it is important to
note that CE is also a function of current density. If the current density is too high, the CE
will be poor regardless of the electrolyte gold concentration. In Australia, the current
required by a gold EW system is generally calculated assuming an average CE in the range

RRII-110010-0 16 Renovare International, Inc.

8-12.5%. Corresponding values for RenoCell® are much higher and levels unreachable
(<0.5mg/l and sometimes depending on system design <.02mg/l).

As noted in previously, the silver cyanide complex is more electropositive than gold.
Consequently, it is reduced at the cathode in preference to gold during conventional EW. CE
for silver deposition is generally assumed to be approximately 20%. RenoCell® is more
efficient and also allows selective EW.

2.5 MINTEK EW CELL

The design of most EW cells used in the gold mining industry around the world has been
derived from the Mintek cell. The Mintek cell is rectangular and consists of a series of
alternately-placed anodes and cathodes arranged parallel to each other. In this type of cell,
the direction of eluate flow is parallel to the direction of current flow. Typically, the anodes
used are fabricated from stainless steel wire mesh or punched plate. The cathodes consist
of a porous packed bed of very fine mild steel wire, or wool made by winding the steel wool
around a cathode. Layers of woven stainless steel wire are also used as cathode material.
Packed cathodes of steel wool or stainless steel wire provide a very high cathode surface
area while maintaining good cathode porosity (trying to get improved performance like
that reached by the RenoCell®).

In Mintek-type cells, the potential drop that occurs across the cathode bed limits its
thickness. The rate at which the potential falls as the distance from the anode increases is
dependent on the conductivity of the electrolyte. As the potential falls, the rate of gold
reduction at the cathode surface moves from mass transport control to electrochemical
(kinetic) control. If the cathode bed is too thick, the potential continues to fall until gold
deposition stops and electrical bypassing occurs. Paul et al have noted that in the range –
1.0V to –1.3V, the deposition rate is determined by the electrode potential, while at
potentials more negative than –1.3V, the rate is mass transport controlled.

A cathode is at its most electronegative on the two sides that face an anode. In these
regions, the rate of gold reduction is mass transport controlled while in the other regions of
this type of cathode, the rate of reduction is electrochemically controlled and in some parts
of these regions, deposition does not occur. To ensure the region of mass transport control
is maximized, the thickness of most packed bed cathodes is limited to between four and six
centimeters. It is worth noting that there is a cathodic shift in the equilibrium potential for
gold deposition of –0.12V for every tenfold decrease in gold concentration in the eluate. As
a result, as gold concentration in the eluate decreases, an increasing proportion of the
cathode becomes inactive for the reduction of aurocyanide ions to metallic gold in the
Mintek-type cell.

RRII-110010-0 17 Renovare International, Inc.

2.6 SINGLE PASS OPERATIONS

For a gold EW cell utilizing packed bed cathodes, the cell design revolves around single
pass extraction, E. Single pass extraction is defined as the fraction of an electroactive
species removed from the eluate in a single pass through an EW cell. Single pass extraction
is defined as:

E= 1 – cout / cin = 1 – exp (-L/λ)

where cout and cin are the concentrations of the electroactive species entering and leaving a
conventional EW cell respectively, L is the total length of packed bed cathode, and λ is
known as the characteristic length.

The calculation of characteristic length (λ) that is dependent on the cathode surface area,
the diffusion coefficient of aurocyanide, eluate linear flow rate, diffusion layer thickness,
and voidage in the packed bed cathode. The characteristic length can be determined
experimentally and varies proportionally with eluate linear flow velocity (u) and the
thickness of the diffusion layer (δ) at the electrode surface. The value of δ is inversely
proportional to the linear flow velocity raised to some power. As a result the value of the
characteristic length can be expressed according to the equation λ = kux where k, the mass
transfer coefficient, is a constant. The value of the power, x, has been reported by various
sources as having a value between 0.5 and 0.65. By assuming:

• Constant void space in the cathode bed,

• Constant cathode surface area, and
• An eluate flow rate approaching the practical flow limit (approximately 400
L/m2/min).

Paul has calculated a typical characteristic length to be approximately 31cm. From a

practical viewpoint, it is important to note that characteristic length increases with the
square root of the flow rate (approximately). The RenoCell® performance is optimized for
low concentrations, which are expected from DEW from gold heap operation or other low
concentration operation that allow single pass operations.

