CURSO DE ACTUALIZACION

INNOVACIONES METALRGICAS EN LA RECUPERACION DE ORO Y

PLATA.
Avances en los mtodos de recuperacin de oro y plata de minerales
refractarios.
Pressure cyanide leaching for precious metals recovery.
Detoxification of cyanide using titanium dioxide and hydrocyclone
sparger with chlorine dioxide.
Estudio cintico de la extraccin de oro de un mineral piritoso mediante
oxidacin y lixiviacin simultnea a presin.
Continuous laboratory gold solvent extraction from cyanide solutions
using LIX 79 reagent.
Enhance cyanide recovery by using air-sparged hydrocyclone.
Estudio de la resina Aurix 100 de intercambio inico para recuperar oro
en las soluciones cianuradas.
Extraccin de oro por solventes en un circuito contino.
Gold solvent extraction from alkaline cyanide solutions, using LIX 79
extractant.
New technology for recovery of gold and silver by pressure cyanidation
leaching and electrocoagulation.
Uso de resina de intercambio inico para la recuperacin del complejo
oro tiosulfato desde soluciones acuosas.
Tostacin de un concentrado refractario de oro y plata.

.
.

Zinc-dust cementation of silver from alkaline cyanide solutions- analysis

of Merril-Crowe plant data.
Kinetic aspect of gold and silver recovery in cementation with zinc power
and electrocoagulation iron process.
Recovery of silver and gold from cyanide solution by magnetic species formed
in the electrocoagulation process.

Aqueous Processing

Research Summary

Pressure Cyanide Leaching for

Precious Metals Recovery
Jos R. Parga, Jess L. Valenzuela, and Francisco Cepeda T.

A novel method demonstrates that the

oxidation and dissolution of gold and
silver in alkaline cyanide solution can
be conducted simultaneously in the same
autoclave in less than 90 minutes with
a recovery that exceeds 96%. Because
mild operating conditions of 80C and
0.6 MPa oxygen pressure are used in this
process, low cost materials of construction can be utilized for the autoclave.
INTRODUCTION
Durango is the second largest goldsilver producing state in Mxico. The
Bacs mine in particular produces a pyrite
concentrate rich in silver and gold.
During the mines short history, efforts
have been made to reduce costs and
increase production through improved
process developments.1,2 At the present
time, cyanidation has superseded all
previous leaching processes, particularly
chlorination,3 because of its ability to
effectively and economically treat ores
containing as little as 13 g/ton gold.
The precious metals are dissolved in a
dilute solution of sodium cyanide, which
is recycled after precipitation of the precious metals with zinc dust. A bleed of
this barren solution is often required to
control the accumulation of deleterious
impurities.
Refractory gold-silver ores contain
precious metals locked up in a matrix of
pyrite and/or arsenopyrite. Such ores are
not amenable to cyanidation. To liberate
the gold-silver from the sulfide matrix
and render it accessible to cyanidation,
it is a common practice to subject them
to a preoxidation in order to enhance the
recovery of the precious metals.4,5
Although effective, these techniques
result in the production of large quantities of environmentally hazardous substances such as SO2 or H2SO4, which can
cause difficulties in compliance with
2007 October JOM

environmental pollution regulations.

After review of the literature,49 it is
clear that of the refractory gold treatment
plants installed during the past 25 years,
pressure oxidation has been the most
popular (see Table I). This process, which
is used in many commercial plants
around the world, involves the recovery
of the precious metals by oxidation
pretreatment followed by traditional
cyanidation. It should be remembered
that the pressure oxidation technology
is not used to leach the gold and silver
but only to make it accessible to the
cyanide in the host mineral.
See the sidebar for experimental procedures.
PROCESS CHEMISTRY AND
LEACHING EXPERIMENTS
Pyrite, arsenopyrite, sphalerite, and
covellite are the most common host
minerals of gold, silver, and electrum. It
is important from a process optimization
standpoint to understand the behavior of

each of these minerals during alkaline

pressure oxidation. This process leads
to dissolution/destruction and subsequent liberation of gold and silver which
would then be available for cyanidation.
Pressure oxidation of pyrite involves
reactions yielding ferrous ion, sulfate
ion, and elemental sulfur as products.10,11
The primary reactions are shown in
Equations 1 and 2. (All equations are
presented in the Equations table on page
46.)
Ferrous ions produced by Equations
1 and 2 are subsequently oxidized to
ferric ions, as shown in Equation 3.
The ferric ions can also contribute to
the oxidation of silver iron sulfide,
argentite, pyrite, pyrrhotite, sphalerite,
and chalcopyrite (see Equations 49,
respectively). The resulting elemental
sulfur may be further oxidized to sulfate
by oxygen or by ferric sulfate, as given
in Equations 10 and 11. This results in
the formation of a porous, but nonprotective, elemental sulfur layer, thus allowing

Figure 1. A schematic of the mechanism of gold and silver leaching.

43

cyanide and dissolved oxygen to access

to the previously locked gold, silver, and
electrum. It was thought that by maintaining high concentrations of CN ions
in the pressure leach reactor it would be
possible to complex gold and silver
(Equation 12) as they became liberated
and thus achieve both objectives (i.e.,
decomposition of refractory minerals
and Au/Ag recovery) in a single stage.
Both gold and silver extractions achieved
were, in fact, greater than 96%. Since
silver in Mexican ores occurs as argentite the cyanidation and sulfide oxidation
reactions are given in Equations 12
through 15.
Sulfide ions are oxidized to thiosulfate
and can contribute with the dissolution
of gold. Also J.S. Graham et al.12 showed
that an alkaline or near-neutral solution
of thiosulfate dissolved gold metal slowly
in the presence of a mild oxidant. The
dissolution of the gold can be written as
in Equation 16, where oxygen is the
oxidant and thiosulfate is the ligand.

Figure 2. A comparison of silver

extraction at ambient conditions
and high pressure. Conditions:
% solids = 20; pH = 11.0; rpm
= 300.

Figure 3. A comparison of gold

extraction at ambient conditions
and high pressure. Conditions:
% solids = 20; pH = 11.0; rpm
= 300.

Better extractions of gold with thiosulfate are achieved when elevated

temperatures (e.g., 65C) are used 13 and
also, cupric ion has been found to have
a strong catalytic effect on the rate of

EXPERIMENTAL PROCEDURES
Mineralogical analysis indicates that the sulfide minerals for the Bacs concentrate
include silver iron sulfide, silver sulfide or argentite, pyrite, pyrrhotite, arsenopyrite,
chalcopyrite, covellite, hematite, and magnetite. The non-opaque minerals are quartz,
calcite, apatite, gypsum, fluorite, and barite. Also, several photomicrographs indicate
occlusion and/or dissemination of micrometer-sized gold, silver, and electrum particles
in the sulfide minerals such as pyrite, sphalerite, arsenopyrite, and quartz (Figure A).
The compositions are listed in Table A.

Table A. Analytical Data for the Composite Samples

g/t

Concentrate
Ore

Percent

Au

Ag

Pb

Zn

Cu

Fe

As

87.09
4.12

12,320
289

2.6
0.5

3.8
0.4

0.5
0.04

29.2
3.67

0.15
0.1

32
3.7

Figure A. A photomicrograph of argentite (ARG)

occluded in pyrite, size
60 Mm.

44

oxidation. The proposed physiochemical

aspects of the leaching reaction mechanism for gold and silver dissolution in
relatively mild operating conditions of
80C and 0.6 MPa oxygen pressure are
illustrated in Figure 1. In this figure, the
ore particle displays different diffusing
ions.
All experiments were conducted in a
4 L Parr autoclave assembled with impeller, thermowell, pressure gauge, gas inlet,
and outlet pipes used for simultaneous
oxidation and cyanidation. Samples were
ground to 84% minus 40 Mm or finer,
and pulped with fresh tap water. Depending on test requirements, variables such
as NaCN, lixiviation time, temperature,
particle diameter, pH, and pulp density
were set and the leaching experiments
were undertaken.
RESULTS AND DISCUSSION
Preliminary batch testing had indicated that at ambient conditions (25C,
1 atm.) direct cyanide leaching of the
concentrate with air gave poor silver and
gold recoveries. The results obtained are
shown in Figures 2 and 3.
Figure 4 shows that there is an optimum leach time to achieve both maximum gold and silver extractions. The
optimum leach time appears to be close
to 60 min. at 80C. Increasing time
beyond this value leads to chemical
degradation of the complex cyanide due
to the hydrogen ions produced by the
sulfide oxidation. Also, for prolonged
leaching time there is a significant loss
in cyanide, since the oxygen present
JOM October 2007

Figure 4. The effect of autoclave retention

time on gold and silver extraction.
Conditions: % solids = 20; pH = 11.0;
pressure = 0.6 MPa rpm = 300; temp.
80C.

Figure 5. The effect of cyanide concentration on gold and silver extraction. Conditions: % solids = 20; pH = 11.0; temp.
80C: rpm = 300; pressure = 0.6 MPa;
leach time 60 min.

oxidizes the cyanide to cyanate and

ultimately, to ammonia and carbon
dioxide.
Sodium cyanide addition appears to
be the critical variable for good recovery.
Concentrations of 0.61.1 wt.% sodium
cyanide were used to leach the concentrate in the autoclave. When the concentration of sodium cyanide was less than
0.6%, gold and silver extraction could
not be completed optimally in a single
stage of autoclave leaching. Increasing
the cyanide concentration resulted in an
increase in the gold and silver extraction.
The results are shown in Figure 5.
The concentrate was leached as 20
wt.% solids slurry with 1 wt.% of NaCN
for 60 min. Temperature was varied from
60C to 200C. As the temperature was
increased, the gold and silver extractions
decreased since at temperatures higher
than 80oC, the oxidation of cyanide ions
is too rapid. This results in the formation
of CO2 gas and ammonium ions (see
Equation 17). In this case, cyanide ions
are not available for complexation, as
shown in Figure 6.
A pH range of 10.513 was examined
for the extraction of gold and silver. In
Figure 7, it can be seen that at a pH of
11.5 or above, optimum extractions could
not be maintained. This is because in
alkaline-oxidizing medium the pyrite
and pyrrhotite in the concentrate compete
with gold and silver for consumption of
oxygen. This mechanism may be responsible for the decrease in extraction, as
shown in Equations 18 and 19. Eventually the ferrous sulfate formed is converted to stable, insoluble ferric hydroxide, as given in Equations 20 and 21.
The decrease in the extraction of gold
and silver with increasing pH may also
be due to a decrease in the formation of
ferric sulfate. Ferric sulfate is the reagent

that contributes to the oxidation of sulfide

minerals which occlude gold and silver.
Also, G.A. Deitz14 found that at pH values
between 12 and 13, the silver surface
became coated with a whitish film of
CaO2 and thus the leaching process was
retarded.
The effect of varying the pulp density
in the range of 1530% solids is shown
in Figure 8. Gold and silver extractions
gradually decreased as the pulp density
increased. This was apparently due to
the increased apparent viscosity of the
slurry, which impedes good oxygen
dispersion in the system, and also due
to the excessive acid generation at high
pulp density. As seen, direct pressure
leaching cyanidation is advantageous
over numerous pressure oxidation plants
for the pretreatment of gold/silver ores

2007 October JOM

Figure 6. The effect of temperature on gold

and silver extraction. Conditions: % solids
= 20; pH = 11.2; pressure 0.6 MPa; rpm =
300; leach time 60 min.

and concentrates. It is faster, requires

lower temperatures and pressures, and
uses a stainless-steel autoclave.
The optimum conditions as delineated
in the laboratory study were: solid 20%;
temperature 80C; pressure 5.6 kg/cm2;
rpm 300; cyanidation time 60 min.;
NaCN 1%; pH 10.7; and PbO 100 g/t.
These conditions were used to study the
extraction of gold and silver during a
continuous one-month plant campaign.
A total of 600 t of concentrate was processed and recoveries for both gold and
silver averaged approximately 96%. The
plant data are shown in Figure 9.
The results described by the pilot tests
were in good agreement with the results
obtained in the laboratory autoclave

Table I. Existing Commercial Plants Using Pressure Oxidation48

Operation Data

Feed

Medium

Capacity
(t/d)

T(oC)

P (MPa)

t (min.)