The reader is directed to the original Bulletin 2 to address the calculations and in depth
discussion of optimization of convention EW and the various aspects of design of carbon
systems and elution technology, none of which is required with RenoCell® EW technology.

RRII-110010-0 18 Renovare International, Inc.

3.0 RENOCELL®

3.1 INTRODUCTION AND BACKGROUND

A number of established techniques are available for the treatment of process and
wastewater streams containing metal ions, including: electrodeposition, precipitation, ion
exchange, adsorption and reverse osmosis. These methods have the disadvantages of the
need for additional treatment technology to meet today’s process water specifications and
effluent discharge limits, and/or they produce a secondary effluent consisting of a more
concentrated metal bearing solution or a mixed solid that requires further treatment, and
they have high operational cost and complexity.

The technique of electrodeposition manifested in the RenoCell®6 technology can recover

elemental metal directly from aqueous solution over a very wide range of metal ion
concentration. In many cases, such as high value metals (e.g., Co, Ni) and precious metals
(e.g., Au, Pt, Ag), this can allow the metal to be directly recycled. When the intrinsic toxicity
of the metal (e.g., Cd, Hg) is the problem, removal of the metal from the waste stream in a
single stage process is usually the most cost-effective solution. Where appropriate,
electrochemical methods can also be used in conjunction with the other techniques to treat
their secondary waste streams. A typical example is using RenoCell® to remove metal ions
from ion exchange regenerant wastes allowing its reuse or neutralization and discharge.

3.2 PRINCIPLES OF OPERATION

Electrodeposition of a metal occurs at the cathode of an electrochemical cell while oxygen

is produced at the anode due to the oxidation of water according to the following general
reaction scheme (where M is a heavy or precious metal):

The performance of conventional electrochemical cells is limited at low metal ion

concentrations. These devices are usually based upon metal plate or mesh cathodes in a
tank with some means of mass transfer enhancement, e.g., by moving the electrodes or by
achieving very turbulent solution flow. While this approach can be effective down to metal
ion concentration levels of around 250 - 50 mg/L (often expressed as ppm, 1 ppm = 1
mg/L), effluent discharge limits are typically less than 5 mg/L and often below 1
mg/L(precious metals). Thus additional treatment would be required.

This problem has been addressed by Renovare by use of a patented electrochemical cell
technology known as RenoCell® (see Figure 1). The RenoCell® design, for the first time,

6 RenoCell® is Renovare’s registered trademarked name for the patented electrochemical deposition
technology known as Porocell. Applicable U.S. patents include 5,690,806 and 6,162,333.

RRII-110010-0 19 Renovare International, Inc.

allows effective use of three-dimensional (3-D) cathode materials, in most cases a porous,
carbon or graphite element 7, via the flow path and current distribution embodied in the
patent. The use of a 3-D cathode greatly enhances the performance of the cell since the
carbon fiber element (~1000m2/g surface area) has a much larger effective surface area
than a two-dimensional (2-D) electrode of the same nominal size. The design of the
RenoCell® makes this very high surface area available for metal deposition at higher
current efficiencies, lower current densities and higher deposition rates for a given nominal
cell size than conventional cells with 2-D cathodes. The net result is that RenoCell® can
achieve lower final metal ion concentrations while using less energy to remove a given
amount of metal from a dilute metal-ion bearing solution. In general, RenoCell® is capable
of a factor of 100 to 1000 lower final concentration of metal ions, and three to 10+ times
higher energy efficiency than other commercial electrochemical cells.

The standard RenoCell® is constructed of high performance plastic that is mounted

vertically to assure electrolyzed gases escape with effluent solution discharge. The
RenoCell® can be mounted on a frame attached to a wall or a skid support structure, or
within a cabinet housing.