McLaughlin, California
So Bento, Brazil

Ore
Concentrate

Acid
Acid

2,700
240

180
190

2.76
1.58

90
90

Barrick Mercur, Utah

Getchell Mine, Nevada
Goldstrike, Nevada
Goldstrike, Nevada
Porgera, Papua,
New Guinea
Campbell, Vancouver,

Ore
Ore
Ore
Ore
Concentrate

Alkaline
Acid
Acid
Acid
Acid

790
3,000
1,360
5,450
1,350

225
210
225
225
190

3.26
2.89
3.02
2.75
1.77

70
130
75
75
180

Concentrate

Acid

70

195

2.10

120

Ore
Ore
Ore

Acid
Acid
Acid

2,000
11,580
4,000

220
200
225

3.10
1.37
3.17

100
140
50

Ore

Acid

1,000

120

0.62

60

Concentrate

Acid

2,700

190

1.72

150

Plant Location

Barrick, Toronto
Goldstrike, Nevada
Santa Fe Pacific Gold,
Nevada
Sunshine Mining Co.,
Idaho
Porgera, Papua,
New Guinea

45

Figure 8. The
effect of percent solids in
the extraction
of gold and
silver. Conditions: pressure
0.6 MPa; pH =
11.2; rpm =
300; leach
time 60 min.;
temp. = 80C;
NaCN = 1%.

Figure 7. The
effect of pH on
gold and silver
extraction.
Conditions: %
solids = 20;
pressure = 0.6
MPa; rpm =
300; leach
time 60 min.;
temp. = 80C;
NaCN = 1%.

with low temperature and low pressure.

Under these conditions, less expensive
autoclaves can be used. K.G. Thomas
found15 that a 1,400 t/d acid pressure

oxidation circuit might cost $30 million while the corresponding non-acid
circuit might have a price of only $15
million.

Equations

46

2FeS2 + 7O2 + 2H2O m 2Fe2+ + 4SO42 + 4H+

(1)

FeS2 + 2H+ m Fe2+ + H2S + S0

(2)

2Fe2+ + 1/2O2 + 2H+ m 2Fe3+ + H2O

(3)

AgFe2S3 + Fe3+ m Ag+ + 3Fe2+ + 2S2 + S0

(4)

Ag2S + 2Fe3+ m 2Ag+ + 2Fe2+ + S0

(5)

FeS2 + 8Fe3+ + 4H2O m 9Fe2+ + 8H+ + S0 + SO42

(6)

Fe7S8 + 32H2O + 62Fe3+ m 69Fe2+ + 64H+ + 8SO42

(7)

ZnS + 2Fe3+ m Zn2+ + 2Fe2+ + S0

(8)

CuFeS2 + 4Fe3+ m Cu2+ + 5Fe2+ + 2S0

(9)

2S0 + 3O2 + 2H2O m 4H+ + 2SO42

(10)

S0 + 6Fe3+ + 4H2O m 6Fe2+ + 8H+ + SO42

(11)

Ag2S + 4CN m 2Ag(CN)2 + S2

(12)

S2 + CN + 1/2O2 + H2O m SCN + 2OH

(13)

2S2 + 2O2 + H2O m S2O32 + 2OH

(14)

S2O32 + 2OH + 2O2 m 2SO42 + H2O

(15)

4 Au + 8S2O32 + O2 + 2H2O m 4[Au(S2O3)2]3 + 4OH

(16)

CNO + H2O + 2H+ m CO2 + NH4+

(17)

2FeS2 + 7O2 + 2H2O m 2Fe2+ + 4H+ + 4SO42

(18)

FeS + 2O2 m Fe2+ + SO42

(19)

FeSO4 + Ca(OH)2 m Fe(OH)2 + CaSO4 n

(20)

2Fe(OH)2 + 1/2O2 + H2O m 2Fe(OH)3 n

(21)

Zn + 4CN + 1/2O2 + H2O m Zn(CN)42 + 2OH

(22)

2Au(CN)2 + Zn m 2Au + Zn(CN)42

(23)

Zn + 2H2O + 2Au(CN)2 m 2Au + HZnO2 + 3H+ + 4CN

(24)

RECOVERY OF PRECIOUS
METALS
The cementation of gold and silver by
zinc dust is an electrochemical process,
proceeding by localized anodic and
cathodic reactions. The main reactions
for zinc dissolution are given in Equations 2224.
The MerrillCrowe process is preferred for a very rich pregnant solution
or solutions containing large amounts of
silver.16 Powered zinc is added to the
clarified, deaerated, pregnant cyanide
solution. The zinc particles with gold
and silver are removed from the solution
using a plate and frame filter press. The
mean chemical analysis of the pregnant
solution from plant testing found 0.26
g/t CN; 91 ppm silver, and 0.9 ppm gold.
For both gold and silver cyanide ions,
the recovery by cementation was
99.5%.
CONCLUSIONS
The described study shows that gold
and silver values are associated with
silver iron sulfide, argentite, pyrite, pyrrhotite, sphalerite, and chalcopyrite in
the Bacs concentrate. The dissolution
of gold and silver is due to the strong
complexing capabilities of cyanide
anions combined with the oxidizing
properties of the dissolved molecular
oxygen. The kinetics of the direct pressure oxidation/cyanidation was found to
be strongly dependent on particle size,
concentration of sodium cyanide, temperature, and pH. Single-stage direct
pressure oxidation/cyanidation has
proven to be effective in treating pyrite
refractory gold and silver concentrates
from Bacs mining. For both gold and
silver it was found that the precious
metals recovery exceeded 96%.
JOM October 2007

Figure 9. The results of continuous plant operation.

The relatively mild operating conditions of 80C and 0.6 MPa oxygen pressure offer distinct advantages. For
example, low cost materials of construction can be utilized for the autoclave.
Finally in this process, there is obviously
lower gold and silver inventory.
ACKNOWLEDGEMENTS
The author thanks the management
of Bacs Mining S.A. and CONACYT for
support and permission to publish this
paper. Appreciation is also extended to
Prof. Jan D. Miller of the University of
Utah for his interest in this research.
References
1. J.R. Parga and H. Mercado, Precious Metals

Extraction by Direct Oxidative Pressure Cyanidation of

Bacs Concentrates, Proceedings Randol Gold Forum
(Beaver Creek, OR: Randol International Ltd., 1993),
pp. 209212.
2. J.R. Parga and H. Mercado, Comparative Study of
Direct Pressure Oxidation/Cyanidation and a
Pyrometallurgical Process for the Recovery of Precious
Metals from Sulfide Concentrates, Proceeding of the
17th IPMI, Precious Metals, ed. Rajesh K. Mishra
(Allentown, PA: International Precious Metals Institute,
1993), pp. 5567.
3. N. Geoffroy and F. Cardarelli, A Method for Leaching
or Dissolving Gold from Ores or Precious Metal Scrap,
JOM, 57 (8) (2005), pp. 4750.
4. Anonymous, Refractory Gold Technology, Mining
Magazine (1996), pp. 231234.
5. G.L. Simons et al., Pressure Oxidation Problems
and Solutions: Treating Carbonaceous Gold Ores
Containing Trace Amounts of Chlorine (Halogens),
Mining Engineering (1998), pp. 6973.
6. F. Habashi, Copper Metallurgy at the Crossroads,
Proceedings of the Copper 95-Cobre 96 International
Conference, ed. W.C. Cooper and D.B. Dreisinger
(Montreal, Canada: CIM, 1995), pp. 493510.

7. W. Yernberg, Santa Fe Pacific Gold Targets Millions

Ounces/Year Production, Mining Engineering, 9
(1996), pp. 3943.
8. C.G. Anderson and S.M. Nordwick, Pretreatment
Using Alkaline Sulfide Leaching and Nitrogen Species
Catalyzed Pressure Oxidation on a Refractory Gold
Concentrate, EPD Congress 1996, ed. G.W. Warren
(Warrendale, PA: TMS, 1996), pp. 323341.
9. J. Chen and K. Huang, A New Technique for
Extraction of Platinum Group Metals by Pressure
Cyanidation, Hydrometallurgy, 82 (2006), pp. 164
171.
10. S. Chander and A. Briceo, Kinetics of Pyrite
Oxidation, Minerals and Metallurgical Processing, 8
(1987), pp. 170176.
11. R.G.M.S Berezowski and D.R. Weir, Pressure
Oxidation Pretreatment of Refractory Gold, Mine
Metallurgy Process (1994), pp. 14.
12. J.S. Graham and T.W. James, Cyanide and Other
Lixiviant Leaching Systems for Gold with Some
Practical Applications, Mineral Processing and
Extractive Metallurgy Review, 14 (1995), pp. 193247.
13. R.Y. Wan, M. Le Vier, and J.D. Miller, Research and
Development Activities for the Recovery of Gold from
Non-Cyanide
Solutions,
Hydrometallurgy
Fundamentals, Technology & Innovations (Littleton,
CO: Society for Mining, Metallurgy & Exploration,
1993), pp. 415436.
14. G.A. Deitz and J. Halpern, Reaction of Silver with
Aqueous Solutions of Cyanide and Oxygen, Journal
of Metals, 5 (1953), pp. 11091116.
15. K.G. Thomas, D. Burns, and A.R. Hill, Autoclaving
Technology and Barrick Gold (Paper prepared for the
International Precious Metals Institute, Reno, Nevada,
October 1992).
16. G. Chi, M. Fuerstenau, and J. Maesden, Study of
MerrilCrowe Processing. Part I: Solubility of Zinc in
Alkaline Cyanide Solution, International Journal of
Mineral Processing, 49 (1997), pp. 171183.
Jos R. Parga, Jess L. Valenzuela, and Francisco
Cepeda T. are with the Instituto Tehnologico de
Saltillo in Saltillo, Mexico. Dr. Parga can be reached
at jrparga@its.mx.

HOW TO SUBMIT A PAPER TO JOM

JOM offers its contributors a variety of formats for articles that fall within the technical calendar topics.
These formats include, but are not limited to:
Overview: 48 printed pages (3,2006,400 words). A well-referenced and
well-illustrated introduction to the issues affecting and recent developments occurring in a topical technology. The purpose is to thoroughly introduce the general
reader to the specifics of the field.
Research Summary: 35 printed pages (2,4004,000 words). These
papers outline recent, technically in-depth investigations in materials science
and technology.
Applied Technology: 24 printed pages (1,6003,200 words). These articles communicate information about advancements in commercial products or
processes and are typically submitted by industrial sources.
Design: 24 printed pages (1,6003,200 words). These articles emphasize
the application of the design process in the development of a material system,
process, or product.
Testing and Analysis: 24 printed pages (1,6003,200 words). These
articles emphasize the application of analytical techniques in the study of the
properties and/or performance of a material.
Opinion: 12 printed pages (8001,600 words). Qualified commentary by a
recognized expert on a topical or controversial issue.

Nontechnical Feature: 24 printed pages (1,6003,200 words). These

articles examine pertinent issues in education, professional affairs, and industry
economics.
Conference Reviews: 14 printed pages (8003,200 words). These articles
are synopses of technical presentations at major conferences or symposia.
Industrial Insight: 25 printed pages (1,6003,200 words). An experiencedriven description of the economic, managerial, environmental, engineering, scientific, governmental, international, competitive, etc., factors that influence technology on an industrial scale.
Archaeotechnology: 24 printed pages (1,6003,200 words). These articles
explore materials usage and development throughout history.
Authors should formally notify the editor of their publishing intent by submitting a
300-word abstract by completing the on-line form. An electronic abstract submission
form is available at www.tms.org/pubs/journals/JOM/abstract-author.html. Anyone
wishing to publish in JOM should follow the guidelines established in the JOM Author
Kit. This material, supplied on request, features detailed information on communication, manuscript preparation, and publication procedures. A slightly abridged version
of the Author Kit is available on the World Wide Web at www.tms.org/pubs/journals/
jom/authorguide.html.

for more information: jom@tms.org

2007 October JOM

47

176

Chemical Speciation and Bioavailability (2012), 24(3)

Department of Metallurgy and Materials Science, Institute Technology of Saltillo, V. Carranza 2400, CP. 25000,

Saltillo Coahuila, Mexico

b

Department of Chemical and Extractive Metallurgy, University of Sonora, Hermosillo Sonora, Mexico

*E-mail: jrparga@its.mx

The extraction of gold and silver from minerals and concentrates with cyanide is an important hydrometallurgy process that
has been studied for more than 120 years. This technology, which consists of the dissolutions of the precious metals in
cyanide solutions, followed by the recovery of the values by cementation, activated carbon or ion exchange resin. Most of
complexes, which give them a high degree of toxicity. Appropriate methods for the treatment of cyanide solutions include
This is one of the most innovative ways for the treatment of wastewater containing cyanide. Another is the use of chlorine
dioxide (ClO2) with a gas-sparged hydrocyclone as the reactor. The results show that photodegradation of cyanide was 93%
in 30 minutes using a 450 W halogen lamp, and in the case of ClO2, the destruction of cyanides was 99% in 1 minute. In both
cases, excellent performances can be achieved with the high capacity of these technologies.
: cyanide, titanium dioxide, ClO2, photoelectrocatalysis, gas sparged hydrocyclone
INTRODUCTION

4Ag + 8 CN + O2 + 2H2O

Mexico is the worlds largest producer of silver. According

to annual records, the production of silver in 2011 was 37 x
106 ounces. Mexico, as does the rest of the world, uses the
traditional method of cyanidation to recover gold and silver in
which effluents containing cyanide are generated. This waste
is dangerous for the environment. In the extractive industry,
this method of recovering precious metals is carried out using
a solution of cyanide of 10003000 mg L-1 of NaCN. This
concentration is necessary because the cyanidation of gold
and silver ores is a complex heterogeneous process, where the
leaching behaviour of gold and silver depends upon the nature
of the gold and silver bearer as well of its distribution within
the ore with respect to its ability to be reached by the liquid
phase. The pH is greater than 10 and aeration is necessary
to keep the pulp or solution saturated with oxygen (>7 mg
L-1). The overall reaction for the dissolution of silver may be
expressed by the classic Elsner equation (Jefrey, 2000):

4Ag(CN)2 + 4OH

(1)

The reaction has the following mechanism:

4Ag + 8CN
O2 + 2H2O + 2e
H2O2 + 2e

4Ag(CN)2 + 4e
2OH- + H2O2
2OH

(2)
(3)
(4)

In these reaction mechanisms, the cyanide ion is the

complexing agent or ligand and oxygen is the oxidant. Also,
in this redox process, oxygen removes four electrons from
the silver simultaneous with the transfer of protons (H+)
from water. At room temperature and standard atmospheric
pressure, approximately 8.2 mg of oxygen are present in 1 L
of water. This corresponds to 0.26 x 10-3 mol L-1. Accordingly,
the sodium cyanide concentration (molecular weight of
NaCN = 49) should be equal to 4 x 0.26 x 10-3 x 49 = 0.05 g
L-1 or approximately 0.01%. This was confirmed in practice
at room temperature by a very dilute solution of NaCN of

Doi: 10.3184/095422912X13407902218847

www.chemspecbio.co.uk

CSB1100052.indd 176

7/30/2012 7:05:01 PM

177

Jos R. Parga, Victor Vazquez, Jess L.Valenzuela , Zully Matamoros and Gregorio Gonzalez
0.010.5% for ores, and for concentrates rich in gold and
silver of 0.5 5% (Parga, 2007). Aat the end of this leaching
process, free cyanide enriched solutions, easily dissociable
cyanide compounds, and metallic cyanide complexes are
generated (Botz, 1998). Thus, the cyanide present in either
form has a high degree of toxicity that needs treatment.
In normal conditions, cyanide can be reduced by a natural
degradation mechanism, by means of exposure of the cyanide

solution to solar radiation in large settling ponds or cyanide

removal by volatilisation of free cyanide. Since the natural
degradation process needs proper climatic conditions to be
efficient, the use of a procedure involving chemical oxidation
to accelerate the destruction of cyanide is often mandatory
(Dasai, 1998). A review of these technologies along with their
distinct advantages and disadvantage is show in Table 1. The
most commonly used technology for cyanide destruction is

Table 1 Advantages and disadvantages of various cyanide destruction options (Desai, 1998; Mosher, 1996; Ogutueren, 1999; White, 2000;
Carrillo, 2001; Pavas, 2005)
Detoxification
Advantages
method

Disadvantages

SO2/Air
(INCO)
Process

At least some of reagent savings

are offset by license/royalty
payments

Reagent is very inexpensive and

operational simplicity
For treating aqueous solutions and
gold mine waste sludges
Used over a wide pH range

Hydrogen
peroxide

Excess reagent decomposes to water

and oxygen
Relatively simple to operate
Is not as reactive with thiocyanate

Biological
oxidation

Natural approach, received well

publicly and by regulators
Uses heaps as a reactor, reducing
total wash volumes, and possibly
reach low flow areas of the heap
more effectively
Relatively inexpensive
Can treat total cyanides without
generating another waste stream

Ozonation

Some regeneration of cyanide

possible.
In situ production
Does not produce salts
Solubility in water greater than oxygen

Photocatalytic
degradation
TiO2/Air/UV

Abundant solar energy and the

process not add any toxic pollutant

Strong oxidant and can treat total

cyanides without generating another
waste stream
Compact sealed unit for slurry
treatment

Kg reagent
Kg CN-

Time
(min)

2.5

30

3.8

60

1.9

106

1.9

20

103

5.2

If precipitating ferrocyanides with

copper, must dispose of precipitate
Reagent cost
If precipitating ferrocyanides with
copper, must dispose of precipitate
Requires accurate measurement of
chemical dose
Technology is not well established
Requires combination of metallurgy,
biology and process engineering
Tends to be very site specific, with
each ore type requiring a specific
evaluation and study
Viable cell systems may require
long adaptation and do not function
properly at cyanide concentrations
higher than 200 mg L-1
Produces ammonia
High reagent cost/equipment
Because hydroxide decomposes
ozone, it becomes less efficient at
pH values greater than 11.
Photocatalytic activity of TiO2
influenced by surface area, surface
orientation and crystals structure

Highly economical compared to

artificial UV radiation, which require Difficulty of recovering all titanium
substantial electric power input
dioxide used after the treatment
process
Highly reactive and oxidising
hydroxyl radicals

ClO2 with a
GSH

Process adds sulfates to treated

water

Suitability for
Low CN- High CN-

UV radiation does not

significantly penetrate water and
not available at night and is poor in
the rainy season
Need compressed feed gas (ClO2)
to the GSH
For maximum process efficiency
the porous inner tube need cleaner
every week

High cyanide removal in 1 min

Low-cost reagents

CSB1100052.indd 177

7/30/2012 7:05:01 PM

178

Detoxification of cyanide using TiOs and GSH with ClO2

the Inco cyanide remediation process and more than 90 mines

worldwide now use an Inco SO2/air detoxification circuit to
convert cyanide to the much less toxic cyanate before waste
is discharged to a tailings pond. Typically, this process blows
compressed air through the tailings while adding sodium
metabisulfite which releases SO2, lime to maintain the
pH at around 8.5, and copper sulfate as a catalyst if there
is insufficient copper in the ore extract. This procedure can
reduce concentrations of "weak acid dissociable" (WAD)
cyanide to below the 10 ppm, as mandated by the EU's
Mining Waste Directive (Robbins, 1996).
All these methods (see Table 1) are based on cyanide
recovery by acidification and/or chemical oxidation
destruction, however, none of the above-mentioned chemical
processes is fully acceptable for cyanide detoxification
and a combination of processes, in sequence, is required
to meet the targeted cyanide concentration. Any chemical
process may leave an excess of other undesirable chemicals
in the wastewater stream. Also residence times required for
biological process are typically much greater than those
required for mass transfer. As mentioned previously, in many
cases, the process involves a high cost of chemicals and
royalty payments, in this regard, two promising alternatives
to these processes can be found in the cyanide detoxification
of effluents by the use of photocatalytic detoxification of
cyanide (Blanco,2004) and the use of chlorine dioxide (ClO2)
with a gas-sparged hydrocyclone (GSH) as the reactor.

TiO2 photocatalyst
In past few years, photocatalysis by polycrystalline
semiconductors irradiated by near-UV light has been found

to be effective in oxidising certain organic and inorganic

pollutants to less dangerous species in mild reaction conditions
(Shifu et al., 2011; Xiong et al., 2011). This method was
found to be suitable for the oxidation of free and complex
cyanides dissolved in wastewater. The process works by
exposing wastewater to the combined forces of sunlight
and semiconductor catalyst. A commonly used catalyst is
titanium dioxide (TiO2) (Pavas, 2005). This catalyst may be
mixed into the water, creating slurry, or fixed onto latticetype structure where the water flows through. The TiO2 is
the semiconductor most used in photocatalysis because it
is chemically and biologically inert, it is not poisonous,
it is stable to photochemical and chemical corrosion, it is
abundant in nature and also possess a band of energy of 3.2
eV that can be excited by UV light of <387nm which can be
supplied by solar light (Pavas, 2005).
The mechanism of photocatalysis is carried out when the
nanoparticles of TiO2 are illuminated by UV light, in which,
photons excite the band that contains the valence electrons
and these cross the conductance band, leaving spaces or
holes (h+), a characteristic feature of semiconducting metal
oxides is the strong oxidation power of their holes h+. If
the semiconductor (TiO2) is in an aqueous medium, those
spaces will react with the water molecules (H2O) producing a
hydroxyl radical (sOH) (Blanco, 2004), capable of oxidising
cyanide to cyanate (CNO). Figure 1 shows the interrelation
of energy and the redox mechanism in the surface of TiO2
with the presence of oxygen.
In an aqueous medium with cyanide, the first product
of the photocatalytic oxidation using nanocrystals of TiO2
is CNO- (Augugliaro, 1999). The chemical reactions that
represent this oxidation process are as follows:

Figure 1 Scheme of photocatalytic process over TiO2 surface (Augugliaro, 1999).

CSB1100052.indd 178

7/30/2012 7:05:01 PM

Jos R. Parga, Victor Vazquez, Jess L.Valenzuela , Zully Matamoros and Gregorio Gonzalez
Formation of spaces with UV light (solar light or artificial
source):
TiO2 + hv

h+ + e

(5)

Reaction of valence band spaces (h) with cyanide ion

CN + 2 h+ + 2 OH

CNO + H2O

(6)

Finally oxygen reduction consumes the electrons generated

by reaction (5)
O2 + 2e + 2 H2O

H2O2 + 2 OH

(7)

Hydroxyl radical oxidation is considered to be the primary

mechanism for the destruction of the cyanide ion. The UV
required for photocatalytic processes may come from an
artificial source or the sun. The abundant solar energy
available in Mexico, South America, African countries,
Australia, etc. can be used effectively as a concentrated solar
radiation in a photocatalytic and photochemical processes for
the degradation of cyanide ions (Pavas, 2005). This radiation,
however, is obviously not available in the night and is poor in
the rainy season.

Gas-sparged hydrocyclone technology

The GSH technology was originally developed at the
University of Utah for the fast and efficient flotation of fine
particles from suspensions (Miller et al., 1989). Recent
studies indicate that the fluid flow conditions inside the GSH
system can be effectively exploited for air stripping of VOCs
from contaminated water (Miller, 1996).
The GSH unit, shown schematically in Figure 2, consists
of two concentric right-vertical tubes and a conventional
cyclone header at the top. The porous inner tube is constructed
of any suitable material such as plastic, ceramic, or stainless

179

steel and allows for the sparging of air or any other gas or
steam. The outer nonporous tube simply serves to establish
a gas jacket and provides for the even distribution of the
ClO2(g) through the porous tube. Thus, the GSH reactor can
be used for chemical oxidation in which case the destruction
of cyanide can be achieved with an oxidising gas such as
ClO2(g) which is considered here. The cyanide solution is fed
tangentially at the top through the cyclone header to develop
a swirl flow adjacent to the inside surface of the porous
tube, leaving an empty air core centred on the axis of the
GSH unit. The high-velocity swirl flow shears the sparged
air to produce a high concentration of small bubbles and
intimate interaction between these numerous fine bubbles
of ClO2(g) and the cyanide solution. Gaseous products are
then transported radially to the centre of the cyclone (Miller,
1989). The major portions of the gas phase move towards
the vortex finder of the cyclone header, and are vented into
an appropriate post-treatment device. The specific capacity
of the GSH system is at least 300400 gallons per minute
per cubic foot of equipment volume, 100600 times that of
conventional gas-stripping equipment. The GSH equipment
requires an operating space significantly less that of a reactor
tank, packed tower or other air stripping devices, which result
in a significant savings in capital cost (Miller, 1996).