The standard RenoCell® Model 500 for industrial applications consists of a cylindrical
cathode enclosed in a 0.5m long polypropylene housing. The area of the cathode in this
device, on a 2-dimensional basis, is approximately 0.1 m2 while the actual plating area is at
least 50 m2. For certain applications, a variation of the standard Model 500 is used—the
“divided” Model 500/D, which has a hydroscopic membrane (normally a cation-exchange
membrane) positioned concentrically between the cathode and the anode. In this case, two
electrolyte solutions, anolyte and catholyte, and consequent dual solution storage,
circulation and control systems, are required. In most situations, the anolyte will consist of
a small volume of compatible acid or salt solution. The divided cell system is applied to
solutions containing chemical reactants that can be adversely oxidized at the anode or that
would interfere with the cathodic deposition process, e.g., chlorine gas formation from
chloride solution.

When the carbon element cathode is completely plated with metal to the point of reducing
or blocking flow through the cell, as indicated by high pressure drop (typically about 0.7
bar) across the catholyte side of the cell, the cathode must be replaced. The spent cathode
is removed from the RenoCell® by switching off the power supply and pumps, draining the
cell of all fluids, disconnecting the outlet pipe or hose, removing the top end plate, and then
extracting the metal-laden cathode cartridge assembly. A new cathode cartridge assembly

7 Other porous materials are utilized for special applications.

RRII-110010-0 20 Renovare International, Inc.

is then inserted into its locating position within the cell, the end plate, outlet hose and
current feed connections re-attached, and the cell is ready for operation.

Post Electrode
Connector

Cathode
Current Feeder
Anode
Plastic
Outer Support

Carbon Fiber
Plating Element

Anode

DIN: DRII-6002-1 Porous diffuser core

Electrolyte Flow Path

Figure 1: Schematic cross-section of standard RenoCell® (undivided)

The metal can be recovered from the cathode cartridge by removing the metal-laden
carbon element and direct recovery in a furnace. The carbon is consumed in the furnace
leaving only metal, and actually improves the quality of the melt by scavenging oxygen or
other constituents that would otherwise reduce the final metal quality. As an alternate
recovery methodology, the recovered metal can be re-dissolved anodically or chemically as
a concentrated solution for: 1) recycling to the source process; 2) re-plating in a plate and
frame type tank cell as a metal foil or sheet; or 3) precipitated as a salt. The cathode
support and current feeder assembly can then be quickly refitted with a new carbon
element and readied for reuse in subsequent cathode change-outs.

RRII-110010-0 21 Renovare International, Inc.

4.0 DIRECT ELECTROWINNING (DEW)

Direct electrowinning of precious metals directly from dilute (0.5 – 10 ppm Au) pregnant
leach solutions. RenoCell® advanced electrowinning technology makes it commercially
practical to directly electrowin precious metals from these mining and process solutions by
providing significantly higher Faraday current efficiencies to recover precious metals
concentrations to 0.1 ppm and below. The RenoCell’s® patented design enables effective
use of very high surface area three-dimensional (3-D) cathode materials. This unique
design enables the economic recovery of gold, silver, and platinum group metals by direct
electrowinning to below 0.1 ppm, often to less than 0.01 ppm, by providing:

• Porous cathode with very high active surface area,

• Replaceable cathode cartridge for easy metal recovery,

• Industry standard components in a compact, robust design,

• Optional divided cell configuration where required, and

• Significantly improved performance applicable to all electroplatable metals or

electroprecipitable metal hydroxides and oxides.
RenoCells®, commercially used since 1998, are used successfully by the electronics, metal
plating, and metal recovery industries in process and wastewater management
applications. RenoCell® improves process quality and economics, and can meet metal
effluent release limits in a single step. Base metals such as copper, cadmium, lead, tin, and
zinc, and precious metals including gold, silver, palladium, platinum, and rhodium, in
various leach or process electrolytes are being successfully removed and or recovered,
often to below detection limits. Over 175 RenoCells® are in operation worldwide.

4.1 RENOCELL® PERFORMANCE

RenoCells® have been tested and are operating on a number of high-value metal recovery
applications, primarily in the industrial process industries. The table below summarizes
the recovery performance of the RenoCell® in four of these applications for precious metal
recovery.

Table I: Typical RenoCell® Operating Experience

Initial Final
Source Stream Metal
(mg/L) (mg/L)
Cyanide liquor Au 380 < 0.1
Acidic liquors Pt 24 1
(simultaneous recovery) Pd 110 0.01
Acidic liquors Pt 2000 0.5

RRII-110010-0 22 Renovare International, Inc.