MATERIALS AND METHODS

Photocatalytic oxidation test
The cyanide photocatalytic oxidation tests were carried out
in a 400 mL beaker. Catalyst concentrations of 1.25, 1.0,
0.75 and 0.5 g L-1 of TiO2 (Degussa P-25) were used with
an average particle size of 30 nm and BET surface area of

HCN
GAS

GSH
Barren

GAS

Solu on of
cyanide

SO2

pH=9
Tank

Ca(OH)2

Under ow

NaOH

Over ow

Figure 2 Schematic representation of the gas-sparged hydrocyclone reactor.

CSB1100052.indd 179

7/30/2012 7:05:16 PM

180

Detoxification of cyanide using TiOs and GSH with ClO2

about 55 m2 g-1. The initial concentration of cyanide was

400 ppm, the solution was prepared using a NaCN, reagent
grade (95%), (Monterrey chemical products), a 450 W
halogen lamp was used as the UV light source, the solution
tests were equilibrated by stirring for 30 minutes in the dark
before exposing the reactor assembly to the concentrated
light from the lamp on the top of the beaker. Then, a sample
was removed for analysis. The concentration of cyanide in
this filtered sample was treated as the zero time concentration
in each experiment before exposure to UV light. Cyanide
determinations were carried out using the selective ion
electrode technique adjusting the pH to 11 in order to avoid
HCN formation. The setup used for the photocatalytic cyanide
detoxification process is shown in Figure 3. The reactor was
enclosed inside an aluminum reflecting compartment.

Experimental procedure of cyanide oxidation by ClO2

The properties of ClO2, like those of chlorine, must necessarily
be considered both in the gas phase and in the aqueous phase
(Perry, 1990). ClO2 has a disagreeable, irritating odour
similar to chlorine. ClO2(g) and may be readily decomposed on
exposure to UV light, therefore, it is always stored in the dark.
The sensitivity of gaseous and liquid ClO2(g) to temperature
and pressure has mitigated against its bulk shipment. ClO2(g)
can be handled safely in the gas phase by diluting with air
or nitrogen to keep its concentration below about 10%. For
potable water and wastewater treatment process, it is only
used in aqueous solutions and is generated on site.
Finally, the environmental impacts associated with the use
of ClO2(g) as wastewater disinfectant or waste treatment are
not well known. It has been reported that the impacts are less
adverse than those associated with chlorination (Freeman,
2006). Since it does not react with water, its oxidation potential
and strength are not pH dependent. Consequently, ClO2(g) is
superior to chlorine particularly for wastewater of relatively

high pH in which the concentration of hypochlorous acid is

low (Chang, 2000).
Experiments for cyanide oxidation by ClO2, at the Institute
Technology of Saltillo pilot plant included preparation of the
barren solution with SO2 gas (pH=211) and stripping with
a 2-inch diameter GSH unit. Chemical analysis for cyanide
in the effluent streams was accomplished with a reflux
distillation method. The collected cyanide was quantified by
titration with silver nitrate standard solution and/or the ion
selective electrode technique.
During the experiments two streams had to be delivered to
the GSH; the cyanide solution and the air. Cyanide solution
was provided by a sump pump mounted on a 300 L retention
tank. The cyanide solution flow rate was adjusted using a
regulated return flow to the tank. Using an air compressor,
airflow was evenly distributed between the upper and lower
sections of GSH and all parts were sealed with gaskets.
Operators were provided with personal HCN gas monitor/
alarm units (Ogutueren, 1999).
The method used for generating on-site ClO2(g) consists
of blending a 45% solution of sodium chlorate with 66Be
sulfuric acid in the top of a reaction vessel. Air containing
10% SO2(g) was blown into a diffuser at the bottom of this
vessel and ClO2 plus air was extracted at the top of the vessel
(ClO2 content was between 6 and 10%). This is the so-called
Mathieson process (Perry,1990 ; Kesting, 1953). The basic
reactions are:
2NaClO3 + H2SO4
2HClO3 + SO2(g)

2HClO3 + Na2SO4
2ClO2(g) + H2SO4

(8)
(9)

Side reactions also take place, including:

2NaClO3 + 5SO2(g) + 4H2O

Cl2(g) +3H2SO4 + 2NaHSO4 (10)

Operating conditions are optimised to suppress the latter

reaction as much as possible, since this produces only chlorine.
The exit gases are reacted with the cyanide solution in the
GSH reactor where the oxidation or destruction of cyanide is
expected to occur according to the following reaction:
CN-+ 2ClO2(g) + 2 OH-

CNO- + 2ClO2- + H2O

(11)

The stoichiometry of the reaction shows that 5.2 kg., of ClO2

is needed to neutralise 1 kg. CN-.

RESULTS AND DISCUSSION

Results of the photocatalytic technique for destruction of

cyanide

Figure 3 Experimental setup for photocatalytic oxidation of cyanide.

CSB1100052.indd 180

For cyanide determination, a calibration curve was

constructed initially, the results are shown in Figure 4. The
cyanide oxidation results using the photocatalysis technology
with TiO2 nanoparticles are shown in Table 2. Blank tests
indicated that the cyanide conversion percentage were less
than 1% without either UV light or TiO2 catalyst.

7/30/2012 7:05:17 PM

181

Jos R. Parga, Victor Vazquez, Jess L.Valenzuela , Zully Matamoros and Gregorio Gonzalez

Figure 4 Calibration curve for measurement of cyanide.

Figure 5 Effect of pH in cyanide destruction.

In Table 2 we can observe that cyanide oxidation using the

photocatalysis technology is a viable option to eliminate this
water pollutant at pH = 11.2. Also, it can be ascertained from
Table 2 that efficiency increased rapidly when the weight
of the catalyst is less than 500 mg. Results indicated that
the cyanide oxidation was held at 93% within a 30 minutes
period. This is due to the fact that an optical saturation
happens with an increased concentration of TiO2 catalyst,
a phenomena that was also observed by other investigators
(Blanco, 2004). Laboratory experiments are performed in
small reactors and the results from these experiments cannot
be directly extrapolated for the design of a larger industrial
ponds.

The combined cyanide CNx is destroyed most effectively at

high pH values.

Cyanide destruction with a GSH reactor

Effect of pH on cyanide destruction
One of the primary process variables for cyanide destruction
with ClO2(g) is the pH of the solution. Table 3 shows the
results of a set of experiments for the effect of pH on cyanide
destruction. The effluent cyanide concentration (both free and
combined cyanide) is plotted as a function of pH in Figure 5.
It is evident that free cyanide is destroyed at all pH values.
Table 2 Percent cyanide destruction results
[TiO2]
(g L-1)

[CN-]IN
(mg L-1)

[CN-]OUT
(mg L-1)

Destruction of CN
(%)

0.5

400

28

93

0.75

400

40

90

1.0

400

52

87

1.25

400

48

88

Effect of NaCl in cyanide destruction

The use of NaCl was considered. These experiments were
designed to eliminate the use of sulfur dioxide (SO2) for the
ClO2 generation and minimise the danger of explosion. The
basic reaction for this process is:
2NaClO3 + 2NaCl + 2H2SO4

2ClO2(g) + Cl2(g)
+ 2Na2SO4 + 2H2O

(12)

Air is blown into the bottom of the vessel driving off the
gas formed which is then diluted by the incoming air. Then
the mixture of ClO2/Cl2 gas, which is extremely volatile, is
stripped from the aqueous solution by the air and is then
circulated through the GSH reactor. The data are presented in
Table 4. The results show 99.9% destruction of free cyanide
and the response is similar to that when SO2 was used for
ClO2 generation.

CONCLUSIONS
It has been shown that cyanide destruction with
photocatalytic oxidation can be achieved in an economical
and environmentally acceptable manner.
Results show that the photocatalysed oxidation of cyanide
waste with TiO2 semiconductor is very efficient for the
destruction of cyanide. Over 90% of cyanide depletion was
observed in the cyanide concentration range studied.
The use of ClO2 in the GSH reactor has been tested in
bench and pilot plant scale applications and has been proven

Table 3 Effect of pH on cyanide destruction

Feed solution = 250 mg L-1 total cyanide
Solution flow rate = 40 L min-1
Gas (6% ClO2) flow rate = 100 L min-1
Cyanide solution (mg L-1)
Final effluent (mg L-1)
% Destruction
pH
Total cyanide
Free cyanide
Combined cyanide
Free cyanide
Combined cyanide (CNX)
11.23
9.20
2.57

250
250
250

0.12
0.19
0.11

52.54
103.0
187.0

99.9
99.9
99.9

78.8
58.8
25.2

CNX = CNO-, HCNO, Fe(CN)6-4, etc.

CSB1100052.indd 181

7/30/2012 7:05:17 PM

Detoxification of cyanide using TiOs and GSH with ClO2

182

Table 4 Effect of NaCl in cyanide destruction

Feed solution = 250 mg L-1 Total cyanide.
Gas (ClO2/Cl2) flow rate = 100 L min-1
Barren bleed (mg L-1)
Total cyanide
NaCl (g L-1)
1.23
250
0.80
250
0.40
250
0
250

Solution flow rate = 40 L min-1

pH = 11.2

Final effluent (mg L-1)

Free cyanide
Combined cyanide
0.02
52.54
0.10
149.0
0.09
193.0
0.10
222.0

% Destruction
Free cyanide
Combined cyanide
99.9
78.8
99.9
40.4
99.9
22.8
99.9
11.2

CNX = CNO-, HCNO, Fe(CN)6-4, etc.

to be effective for the destruction of cyanide in solution and

slurries, the results show 99.9% destruction of free cyanide
and the response is similar to that when SO2 was used for
ClO2 generation.
Finally, the economics of the ClO2 process are quite
attractive because there are cost savings due to the short
residence time, decreases in operating staff and other chemical
utilised (i.e. copper sulfate and NaOH) in the other processes.

ACKNOWLEDGEMENTS
The authors wish to acknowledge support of this project to the
National Council of Science and Technology (CONACYT)
and to Direccin General de Educacin Superior Tecnolgica
(DGEST).

REFERENCES
Augugliaro, V., Blanco, J. and Caceres, J. (1999) Catalysis Today, 54,
245-253.
Blanco, J. and Malato, S. (2004) PhD thesis, Plataforma Solar de
Almera, 14.
Botz, M. and Stevenson, J. (1995) Eng. Min. J., 44-47.
Chang, C.Y., Hsieh, Y.H., Hsu, S.S., Hu P.Y. and Wang, K.H. ( 2000) J.
Hazard. Mater., B79, 89-102.
Carrillo, F.R., Pedroza, M.J. and Soria, A. (2001) Eur. J. Min. Process.
Envir. Protect., 1, 55-63.