 Acidic liquors Pd 500 < 0.5

In 18 test cases at a South African gold mine, the gold concentration in a carbon column
eluant was reduced by the RenoCell® from ~350 mg/L Au to <1.0 mg/L Au in less than 30
minutes, and in most cases in less than 15 minutes. In several tests the end concentration
was reduced to less than 0.1 mg/l, the lower detection limit for the assay method
employed. By comparison, the recycle time in the existing electrolytic cells was about 12
hours with the terminal gold concentration about 16 mg/L.

Table J: South African Gold Mine Carbon Column Gold Elute Test Solution
Time (min.) Au (mg/L) pH

0 331 12.5

5 144 12.4

10 17.5 12.5

15 0.3 12.5

31 0.2 12.6

45 < 0.1 12.6

Overall current efficiency from 331 to 0.1 ppm was 13.3%.

Tests were also conducted on a printed circuit board line where a RenoCell® system was
installed to recover gold from gold tab plating baths. The results of one test are shown
below, and the photo shows gold deposited on the RenoCell® Model M100 cathode carbon
element.

Table K: Gold Recovery from Process Solutions

Time (min.) Au (mg/L) CN-

(mg/L)
0 480 150
15 24 69
25 0.8 60
35 0.5 55

Overall current efficiency from 480 to 0.8 ppm is 10.5% in 25 min.

RRII-110010-0 23 Renovare International, Inc.

Also note the rapid CN destruction via oxidation at the anode in an undivided RenoCell®
(see Figure 2).

Figure 2: Loaded cathode

The RenoCell® attains major performance improvements through effective use of a unique
3D cathode design, including:

• High active cathode surface area produces compact design and efficient conversions
even at low metal concentrations,
• High current efficiency to minimize energy use,
• High current density to allow rapid metal recovery,
• Ease of product removal,
• Safety and ease of control, and
• Lower operating and capital costs.

4.2 RENOCELL® DEW CASE STUDY

In a recent DEW Case Study with an Australian engineering firm for an Indonesian CN heap
leach gold mining project, a series of performance and cost studies were conducted for a
planned heap operation with the recovery of gold from ~2 ppm to 0.1 ppm at a flow rate of
100m3/hr.

The performance study revealed that this plant capacity could be provided by 24 Model
M1000-SP (single-pass) RenoCells® operating at a flow rate of 70 liters per minute (Lpm)
each. Each cell will operate at a current density (CD) of 150A/m2 and voltage of ~10V.
The 24 cells would be configured in modules of 6 (4 groups) and each module of 6

RRII-110010-0 24 Renovare International, Inc.

RenoCell’s® cathodes would be changed every four days. Each cathode would contain four
operating days of gold recovery or ~18.2 kg at 3 kg per cell.

The capital and operating cost evaluation for three alternative recovery processes was
carried out for the project. This included Case A - Carbon-In-Pulp (CIP), Case B - Carbon-In-
Leach (CIL) and Case C - RenoCell® Direct electrowinning (DEW). The CIP and CIL activated
carbon processes both included activated carbon adsorption, elution, goldroom, carbon
regeneration, detox unit process operations, as well as working capital, etc. as required for
each type of recovery plant. The Capex were within 20% of each other, while the Operating
Costs were A - $9/Toz, B - $15/TOz and C - $2.50/TOz.

Typical RenoCell® gold recovery rates in grams/day for metal concentrations ranging from
1 to 12 mg/l (= ppm) are shown below based upon an analysis of RenoCell® performance
achieved during gold recovery tests conducted in South Africa using a RenoCell® bench
scale system. For gold concentrations of 0.5 ppm, the M1000-SP is expected to recover
about 40 g/day of gold based upon a 70 Lpm flow rate.

4.3 SOUTH AFRICAN GOLD RECOVERY TESTS

Recovery of Au from CN heap leach carbon column elute at a South African mine was
evaluated using a RenoCell® bench scale system. The test series were conducted at 1 and 2
Lpm flow rates and 150 and 225 A/m2 current densities. The results of 10 of these test

RRII-110010-0 25 Renovare International, Inc.

runs plotted as Incremental Current Efficiency versus Au Concentration in ppm are plotted
below and show a consistent performance range for the RenoCell®, recovering from 300 to
less than 1 ppm, at times to 0.1 ppm, in all cases with practical recovery efficiencies. The
incremental current efficiencies (ICE) plotted are equivalent to what can be expected in
single pass operations at concentrations below 6 – 10 ppm, and show CE values as high as
10% at 3 ppm and 0.1% at 0.1 ppm.

These tests also showed, as expected, somewhat better performance at the higher flow rate
of 2 Lpm (orange curves) versus the lower 1 Lpm (black curves). It should also be noted
that the 0.1 ppm end point is not necessarily representative of the RenoCell’s® capabilities
but rather the lower detection limit for the analytical method and AA mass spectrometer
instrument used for analysis of the test samples. Overall current efficiencies (not shown)
ranged from 5% to 10%, over the recovery range of 300 to less than 1 ppm.

4.4 RENOCELL® PGM RECOVERY TEST

A test program to determine RenoCell® recovery performance for a mixed Pt, Pd and Rh
source stream resulting from the acid leach of scrapped automotive exhaust gas catalysts

RRII-110010-0 26 Renovare International, Inc.

was conducted using a RenoCell® bench scale test system. The test recovered 111.03 grams
of material, assuming PGMs 8, into the cathode. The cathode became quite stiff and
noticeably heavier. The test solution, 40.7 gal., was contained in a 55 gallon drum. A
MasterFlex pump delivered solution from the drum into the cathode feed tank of the bench
system, and then the hose drain on the back of the bench unit was used to allow catholyte
to return to the drum by gravity. The flow rate was about 1 liter/min to and from the drum
to the catholyte tank of the bench system. The pump recirculation rate for the cathode side
was 6 liters/min during the entire test. The anode side was maintained at 3 liters/min.

Pt Rh Pd Totals

Grams in Solution at Start 41.14 (267 ppm) 3.48 (22.6 ppm) 32.51 (211 ppm) 77.13

Grams in Solution at End 5.25 (34.1 ppm) 1.12 (7.3 ppm) 0.02 (0.13 ppm) 6.40

Grams Platted 35.89 2.36 32.49 70.73

% Platted 87.23 67.68 99.94 91.71

Figure 3: Comparison photograph of new cathode (left) and PGM-loaded cathode

(right)

The electrolysis was run for 66 hours in constant current mode since there were no known
other metals in solution. The current was set and maintained at 7.75 amps and voltage
varied from a starting voltage of 2.27 to a 2.97 ending voltage. The electrolysis was run
over a period of about 2 weeks at 8 hrs per day. It was not run during the night or
weekends. The cell was drained each night and the cathode was rinsed in DI water and set
aside till the following morning where it was reinstalled into the unit and exposed to
electrolysis.

8 Other metals: Pb = 12.9% wt/wt, Cu = 4.52% wt/wt, unknown source – believed to have been in water
source used in the leach chemistry.

RRII-110010-0 27 Renovare International, Inc.

For comparison, the use of sodium borohydride (SBH) precipitation in the existing
production environment resulted in the recovery of 88% of Pt, 100% of Pd, and 34% of Rh
from the leach solution. SBH is being replaced in the expanded production environment by
EW using RenoCell® technology due to its equal or better recovery, much simpler and
cleaner operations, and substantially lower operating costs. It should also be noted that the
EW tests were not carried to completion but rather terminated for convenience. EW
operations 24/7 and process optimization is expected to result in significantly improved
performance with recovery in the ppb level for all metals.

5.0 ‘GREENER’ ALTERNATIVE LIXIVIANTS

It was reported by Marsden (2006) that agitated cyanide leaching accounted for
approximately 50% to 55% of gold extraction around the world. But pressure to ban or
limit the operation of cyanidation is increasing due to a negative public perception about
the environmental impact of the cyanide toxicity. An increase in the research into
alternative lixiviants has increased in last few decades. The alternative lixiviants include
thiourea, chlorine, bromine, iodine, and thiosulfate, among others.