CSB1100052.indd 182

Desai, J.D., Ramakrishna, C., Patel, P.S. and Awasthl, S.K. (1998) Chem.
Eng. World, XXXIII, 6,115-121.
Freeman, H.M. (1988) Standard handbook of hazardous waste treatment
and disposal. McGraw-Hill, New York.
Jeffrey, M.I. and Ritchie, I.M. (2000) J. Electrochem. Soc. I, 147, 32573262.
Kesting, E. ( 1953) TAPPI, 36, 176-171.
Miller, J.D. and Kinneberg, D.J. (1984) International Conference on
Recent Advances in Mineral Science and Technology, pp. 337-338.
Johannesburg.
Miller, J.D. and Ye Yi (1989) Miner. Proc. Extract. Metall. Rev., 307-309.
Miller, J.D., Lelinski, D. and Parga, J.R. (1996), Final report-CX
823711, Advance Process Technology for the Wastepaper Recycling
Plants and Pulp/Paper Plants. Southwest Centre for Environmental
Research and Policy.
Mosher, J.B. and Figueroa, A. (1996) Miner. Eng., 5,573-581.
Robbins, G.H. (1996) CIM Bull., 9, 63-69.
Ogutueren, U.B., Toru, E. and Koparal, S. (1999) Water Res., 33, 18511856.
Parga, J.R., Valenzuela, J.L. and Cepeda, F. (2007) J. Metals, 10, 43-47.
Pavas, E. Camargo, M. and Jones, C. (2005), MSc thesis, Universidad
EAFIT, 11,7.
Perry, W.L. andEckenfelder, W.W. (1990) Toxicity reduction in industrial
effluents. New York: Van Nostrand Reinhold Co.
Shifu, Ch. Yunguang, Y. and Wei, L. (2011) J. Hazard. Mater., 186,
1560-1567.
White, D.M., Pilon, T.A. andWoolard, C. (2000) Water Res., 34, 21052109.
Xiong, Z. Ma, J., Ng, W.J., Waite, T.D. and Zhao, X.S. (2011) Water
Res., 45, 2095-2103.

7/30/2012 7:05:17 PM

09 a 12 de setembro de 2012
Bzios, RJ

ESTUDIO CINETICO DE LA EXTRACCIN DE ORO DE UN

MINERAL
PIRITOSO
MEDIANTE
OXIDACIN
Y
LIXIVIACIN SIMULTNEA A PRESIN
J.L. VALENZUELA G.1, L.S. QUIROZ C.1, J.R. PARGA T.2, P.J. VALENZUELA G.3,
P. GUERRERO G.1
1

Universidad de Sonora, Departamento de Ingeniera Qumica y Metalurgia, Mxico.

Instituto Tecnolgico de Saltillo, Departamento de Metalurgia y Materiales, Mxico
3
Minas de Oro Nacional, Mulatos, Sonora, Mxico.
E-mail para contacto: jvalen@iq.uson.mx

RESUMEN Oxidacin a presin es un pre tratamiento oxidativo

hidrometalrgico utilizado para menas refractarias sulfurosas. Se realiz un
estudio de la oxidacin a presin en medio alcalino y lixiviacin simultnea con
cianuro de sodio a un mineral piritoso proveniente de la mina Mulatos, localizada
en el municipio de Sahuaripa, Sonora, Mexico. Se muestran los resultados de
caracterizacin del material y de los procesos de lixiviacin, en los cuales las
variables a modificar utilizadas fueron temperatura, presin y concentracin de
cianuro. La caracterizacin del material indic la presencia de pirita como mineral
principal. Se llevaron a cabo pruebas en rangos de temperatura de 60 80 C,
presin de 87.5 a 150 psi, utilizando oxgeno, y concentracin de cianuro de 0.8%
a 1.2% en peso, utilizando un reactor a presin Parr de 2 litros.

1. INTRODUCCIN
En la extraccin de metales preciosos utilizando hidrometalurgia, el proceso ms
comnmente utilizado es la lixiviacin con cianuro de sodio, se muestran las reacciones para
oro y plata, Fleming (1992), Marsden y House (2006).
4Au + 8CN- + 2H2O + O2 4 Au(CN)2- + 4 OH-

(1)

4Ag + 8CN- + 2H2O + O2 4 Ag(CN)2- + 4 OH-

(2)

Existen minerales de oro y plata llamados refractarios los cuales se encuentran en una
matriz piritosa, para los que la cianuracin no es efectiva, por lo cual se recurre a pretratamientos oxidativos a fin de convertir los minerales sulfuros a xidos porosos en las que la
cianuracin funciona ms eficientemente. La reaccin (3) muestra la oxidacin de pirita en
medio alcalino y la formacin del xido poroso, Koslides y Ciminelli (1992).
2FeS2 (s) + 15/2 O2 (g) + 8H-(aq) Fe2O3 (s) + 4SO42-(aq) +4H2O(l)

(3)

Se ha utilizado el tratamiento de oxidacin qumica a presin y lixiviacin con cianuro

en simultneo para un concentrado de flotacin producido en la mina de Bacs, Durango con
buenos resultados Parga et al. (2007). Se propone utilizar este tratamiento para un mineral

09 a 12 de setembro de 2012
Bzios, RJ
refractario piritoso de la regin de Mulatos, Municipio de Sahuaripa, Sonora, Mxico,
manipulando variables tales como presin, temperatura y concentracin de NaCN, para
encontrar las mejores condiciones de oxidacin lixiviacin.

2. METODOLOGA
Se obtuvo la muestra del mineral de Mulatos, la muestra se denomin SAS-1, un sulfuro
silicificado con contenido de oro y plata. La muestra fue reducida de tamao hasta un
intervalo entre 45 y 53 m. Se caracteriz el mineral con las tcnicas de Difraccin de Rayos
X, Microscopa Electrnica de Barrido, Espectroscopa de Absorcin Atmica,
Espectroscopa de Dispersin de Energa de Rayos X para la determinacin de especies
minerales y elementales, junto con pruebas metalrgicas de lixiviacin agitada, cianuracin en
caliente y ensaye al fuego para determinar porcentajes de extraccin del oro, metal de inters.
El sistema experimental consisti en un reactor a presin Parr de 2 litros con
intercambiador de calor, agitacin y vlvulas de control para entrada y salida de gases, Figura
1. El mineral se mezcl con agua para formar una pulpa, a la cual se aadieron los reactivos y
se introdujo al reactor. Se utiliz oxgeno puro para el reactor a presin, se aadieron cianuro
de sodio como lixiviante y cal, para mantener un pH superior a 11, con el propsito de evitar
la reaccin de produccin de cido cianhdrico, el cual es voltil y venenoso; sta ocurre a pH
menores a 9.5, ilustrada en la ecuacin (4).
H+ + NaCN HCN + Na+

(4)

Las pruebas se realizaron con el reactor completamente agitado. Posterior al tiempo de

reaccin dentro del recipiente a presin, el contenido del reactor se filtr al vaco para separar
slido y lquido para su posterior anlisis. Se calcul el porcentaje de extraccin de oro en
base a los resultados obtenidos.

Figura 1. Reactor Parr utilizado en la Experimentacin, equipado con chaqueta de

calentamiento y agua de enfriamiento para control de temperatura.

09 a 12 de setembro de 2012
Bzios, RJ

2.1 Caracterizacin del Mineral

Los resultados de la caracterizacin indicaron la presencia de pirita (FeS2) como principal
componente mineral, as como cuarzo. El mineral tiene un contenido de oro, plata y otras
especies elementales como se muestra en las Tablas 1 y 2. Los anlisis de DRX y EDS
confirmaron la presencia de sulfuro de hierro FeS2 y SiO2 como principales especies, como se
muestra en las Figuras 2 y 3.
Tabla 1 Resultados de Ensaye al Fuego y Espectroscopia de Absorcin Atmica para la
Muestra SAS-1
Au (g/t)
Ag (g/t)
Cu (%)
Fe (%)
Pb (%)
Zn (%)
SAS-1
4
23
0.029
6.33
0.061
0.0068
Tabla 2 Resultados de Contenido de Oro y Azufre y Consumos de Reactivo
Au (g/t)
Extraccin Au (%) Consumo (kg/t)
Muestra
Ensaye
Calculada
S (%)

SAS-1

Cabeza

Cola

Cabeza

Ens

Calc

CaO

NaCN

3.97

1.65

3.96

57.4

58.43

4.98

0.86

16.32

Figura 2. Imgenes de Microscopa Elecrnica de Barrido y Espectroscopa de Dispersin de

Energa de Rayos X de la muestra SAS-1.

d=3.36415 d=3.34139

09 a 12 de setembro de 2012
Bzios, RJ

SAS_1

400

d=1.63377

d=1.67135

d=1.81790

d=1.97899

d=1.91537

d=2.12659

d=2.28058

d=2.70832

d=3.12729

d=3.57523

d=7.15589

100

d=2.23693
d=2.21156

200

d=2.45529
d=2.42249

d=4.25261

Lin (Counts)

300

0
10

20

30

40

50

2-Theta - Scale
(Room) - Time Started: 18 s - 2-Theta: 5.000 - Theta: 2.500 - Chi: 0.00 -

Figura 3. Resultado de Difraccin de Rayos X para la muestra SAS-1. El espectro indica la

presencia de cuarzo y pirita, SiO2 y FeS2 respectivamente.
Los resultados de SEM y DRX indican altos contenidos de hierro, azufre y silicio, los
cuales se encuentran en las especies de pirita y cuarzo. Como se aprecia en la microfotografa,
las partculas con aspecto brillante son las que contienen mayor cantidad de Fe y S.

3. RESULTADOS Y DISCUSIN
3.1. Pruebas experimentales
Las pruebas de lixiviacin a presin atmosfrica revelan porcentajes de extraccin bajos
relativamente, as como las pruebas de cianuracin caliente en el rango de 40 80C. Las
pruebas de lixiviacin atmosfrica se llevaron a cabo bajo las siguientes condiciones:
porcentaje de slidos 30% w/w, concentracin de NaCN 300 mg/L, pH 10.5 (CaO), tiempo
lixiviacin 72 h, tamao de partcula p80 3/16 (100%-3/8). Las pruebas de cianuracin
caliente se realizaron bajo condiciones de: concentracin de NaCN 1%, adicin de CaO para
control de pH de 10 Kg/ton, temperatura del rango de 40C - 80C, porcentaje de slidos de
30%, tiempo de 2.5 horas, tamao de partcula de - 270 mesh (55m). Las pruebas de
oxidacin y lixiviacin a presin en simultneo se realizaron con variables modificadas de
presin en rango de 87.5 200 psi, temperatura en el rango de 60 150C, y concentracin
de cianuro de 0.8 1.2 %w., tiempo de 1 hora y pH superior a 11.

09 a 12 de setembro de 2012
Bzios, RJ

40%

Extraccin de Au

35%
30%
25%
20%
15%
10%
5%
0%
0

20

40
Tiempo, h

80

60

Figura 4. Resultados de lixiviacin a presin atmosfrica de la muestra SAS-1

55%
40C

Extraccin de Au

54%

60C

53%

80C

52%
51%
50%
49%
48%
0

0.5

1.5
Tiempo, h

2.5

Figura 5. Resultados de la cianuracin caliente de la muestra SAS-1

Extraccin de Au, %

09 a 12 de setembro de 2012
Bzios, RJ

100
90
80
70
60
50
40
30
20
10
0

P = 87.5 psi
P = 120 psi
P = 150 psi
P = 200 psi

50

100
Temperatura, C

150

200

Extraccin de Au, %

Figura 6. Curvas de extraccin contra temperatura a presin constante para

concentracin inicial de cianuro de 0.8 %w.

100
90
80
70
60
50
40
30
20
10
0

P = 87.5 psi
P = 120 psi
P = 150 psi
P = 200 psi

50

100
Temperatura, C

150

200

Figura 7. Curvas de extraccin contra temperatura a presin constante para concentracin

inicial de cianuro de 1.0 %w.
Al comparar la extraccin en los procesos de lixiviacin a presin atmosfrica y
lixiviacin oxidacin a presin, puede apreciarse que los obtenidos en el reactor a presin se
obtiene una mayor extraccion (%), y obtenidos en un tiempo mucho menor. Se ha apreciado
un efecto similar en el estudio de las operaciones de oxidacin y lixiviacin con cianuro por
separado, donde los porcentajes de extraccin son directamente afectados por la oxidacin de
los sulfuros, y ocurra un aumento del 20% al 70% de extraccin de oro, como lo presenta Li
et al. (2006).