In recent years thiourea has attracted considerable attention in hydrometallurgy of the

precious metals, primarily gold. One of the reasons is the kinetic superiority of thiourea
leaching compared to cyanide leaching. Another is thiourea’s substantially less toxic nature
compared to cyanide. Thus, thiourea may very well be used as a ‘greener’, more
environmentally-sound substitute for cyanide in many hydrometallurgical applications. To
recover gold and other PMs from precious metal-bearing materials including ores, leaching
residues, flue dust, electronic scrap, jewelry scrap, etc., the gold and other PMs can be
extracted from the precious metal-bearing materials with a thiourea solution to form a
thiourea leach; the thiourea leach is then contacted with carbon to adsorb the gold and
provide loaded carbon.

The use of thiourea as an alternative non-polluting reagent for gold leaching is very well
known. The recovery process for removing precious metals from precious metal-bearing
mixtures, such as silver-containing and gold-containing ores, commonly included crushing
the ore, washing or frothing the crushed ore to eliminate clays and other contaminants, and
then solubilizing the ore in an aqueous cyanide solution, an aqueous thiourea solution, an
aqueous ammonium thiosulfate solution, or aqua regia. Thereafter, these solubilized
(dissolved) precious metal-bearing solutions can be treated for recovery of the precious
metals through methods such as carbon absorption, carbon-in-pulp absorption/desorption,
amalgamation, ion exchange, electrowinning, or precipitation. However, the processes of
gold recovering from thiourea solutions, particularly the electrowinning (EW) process,
have received little attention.

RRII-110010-0 28 Renovare International, Inc.

Gold EW from thiourea solutions has been studied by others based upon standard EW
techniques. For potentials more cathodic than 0 mV vs. SCE, gold reduction is typically
mass transport-controlled and limited with standard EW. The estimated diffusion
coefficient for the complex gold (I)-thiourea at 25°C was 1.0 × 10−5, cm2s−1. Passivation
due to thiourea adsorption on the electrode surface was observed at −300mV vs. SCE.
Experiments show that gold reduction is favored by low thiourea and formamidine
disulfide concentrations, and, thus, RenoCell® would be expected to perform better.
Measurements indicated the presence of an adsorption step before the reduction of the
complex gold (I) -thiourea, although the reduction of the species in solution is also feasible.
This type of condition is often found with complex chemistry matrices such as Electroless
Ni, and RenoCell® has been successfully employed. The influence of Current Density on the
cathodic Current Efficiency and gold structure may be an issue. The influence of gold,
thiourea and formamidine disulfide concentrations on the cathodic behavior of gold is the
unknown with the RenoCell® (we need the Divided RenoCell®), but like other RenoCell®
applications, the fact that other forms of EW have been successful, even with inadequate
results, has always shown that the RenoCell® will perform better. This is especially the case
for the more primitive forms of EW typically used to date for precious metals recovery.

For example, laboratory investigations by others on the kinetics of gold EW from acidic
thiourea solutions obtained by gold elution from activated carbon in the processing of gold-
bearing raw materials have been carried out as depending on temperature, current density,
and the type of cathode material. It has been found that a high gold recovery could be
obtained under suitable conditions, 45 mg/L Au in 6 g/L thiourea (especially at elevated
temperature of 60C). The current efficiencies were as high as 0.5% to 1%, and the energy
consumption can be less than 15 kW h kg−1 of gold using a platinum mesh cathode. Our
expectations for RenoCell® would be essentially ~100% gold recovery, and CE 10-30 times
greater with no Pt cathode.

The step of contacting a loaded thiourea carbon bed with an alkaline solution of the
thiousulfate ion with the loaded thiourea carbon involves desorbing the PMs from the
carbon (thiourea apparently does not desorb loaded carbon.) An additional step often
includes adding a salt to the aqueous thiousulfate solution; this includes protecting the
thiousulfate ion from any oxidizing agents and is done by adding a reducing agent such as
sodium sulfite to the thiousulfate solution.

When copper is present, removing the copper from the carbon is required prior to exposing
the carbon to the thiourea solution containing the precious metal.

The hydrometallurgy techniques using thiourea share similarities to the already well
known cyanidation techniques. In other words, thiourea can be used in similar types of unit
operations that are used with cyanide as noted above. However, a significant difference

RRII-110010-0 29 Renovare International, Inc.

between thiourea and cyanide leaching techniques is the pH of the leach solutions that are
used. Cyanide must be used in basic solutions to prevent evolution of toxic gaseous
hydrogen cyanide. In contrast, thiourea is used in acidified solutions. The main unit
operations are similar in a thiourea leaching method. In general, there has been very little
work done on the elution of gold from activated carbon where the precious metals are
loaded from thiourea solutions. We would expect to direct electrowin Au from the thiourea
leach with the RenoCell® and bypass the use and recovery from carbon steps-all expensive
and time consuming steps.

Au can be electrodeposited from acidic thiourea (and potentially thiocyanate and, of

course, thiosulfate) solutions; however, a divided EW cell (such as the Divided RenoCell®)
is required to avoid excess oxidation of the reagents at the anode as well as other
deleterious reactions at the cathode in a standard EW cell involving sulfur species which
may contaminate the solution and impact CE.

Even in the process of cyanidation of gold, the elution step has serious deficiencies,
primarily with respect to kinetics. The elution of gold from a cyanide solution can last from
10 hours to 4 days. The reason for the slow elution rate of the cyanide metal complexes is
the strong adsorption of gold cyanide complexes on activated carbon.

For example, a complex desorption process was reported in the literature wherein
thiosulfate ion was employed for desorbing silver from carbon loaded from a cyanide
solution. The first desorption step employs alkaline thiosulfate solution, and the silver is
preferentially desorbed by three alkaline thiosulfate elutions leaving essentially all of the
gold on the carbon. The gold is then desorbed by a second desorbing solution comprised of
alkaline sodium cyanide. Although the principles described primarily in the context of
recovering precious metals from raw materials which bear precious metals, it is
understood that the same principles can be applied to the separation and recovery of
precious metals generally.

More specifically, a thiosulfate elution step has been applied to the recovery of gold and
silver from carbon loaded with a thiourea leach. Apparently, thiourea derivatives, instead
of or in conjunction with generic thiourea, have also been explored. It is apparently
expected that such thiourea derivatives would be used if they became less expensive and
more readily available in the future. The important characteristics of the thiourea
derivatives are that they dissolve both gold and other PMs in a precious metal-bearing
material in an acidified solution and that they load carbon with gold and silver complexes
that are leachable by thiosulfate. Some referenced thiourea derivatives include: N-
methylthiourea, N-ethylthiourea, N-isopropylthiourea, N-(n-butyl)-thiourea, N-
phenylthiourea, N-benzylthiourea, N-naphthylthiourea, N-tolylthiourea, N-(o-
chlorophenyl)-thiourea, N-(p-hydroxyphenyl)-thiourea, N-(p-ethoxyphenyl)-thiourea, N-

RRII-110010-0 30 Renovare International, Inc.

(2,4-dimethylphenyl)-thiourea, N-acetylthiourea, N-benzoylthiourea, N,N-
dimethylthiourea, N,N-diethylthiourea, N,N-dipropylthiourea, s-dimethylthiourea, s-
diisopropylthiourea, s-di-n-butylthiourea, s-diphenylthiourea, s-ditolylthiourea, N,N-
phenyltolylthiourea, N,N,N’-trimethylthiourea, N,N,N’-triethylthiourea, and N,N,N’-
tripropylthiourea, among others.

The particular acid that is used for acidifying the thiourea is not critical; for example,
sulfuric acid, hydrochloric acid, and nitric acid can be used and sulfuric would probably be
preferable. This method for recovering is for such precious metals as gold, silver,
palladium, platinum and rhodium from precious metal-bearing mixtures such as ores and
tailings.

The affinity of activated carbon towards all other gold complexes is different. The
effectiveness of activated carbon in removing gold complexes from aqueous solutions
decrease in the following ligand order: SCN->SC(NH2)2>CN->> S2O32-. The gold thiosulfate
complex has the lowest affinity to adsorb on the activated carbon, 15% to 17% gold
recovery. Yen et al. (2002) reported that gold recovery from the thiosulfate solution was
less than 20% when using 20 g/L or 40 g/L activated carbon. It requires 60 g/L carbon to
recovery 95% gold with the loading of less than 2 mg Au/g, which is not feasible in the
practical operation.

Gold thiosulfate complex differs from gold cyanide complex, which is easily adsorbed on
activated carbon while gold thiosulfate complex cannot be satisfactorily recovered by
activated carbon. However, gold thiosulfate could be recovered by activated carbon if
cyanide is added into the thiosulfate solution. Thus, the potential of direct electrowinning
with the RenoCell® would greatly reduce the complexity and potential of this greener
leach technology.