Extraccin de Au, %

09 a 12 de setembro de 2012
Bzios, RJ

100
90
80
70
60
50
40
30
20
10
0

P = 87.5 psi
P = 120 psi
P = 150 psi
P = 200 psi

50

100
Temperatura, C

150

200

Figura 8. Curvas de extraccin contra temperatura a presin constante para concentracin

inicial de cianuro de 1.2 %w.
Los resultados experimentales arrojaron que el efecto de la temperatura es mayor que el
efecto de la presin en los porcentajes de extraccin. Es posible que el tiempo de reaccin de
una hora, considerado como suficiente para un caso ya estudiado por Parga et al. (2007), no
haya bastado para formar la capa porosa de producto oxidado vista para la pirita en solucin
alcalina Koslides y Ciminelli (1992), debido a diferencias en la mineraloga. Cabe mencionar
que posiblemente por estas condiciones de oxidacin parcial, la presin de oxgeno no mostr
tener un efecto mayor en el porcentaje de extraccin.
100

Extraccin de oro, %

90
80

70
60
50

110C

40

90C

30

120C

20
10
0

20

40

60

80

100

Tiempo, min

Figura 9. Resultados de pruebas de oxidacin y lixiviacin a presin, para extraccin de oro

contra tiempo a tres distintos valores de temperatura. Condiciones de 0.8%w de NaCN y
87.5 psi.

09 a 12 de setembro de 2012
Bzios, RJ

3.2. Ajuste a un Modelo Cintico de Lixiviacin

Se presentan los resultados de las pruebas cinticas continuas en la Figura 9, donde se
muestra la extraccin de oro a tres distintas temperaturas. Posteriormente se toma la ecuacin
del modelo de ncleo decreciente para control por difusin a travs de la capa de producto
Sohn y Wadsworth (1986), Ballester et al.(2007), utilizando como la fraccin reaccionada
de la mena y t como el tiempo de reaccin.
2
2
1 - a - (1 - a ) 3 = kt
3

(5)

Al graficar la parte izquierda de la ecuacin contra el tiempo (Figura 10), se obtiene una
grfica recta con una pendiente que equivale a la constante cintica, k, que se utiliza en el
clculo de la energa de activacin (Tabla 3).
0.25

1-2/3-(1-)^(2/3)

0.2

y = 0.002x + 0.019
R = 0.941
90C

0.15
y = 0.001x + 0.017
R = 0.842
0.1

110C

120C
Lineal (90C)
Lineal (110C)

0.05

Lineal (120C)
y = 0.000x + 0.001
R = 0.952

0
0

10

20

30

40

50

60

70

Tiempo, min

Figura 10. Grfica de los datos de extraccin de oro contra tiempo, para los tres valores de
temperatura estudiados en un perodo de tiempo de 60 minutos, utilizando el modelo de
ncleo decreciente de control por difusin a travs de la capa de producto.
Posteriormente se construye una grfica de Arrhenius (Figura 11) para determinar el
valor de la energa de activacin, el cual permite saber si la cintica de la reaccin qumica
est controlada por el transporte por difusin de los reactivos hacia la superficie de la
partcula o por la reaccin qumica superficial, con valores menores a 20 kJ/mol y mayores a
40 kJ/mol para cada etapa controlante respectivamente. La ecuacin de Arrhenius (Ec. 6) en
su forma logartmica nos indica que los datos de las constantes cinticas k contra el inverso de
los valores de temperatura absoluta, nos da una grfica cuya pendiente negativa es igual a la
energa de activacin de la reaccin sobre la constante de los gases ideales, con la cual se hace
el clculo, expresando en kJ/mol el valor de .

ln k = ln A -

Ea 1
R T

(6)

09 a 12 de setembro de 2012
Bzios, RJ
El ndice de correlacin de los datos cinticos en cuanto a si hay concordancia con el
modelo, para las temperaturas de 90 y 110C, se considera baja, del orden de 0.62 a 0.70 para
90 minutos de reaccin. Cabe mencionar que para los primeros 60 minutos a estas dos
temperaturas, la concordancia con el modelo es del orden de 0.92 a 0.96. El comportamiento
de la reaccin a esas temperaturas a tiempos mayores de 60 minutos podra deberse a que la
oxidacin de la partcula ha llegado a un punto donde la partcula comienza a exponer las
superficies de las partculas de oro y la lixiviacin se vuelve ms eficiente. Quiroz (2010).
Los valores de las pendientes k para las ecuaciones del modelo de control por difusin y
las tres distintas temperaturas se expresan en la Tabla 3.
-6
-6.2

2.5

2.55

2.6

2.65

ln k

-6.4

2.7

2.75

2.8

y = -4.5744x + 5.3842
R = 0.8227

-6.6
-6.8
-7
-7.2
-7.4

1000/T, K

Figura 11. Grfica de Arrhenius para el clculo de la energa de activacin de la oxidacin y

lixiviacin a presin usando el modelo de control por difusin a travs de la capa de producto.
Tabla 3 Clculo de la energa de activacin segn grfica y ecuacin de Arrhenius para el
modelo de control por difusin a travs de la capa de producto.
T, C
90
110
120

pendiente, k
0.0008
0.0011
0.0023

T, K
363.15
383.15
393.15

1000/T
ln k
2.75368305 -7.1308988
2.60994389 -6.8124451
2.54355844 -6.0748461

(- /R)
-4.574

, kJ/mol
38.0303949

4. CONCLUSIONES
El tratamiento de oxidacin y lixiviacin simultnea a presin ha mostrado mejoras
considerables en los porcentajes de extraccin de oro, en comparacin con la lixiviacin a
presin atmosfrica, en tiempos mucho menores y a condiciones de presin moderadas, lo
cual es un factor importante a considerar al hacer el escalamiento hacia un nivel de planta
piloto.

09 a 12 de setembro de 2012
Bzios, RJ
A condiciones normales de cianuracin, la disolucin del oro fue de 38-39%, en la
cianuracin utilizando temperatura de 40 80C la disolucin del oro se increment a 5054%, y finalmente utilizando oxidacin y lixiviacin a presin de 87.5 psi, dio una disolucin
final del 81-86%.
La oxidacin y lixiviacin a presin simultnea produjo un aumento en los porcentajes
de extraccin de oro a comparacin con las pruebas a condiciones normales.
Las condiciones ms adecuadas que se determinaron son: T = 90C, P =87.5 psi,
[NaCN] = 8 g/L, t = 1 hora, pH > 11 y agitacin constante.
El anlisis cintico de los datos obtenidos de la experimentacin nos demuestran que el
proceso controlante de la lixiviacin oxidante a presin se ajusta a un modelo de ncleo
decreciente de control mixto, ya que los valores de la energa de activacin fueron de 30 38
kJ/mol. Finalmente se concluye que para este mineral sulfuro altamente silicificado, la
temperatura y presin oxidante tienen un efecto altamente significativo, ya que la disolucin
del oro se increment en un 45%.

5. RECONOCIMIENTOS
Se extiende un agradecimiento y reconocimiento al Departamento de Ingeniera
Qumica y Metalurgia de la Universidad de Sonora, a la empresa Minas de Oro Nacional por
su colaboracin con el suministro de muestras y ensayes metalrgicos, as como al proyecto
PIFI 2011 de Fortalecimiento Institucional de la SEP de Mexico.

6. REFERENCIAS
BALLESTER A., VERDEJA L.F., SANCHO J. Metalurgia Extractiva, Vol.1 Fundamentos.
Madrid: Editorial Sntesis, 2007.
FLEMING, C.A. (). Hydrometallurgy of precious metals recovery. Hydrometallurgy, v.30, p.
127-162, 1992.
KOSLIDES, T.; CIMINELLI, V.S.T. Pressure oxidation of arsenopyrite and pyrite in alkaline
solutions, Hydrometallurgy, v. 30 p. 87-105, 1992.
LI, J.; DABROWSKI, B.; MILLER; J.D., ACAR; S., DIETRICH, M.; LEVIER, K.M.; WAN,
R.Y. The influence of pyrite pre-oxidation on gold recovery by cyanidation. Minerals
Engineering, v.19, p. 883-895, 2006.
MARSDEN, J.O.; HOUSE, C.I. The Chemistry of Gold Extraction. Litleton, Colorado, USA:
Ed. SME, 2006.
PARGA, J.R.; VALENZUELA, J. L.; CEPEDA T. F. (). Pressure cyanide leaching for
precious metals recovery, JOM v. 59, 43-47, 2007.
QUIROZ C., L.S. Tesis de Maestra, Depto. Ingeniera Qumica y Metalurgia, Universidad de
Sonora, 2010.
SOHN H.Y.; WADSWORTH M.E. Cintica de los Procesos de la Metalurgia Extractiva.
Mxico: Editorial Trillas, 1986.

<=99 '(>,)

!"#$"%& '($")*& +&%,-&.( /( 01)"2 3).456$.2&* 7(*.,%(%8,"&

!" !"#$ %& '()*( +")),## $%& -(./0 1& 2"34,
'()$% *+$,-* $%& +%./01%)+%-$, 21%2+0%3 &/2-$-+ -*$- /%&(3-0/$, 4012+33+3 5+ /)401.+& 10 0+4,$2+&6 7+21.+0" 10 0+2"2,/%8 /3 $%
/)410-$%- $2-/./-" -*$- $,,193 2"$%/&+ 0+3/&(+ :01) -*+ /%&(3-0/$, 4012+33+3 -1 5+ 0+;(3+&< 0+&(2/%8 /-3 401&(2-/1% 213- $%&
&/3413$, 4015,+)36 =% -*/3 0+8$0&< -*+ $/0;34$08+& *"&012"2,1%+ >?@'A *$3 5++% (3+& $3 $ 0+$2-10 :10 -*+ -0+$-)+%- 1: 2"$%/&+
31,(-/1%3 :10 2"$%/&+ 0+2"2,/%8 5" $2/&/:/2$-/1%B.1,$-/,/C$-/1% (3/%8 -*+ D+E/2$% )1&/:/2$-/1% 1: -*+ D/,,3;F019+ 4012+336
?G(+1(3 2"$%/&+;/1% 21%2+%-0$-/1% 2$% 5+ 0+&(2+& :01) HIJ 44) -1 5+,19 HJ 44) /% -*+ ?@' 9/-* 0+21.+0/+3 80+$-+0 -*$% KJ L
/% $ 3/%8,+ 3-$8+6

9 :";.,*<%;),"

?( [ H FQU ] ?(>FQAHU [ +U

>HA

? .$0/+-" 1: /%&(3-0/$, +::,(+%-3 $0+ M%19% -1 21%-$/%

2"$%/&+36 N*+3+ .$0/1(3 9$3-+ 3-0+$)3 $0/3+ :01) &/::+0+%4012+33 /%&(3-0/+3< 3(2* $3 -*13+ 9$3-+3 :01) )$%(:$2-(0/%8
3"%-*+-/2 :/5+0 >$20",1%/-0/,+A< 21$, 21%.+03/1% 9$3-+3 10
21M/%8 +::,(+%-3 >:01) -*+ /01% $%& 3-++, /%&(3-0/+3A< +,+2-01;
4,$-/%8 9$3-+ $%& 9$3-+3 :01) -*+ 4+-01,+() /%&(3-0"6 N*+
)13- 3/8%/:/2$%- 31(02+ 1: *$C$0&1(3 2"$%/&+ 9$3-+ /3 -*+
)+-$, :/%/3*/%8 /%&(3-0" $%& 9$3-+3 :01) -*+ 4012+33/%8 1:
40+2/1(3 )+-$,3 0+31(02+3 5" 2"$%/&$-/1%6 ?,, -*+3+ 9$3-+3
*$.+ .$0/+& 2*$0$2-+0/3-/23 $%& $0+ -*+0+:10+ 3(5O+2- -1
&/::+0+%- 4012+33/%8 $%& -0+$-)+%- 3-0$-+8/+3 -*$- &+4+%&
(41% -*+ 21%2+%-0$-/1% 1: 2"$%/&+3 $%& -*+ :,19 0$-+ 1: -*+
9$3-+ 3-0+$)6
N*+ 2"$%/&+ 4012+33 *$3 5++% /% ,$08+;32$,+ (3+ /% )$%"
4$0-3 1: -*+ 910,& :10 )10+ -*$% PPJ "+$03 $%& /3 ,/M+," 1%+ 1:
-*+ )13- -*101(8*," 3-(&/+& $%& 9+,,;(%&+03-11& /%&(3-0/$,
2*+)/2$, 4012+33+3< $3 9$3 3*19% 5" D2Q(,--" RPS6 =% )/%/%8
14+0$-/1%3< 2"$%/&$-/1% /3 -*+ 40+&1)/%$%- )+-*1& 5" 9*/2*
81,& $%& 3/,.+0 $0+ 0+21.+0+& :01) -*+/0 10+36 =% 40$2-/2+< -*+
&/331,(-/1% 1: 81,& $%& 3/,.+0 /% $G(+1(3 2"$%/&+ 31,(-/1% /3
-"4/2$,," 2$00/+& 1(- 9/-* J6JTUJ6T L Q$FQ $%& /- /3 (3($,,"
-*+ )13- 3/8%/:/2$%- 0+$8+%- 213-6 V/)+ /3 $&&+& $3 $ 4'
)1&/:/+0 -1 /%20+$3+ -*+ 4' $%& 40+.+%- $3 )(2* $3 4133/5,+
-*+ *"&01,"3/3 1: -*+ 2"$%/&+ /1% -1 *"&018+% 2"$%/&+6 ?,31
$+0$-/1% /3 %+2+33$0" -1 M++4 -*+ 4(,4 10 31,(-/1% 3$-(0$-+&
9/-* 1E"8+% >W X 44)A6 N*+ 1.+0$,, 0+$2-/1% :10 -*+ &/331,(-/1%
1: 81,& $%& 3/,.+0 /% &/,(-+< $+0$-+&< $%& $,M$,/%+ 2"$%/&+
31,(-/1%3 )$" 5+ +E40+33+& 5" -*+ 2,$33/2 Y,3%+0 +G($-/1%

\H [ H 'H\ [ H+U ] H \'U [ 'H\H

>TA

'H\H [ H+U ] H \'U

>ZA

Z ?( [ K FQU [ \H [ H 'H\ ] Z R?(>FQAHUS [ Z \'U

>PA

9*/2* *$3 -*+ :1,,19/%8 )+2*$%/3)^

U
R#S

l6 76 d$08$ N100+3 >$(-*10 -1 9*1) 2100+341%&+%2+ 3*1(,& 5+ $&&0+33+&<

+;)$/,^ &0O04$08$m*1-)$/,621)A< =%3-/-(-+ 1: N+2*%1,18" 1: @$,-/,,1<
`+4$0-)+%- 1: D+-$,,(08" $%& D$-+0/$,3 @2/+%2+< h6 F$00$%C$ HZJJ<
F6d6 HIJJJ< @$,-/,,1 F1$*6 DnE/21o `6 V6 F12M+< V$)$0 a%/.+03/-"<
F*+)/3-0" $%& F*+)/2$, Y%8/%++0/%8 `+4$0-)+%-< !+$()1%- N+E$3
XXXPJ< a@?6

25,6& 78*& +,358"9& :; >HJJTA Z<

=% -*/3 )+2*$%/3)3 2"$%/&+ /1% /3 -*+ 21)4,+E/%8 $8+%- 10

,/8$%&< $%& 1E"8+% /3 -*+ 1E/&$%- RHS6
?:-+0 +E-0$2-/1% $%& 0+21.+0" 1: -*+ 40+2/1(3 )+-$,3<
3(53-$%-/$, $)1(%-3 1: 2"$%/&+ $0+ &+,/.+0+& -1 -$/,/%83 41%&3<
9*/2* 20+$-+ +%./01%)+%-$, 4015,+)3 &(+ -1 -*+ -1E/2/-" 1:
2"$%/&+36 N*+0+:10+< -*+ 0+2"2,/%8 1: 2"$%/&+ /3 $ )$--+0 1:
/%-+0+3- :01) 51-* $% +21%1)/2$, $34+2- $%& -1 401-+2- -*+
0+2+/./%8 9$-+0 :01) 41-+%-/$,," *$0):(, 2"$%/&+< $3 9$3
3*19% 5" _*/-+ RTS6
`(+ -1 -*+ 9/&+340+$& (3+ 1: 2"$%/&+ /% )/%/%8 14+0$-/1%3<
-*+ 0+2"2,/%8 10 &+3-0(2-/1% 1: 2"$%/&+ /3 /)410-$%- 51-* :01)
-*+ +%./01%)+%-$, $34+2-3 1: 9$3-+9$-+0 $%& +::,(+%- -0+$-)+%-<
$%& :01) -*+ +21%1)/2 $34+2-3 $3312/$-+& 9/-* -*+ */8* 0+$8+%21%3()4-/1% 5" -*+ 4012+33 /-3+,:< :10 +E$)4,+< -*+ (3+ 1: $
4012+&(0+ -1 0+21.+0 2"$%/&+ )$" 5+ $ 811& 14-/1% 3/%2+ -*+
)$0M+- 40/2+ 1: 2"$%/&+ /3 5+-9++% a@b P6JJ $%& a@b P6IJ 1%
$.+0$8+ RZS6 N*/3 ,$--+0 3/-($-/1% 9$3 -*+ 2$3+ :10 $ 2"$%/&$-/1%
4012+33 &+.+,14+& $- !$2c3 )/%+ >/% `(0$%81< D+E/21A :10 -*+
0+21.+0" 1: 81,& $%& 3/,.+0 :01) $ 4"0/-+ 21%2+%-0$-+ RIS6 N*+
4012+33 21)40/3+3 -*+ :1,,19/%8 3-+43^ ,+$2*/%8 -*+ 21)4,+E
3(,:/&+ 21%2+%-0$-+ 5" $ 1%+;3-$8+ 40+33(0+ 1E/&$-/1% /% $
*/8*," $,M$,/%+ 2"$%/&+ 31,(-/1% >P L 2"$%/&+A< :/,-0$-/1% $%&
9$3*/%8 -1 3+4$0$-+ -*+ 31,/&< $%& 40+2/4/-$-/1% 1: 81,& $%&
3/,.+0 9/-* C/%2 &(3- :01) -*+ :/,-0$-+6 N*+ :10)$-/1% 1: )+-$,
21)4,+E+3 >2144+0< /01% $%& C/%2A 9/-* -*/12"$%$-+ &(0/%8
40+33(0+ ,+$2*/%8 0+3(,-3 /% 34+2/+3< 9*/2* $0+ 4$0-/2(,$0,"
-1E/26 @/%2+ (,-0$./1,+- ,/8*- &+21)413+3 -*/12"$%$-+ -1 :10)
2"$%/&+< /- /3 -*+% 4133/5,+ -*$- 3(%,/8*- )$" ,/5+0$-+ 2"$%/&+<
9*/2* 91(,& 5+ -1E/2 -1 $G($-/2 ,/:+6 ?,31< /- 3*1(,& 5+ %1-+&
-*$- 2"$%1;21)4,+E+3 1: )1&+0$-+ 3-$5/,/-" 21(,& 5+ 0+$&/,"
&+21)413+& 5" $2/&/:/2$-/1% 10 1E/&$-/1%6
N*+ a@ Y%./01%)+%-$, d01-+2-/1% ?8+%2" *$3 401413+&
$ ,/)/- 1: J6H )8B, 2"$%/&+ /% &0/%M/%8 9$-+06 N*+ e+0)$%
$%& @9/33 0+8(,$-/1%3 *$.+ 3+- ,/)/- 1: J6JP )8B, :10 2"$%/&+
:10 3(0:$2+ 9$-+0 $%& J6I )8BV :10 3+9+03 RfS6 =% D+E/21<
-*+ @+20+-$0" 1: Y%./01%)+%-$, $%& Q$-(0$, 7+21(03+3

! HJJT _=VYg;hF' h+0,$8 e)5' i F16 je$?< _+/%*+/)

JkTJ;XIPfBJTBJZJZ;JP
b PX6IJ[6IJBJ
JkTJ;XIPfBJTBJZJZ;JP
b PX6IJ[6IJBJ

<=99 '(>,)
>@YD?7Q?NA *$3 3+- -*+ ,/)/- :10 2"$%/&+ $3 J6H )8BV6 =%
./+9 1: -*+3+ 21%3/&+0$-/1%3< 2"$%/&+ 0+2"2,/%8 /3 $ %+2+33$0"
4012+33/%8 3-+46

HCN
Air

= 3).456$.2&* 7(*.,%(%8,"& +&$%;,.

! HJJT _=VYg;hF' h+0,$8 e)5' i F16 je$?< _+/%*+/)

Waste
solution with
cyanide

SO2

pH=2

Ca(OH)2

NaOH

Underflow Overflow

Tank

?)2<.& 9@ @2*+)$-/2 &0$9/%8 1: -*+ ?3* 3"3-+) (3+& :10 3-0/44/%8 1: 2"$%/&+6

> '($")*& +&%(%8)"2

q0++ 2"$%/&+ +E/3-3 $3 -*+ (%21)4,+E+& 2"$%/&+ /1%< FQU<
$%& )1,+2(,$0 *"&018+% 2"$%/&+< 'FQ6 N*+3+ 34+2/+3 $0+
0+,$-+& 5" -*+ $2/& &/3312/$-/1% 1: 'FQ^
'FQ>$GA ] FQU [ '[

>IA

N*+ 21%2+%-0$-/1% 1: :0++ 2"$%/&+ /3 -*+ 3() 1: -*+ FQU $%&

'FQ 21%2+%-0$-/1%3< $%& -*+ +G(/,/50/() &/$80$) 3*19% /%
q/86 H /,,(3-0$-+3 -*+ &/3-0/5(-/1%6 N*/3 :/8(0+ 3*193 -*+
401410-/1%3 1: :0++ 2"$%/&+ $3 FQU< $%& 'FQ $3 $ :(%2-/1%
1: 4' $- HI rF6 ?- 4' .$,(+3 5+,19 X< 2"$%/&+ /3 40+&1)/%$%-,"
40+3+%- $3 -*+ (%;/1%/C+& 'FQ )1,+2(,+< 9*/2* /3 +$3/,"
.1,$-/,/C+& 5+2$(3+ 1: /-3 */8* .$410 40+33(0+6 N*+ +G(/,/50/()
/3 &/34,$2+& /% :$.10 1: 2"$%/&+ /1% :10)$-/1% $- 4' .$,(+3
$51.+ X6