Aurothiosulfate ions in the leach solution will migrate to the cathode and form a metallic
gold deposit. The electroreduction of gold thiosulfate to gold is kinetically faster than the
reduction of gold cyanide to gold; gold thiosulfate is reduced at -0.15 V vs SCE and is
independent of pH for values of above 4. However the standard EW is especially
problematic in the presence of a great excess of unwanted cupric and cuprous ions. Also,
the oxidation and reduction reactions of S2O32- occur at the anode and cathode surfaces as
noted previously. Therefore, a standard EW process does not appear to be an attractive
option for gold recovery. The RenoCell®, especially the Divided cell configuration,
eliminates or reduces many of these issues and should allow direct electrowinning to be
performed with substantial benefit in complexity and cost factors.

One alternative involves liquid-solid separation, in which the gold is recoverable by metal
cementation or solvent extraction processes. At Zn/Au ratio of 30, 100% of gold is
recovered and the barren solution can be recycled. The choice of solvent to extract gold is

RRII-110010-0 31 Renovare International, Inc.

esters, amines and the like. Ion exchange process can then extract the gold from either
slurry or clear solution with strongly base anion resins. The gold can be recovered from the
eluted solution by electrowinning or metal precipitation. Clearly, such complexity will
nearly kill all projects either because of risks or high costs.

6.0 CONCLUSION

As operations strive to lower gold production costs, ore throughput and head grade are
typically increased to limits imposed by the nature of the ore body and the capacity of plant
equipment. Unless matched by an increase in the rate of gold removal, increased gold input
results in elevated carbon loadings and a flattening of the carbon loading profile through
the adsorption circuit. Ultimately, soluble gold losses tend to increase. To control soluble
gold losses it is necessary to increase the rate of carbon advance through the adsorption
and stripping circuits. It is not uncommon to find electrowinning cycle time dictating
elution frequency.

In this paper, we have attempted to identify and discuss a number of issues that commonly
impact on electrowinning efficiency. Our aim is to identify a new technology and improved
EW cell that reduces the need for carbon and allows the promise of direct electrowinning
(DEW) to be realized and reduce the cost of processing and extraction.

When the conditions are chosen so that the reduction of gold to gold metal is mass
transport controlled over all the surface of three-dimensional cathode, the current is given
by where the cathode potential is chosen so that the reduction of gold is mass transport
controlled and no other reaction occurs or minimized, (b) the potential distribution is
sufficiently uniform throughout the cathode and (c) the depletion of gold from solution
during a single pass through the cathode is insignificant (except in the Single-pass
RenoCell® 2 option).

It has been shown that it is feasible to electrowin gold from cyanide solutions, even with
low ionic strength, to achieve gold levels below 0.2 ppm with reasonable cell performance
using 3-D carbon cathodes. Furthermore, the power requirements and energy
consumptions for the laboratory cell were low and a further improvement in performance
has been realized with scale-up of the technology.

FOR MORE INFORMATION BE SURE TO VISIT OUR WEB SITE AT:

www.renovare.com

RRII-110010-0 32 Renovare International, Inc.

7. REFERENCES

i. The Chemistry of Gold Extraction; Marsden and House

ii. The Recovery of Gold from Concentrated Aurocyanide Solutions; Paul, Filmer and Nicol

iii. Gold from Eluates; Paul

iv. The Kinetics of the Elution of Gold from Activated Carbon; Adams and Nicol

v. Practical Experience of Gold Electrowinning in Australia; Costello

vi. Experience with the Use of Electrowinning Gold from Pregnant Eluates in the Gold
Mining Industry in Australia; Costello

vii. Actired Process – New Industrially Tested Process which Economically Improves Gold
Elution; Duparque, Louis, Harvey and Van Lierde

viii. Electrometallurgy and Electrochemistry Workshop; Paul, Costello, Ritchie and Spencer

ix. The Electrowinning of Gold from Carbon-In-Pulp Eluates; Filmer

x. A study of the influence of copper on the gold electrowinning process; Steyn and
Sandenbergh

RRII-110010-0 33 Renovare International, Inc.