100
90
80

Percentage of HCN

N*+ ?@' -+2*%1,18" 9$3 10/8/%$,," &+.+,14+& $- -*+

a%/.+03/-" 1: a-$* :10 -*+ :$3- $%& +::/2/+%- :,1-$-/1% 1: :/%+
4$0-/2,+3 :01) 3(34+%3/1% RX<KS6 ?,31< 0+2+%- 3-(&/+3 /%&/2$-+
-*$- -*+ :,(/& :,19 21%&/-/1%3 /%3/&+ -*+ ?@' 3"3-+) 2$% 5+
+::+2-/.+," +E4,1/-+& :10 $/0 3-0/44/%8 1: h\F3 :01) 21%;
-$)/%$-+& 9$-+0 RkS6
7+3(,-3 0+410-+& /% -*+ ,/-+0$-(0+ RPJ<PPS /%&/2$-+ -*$- -*+
80+$-+3- )$33 -0$%3:+0 1: 21)41(%&3 :01) 9$-+0 -1 $/0 /3
$2*/+.+& :10 -*13+ 21)41(%&3< 9*/2* *$.+ */8* .$,(+3 1:
'+%0"p3 ,$9 21%3-$%-3 $%& $0+ 0+,$-/.+," /%31,(5,+ /% 9$-+06 =- /3
3$:+ -1 3$" -*$- 9*+% 21)41(%& 4014+0-/+3 :$.10 $/0 3-0/44/%8<
)$E/)() )$33 -0$%3:+0 9/,, 122(0 /% $/0 3-0/44+03 -*$U )$/%-$/% -*+ 80+$-+3- 4133/5,+ /%-+0:$2/$, $0+$ 5+-9++% 5(,M
,/G(/& -*$- 21%-$/%3 -*+ 'FQ>8A $%& -*+ 3-0/44/%8 $/0o
U /%20+$3+ -*+ )$8%/-(&+ 1: -*+ ,/G(/& )$33;-0$%3:+0 21+::/;
2/+%- 5" 401./&/%8 3(::/2/+%- -(05(,+%2+ -1 )/%/)/C+ -*+
51(%&$0" ,$"+0 -*/2M%+336
N*+ ?@' 0+$2-10 /3 1%+ 1: -*+ %+9< +)+08/%8 3-0/44/%8
-+2*%1,18/+3< 9*/2* 2$% :(,:/,, 51-* 0+G(/0+)+%-3 :10 )$E;
/)() )$33 -0$%3:+06 N*+ ?@' (%/- 21%3/3-3 1: -91 21%2+%-0/2
0/8*-;.+0-/2$, -(5+3 $%& $ 21%.+%-/1%$, 2"2,1%+ *+$&+0 $- -*+
-146 N*+ 4101(3 /%%+0 -(5+ /3 21%3-0(2-+& 1: $%" 3(/-$5,+
)$-+0/$,< 3(2* $3 4,$3-/2< 2+0$)/2 10 3-$/%,+33 3-++,< $%& $,,193
:10 -*+ 34$08/%8 1: $/0 10 $%" 1-*+0 8$3 10 3-+$)6 N*+ 1(-+0
%1%4101(3 -(5+ 3/)4," 3+0.+3 -1 +3-$5,/3* $% $/0 O$2M+- $%&
401./&+3 :10 -*+ +.+% &/3-0/5(-/1% 1: -*+ $/0 -*01(8* -*+ 4101(3
-(5+6 N*(3< -*+ ?@' 2$% 5+ (3+& :10 $/0 3-0/44/%8 9*+0+
.1,$-/,+ 34+2/+3< 3(2* $3 'FQ>8A 9*/2* *$3 $ */8* .$410
40+33(0+ $%& .1,$-/,/C+3 $3 $ 8$3 >'+%0"p3 ,$9 1: 21%3-$%- 1:
f6Z $-)B)1,+A RPHS< 2$% 5+ &/34,$2+& :01) 31,(-/1% 5" $/0<
9*/2* /3 21%3/&+0+& /% -*/3 4$4+06 N*+ 2"$%/&+ 31,(-/1% /3 :+&
-$%8+%-/$,," $- -*+ -14 -*01(8* -*+ 2"2,1%+ *+$&+0 -1 &+.+,14 $
39/0, :,19 $&O$2+%- -1 -*+ /%3/&+ 3(0:$2+ 1: -*+ 4101(3 -(5+<
,+$./%8 $% +)4-" $/0 210+ 2+%-+0+& 1% -*+ $E/3 1: -*+ ?@' (%/-6
N*+ */8*;.+,12/-" 39/0, :,19 3*+$03 -*+ 34$08+& $/0 -1 401&(2+
$ */8* 21%2+%-0$-/1% 1: 3)$,, 5(55,+3 $%& /%-/)$-+ /%-+0$2-/1%
5+-9++% -*+3+ %()+01(3 :/%+ 5(55,+3 $%& -*+ 2"$%/&+
31,(-/1%6 e$3+1(3 401&(2-3 $0+ -*+% -0$%3410-+& 0$&/$,," -1
-*+ 2+%-+0 1: -*+ 2"2,1%+6 N*+ )$O10 410-/1%3 1: -*+ 8$3 4*$3+
)1.+ -19$0&3 -*+ .10-+E :/%&+0 1: -*+ 2"2,1%+ *+$&+0 $%& $0+
.+%-+& /%-1 $% $440140/$-+ 413-;-0+$-)+%- &+./2+6 N*+ 34+2/:/2
2$4$2/-" 1: -*+ ?@' 3"3-+) /3 $- ,+$3- P<IJJ ,/-+03 4+0 )/%(-+
4+0 6JHK 2(5/2 )+-+0 1: +G(/4)+%- .1,()+< PJJUfJJ -/)+3 -*$1: 21%.+%-/1%$, $/0;3-0/44/%8 +G(/4)+%-6 N*+ ?@' +G(/4)+%0+G(/0+3 $% 14+0$-/%8 34$2+ 3/8%/:/2$%-," ,+33 -*$% -*$- 1: $
4$2M+& -19+0 10 1-*+0 $/0 3-0/44/%8 &+./2+3< 9*/2* 0+3(,- /% $
3/8%/:/2$%- 3$./%83 /% 2$4/-$, 213-6 ? 32*+)$-/2 &0$9/%8 1: -*+
?@' (%/- $3 (3+& :10 $/0 3-0/44/%8 1: 2"$%/&+ /3 40+3+%-+& /%
q/86 P6

ASH

Air

70
60
50
40
30
20
10
0
6

10

11

12

pH
?)2<.& =@ YG(/,/50/() &/3-0/5(-/1% &/$80$) :10 2"$%/&+ $3 $ :(%2-/1% 1: 4'6

JkTJ;XIPfBJTBJZJZ;JH b PX6IJ[6IJBJ

25,6& 78*& +,358"9& :; >HJJTA Z

<=99 '(>,)
'"&018+% 2"$%/&+ >'FQA< $,31 M%19% $3 *"&012"$%/2 $2/&<
/3 $ 21,10,+33 8$3 10 ,/G(/& 9/-* $ 51/,/%8 41/%- 1: HI6X rF< $
.$410 40+33(0+ 1: PJJ Md$ $- Hf rF $%& '+%0"s3 ,$9 21%3-$%- 1:
f6Z $-)B)1,+ RPHS< -*/3 )$M+3 'FQ .+0" .1,$-/,+6 N*(3< ,19
4'< */8* -+)4+0$-(0+< ,19 40+33(0+< $%& /%-/)$-+ 21%-$2- 9/-*
$/0< $,, -+%& -1 /%20+$3+ -*+ 0$-+ 1: &/33/4$-/1% 1: 2"$%/&+ :01)
31,(-/1% $3 *"&018+% 2"$%/&+6
=% $&&/-/1% -1 :0++ 2"$%/&+< 1-*+0 21)4,+E+3< 3(2* $3 -*+
)+-$, 2"$%/&+ 21)4,+E+3 :10)+& 9/-* 81,&< )+02(0"< C/%2<
2$&)/()< 3/,.+0< 2144+0< %/2M+,< /01% $%& 215$,-< )(3- 5+
21%3/&+0+&6 N*+3+ $0+ 2,$33/:/+& /%-1 :/.+ 8+%+0$, 2$-+810/+3< $3
3*19% /% N$56 P RPTS6
A$/8& 9@ F,$33/:/2$-/1% 1: 2"$%/&+ $%& 2"$%/&+ 21)4,+E+3 1% -*+ 5$3/3 1: 3-$5/,/-"
RPTS6
F,$33/:/2$-/1%

F1)41(%&

q0++ 2"$%/&+

FQU< 'FQ

@/)4,+ 21)41(%&3
t%>FQAH< F&>FQAH< F(FQ< Q/>FQAH< ?8FQ
$A 0+$&/," 31,(5,+
5A %+(-0$, /%31,(5,+ 3$,-3 Q$FQ < jFQ< F$>FQAH< '8>FQAH
_+$M 21)4,+E+3

t%>FQAZHU< F&>FQATHU< F&>FQAZHU

D1&+0$-+," 3-01%8
21)4,+E+3

F(>FQAHU< F(>FQATHU< Q/>FQAZHU< ?8>FQAHU

@-01%8 21)4,+E+3

q+>FQAfZU< F1>FQAfZU< ?(>FQAHU< q+>FQAfTU

B !C6&.)D&";$8 E.,%&*<.&

N*+ -+0) -1-$, 2"$%/&+ /3 (3+& :10 $,, 2"$%/&+< >:0++ $3 9+,, $3
2110&/%$-+& 2"$%/&+A< 40+3+%- /% $ 3$)4,+6 N*+ 21%2+%-0$-/1%
1: :0++ 2"$%/&+ /% $ 31,(-/1% &+4+%&3 1% -*+ 4' .$,(+ 1: -*+
31,(-/1% $%& /-3 21%-+%- 1: *+$." )+-$,3 2$4$5,+ 1: :10)/%8
2"$%/&+ 21)4,+E+36 _+$M," 21)4,+E+& )+-$, 2"$%/&+3 &+;
21)413+ $- 4' .$,(+3 ,19+0 -*$% Z< 9/-* -*+ +.1,(-/1% 1:
*"&018+% 2"$%/&+6 @-01%8 )+-$,;2"$%/&+ 21)4,+E+3 $0+
(3($,," (%$::+2-+& $- 011) -+)4+0$-(0+ 5+2$(3+ -*+3+
21)4,+E+3 $0+ .+0" 3-$5,+ $%& 0+3/3- 1E/&$-/1%< *19+.+0<
4$0-/$, &+21)413/-/1% 2$% 122(0 9/-* /%20+$3/%8 -+)4+0$-(0+
$%& $2/& 21%-+%-6
N*+ 2"$%/&+ 0+2"2,/%8 4012+33 (-/,/C+3 -*+ .1,$-/,/-" 1:
'FQ>8A $- ,19 4' -1 3-0/4 :0++ 2"$%/&+ :01) 31,(-/1% 10 3,(00"
9/-* $/0 $%& 0+21.+0 /- /% $ 2$(3-/2 31,(-/1%6 N*+ 3/)4,/:/+&
2*+)/3-0" 1: -*+ 4012+33 /3 0+40+3+%-+& 5" -*+ :1,,19/%8
0+$2-/1%3^
FQU [ '[ ] 'FQ>$GA

>fA

'FQ>$GA ] 'FQ>8A

>XA

'FQ>8A [ \'U ] FQU [ 'HJ

>KA

=% -*+ :/%$, 3-+4< -*+ 'FQ>8A &/::(3+3 /%-1 -*+ 3-0/44/%8

31,(-/1% 1: 21%2+%-0$-+& 31&/() *"&01E/&+ $%& 0+$2-3 -1 :10)
$G(+1(3 Q$FQ6

25,6& 78*& +,358"9& :; >HJJTA Z<

=- *$3 5++% $,)13- KJ "+$03 3/%2+ -*+ D/,,3;F019+ 4012+33

:10 2"$%/&+ 0+8+%+0$-/1% 9$3 &+.+,14+& 5" -*+ F1)4$%"
!+%+:/2/$&10$ &+ d$2*(2$< D+E/21 >Y%8,$%& d$-6 Q16 HZPffk<
T6k6HZA RPZS $%& (%-/, -1&$" %1 3/8%/:/2$%- 2*$%8+3 -1 -*+
4012+33 *$.+ 5++% )$&+6 N*+ 3/)4,+3- 4012+33 :10 2"$%/&+
0+2"2,/%8 /%.1,.+3 $2/&/:"/%8 -*+ 2,$0/:/+& 31,(-/1%< -*+%
.1,$-/,/C/%8 1: -*+ 'FQ>8A :10)+& $%& 0+$53105/%8 /- :01)
-*+ $/0 3-0+$) 9/-* $ 2$(3-/2 10 )/,M 1: ,/)+ 340$" -1 401&(2+
$G(+1(3 Q$FQ6
7+2+%-,"< -*+ 21)4$%" D/%+0$ 7+$, &+, D1%-+ RPIS
$2/&/:/+& -*+ 2,$0/:/+& 2"$%/&+ 31,(-/1% 9/-* 3(,:(0/2 $%&
*"&012*,10/2 $2/& >-1 $.1/& 8"43() :10)$-/1%A6 =% -*+
.1,$-/,/C$-/1% 3-$8+ $ 3+0/+3 1: :1(0 3-0/44/%8 -19+03 4$2M+&
9/-* 911&+% 80/&3 $0+ (3+&6 N*+ -19+03 $0+ 21%3-0(2-+& 1: TPf
3-$/%,+33 3-++, $%& )+$3(0+ $51(- kI 2) 1: &/$)+-+0 5" K ) /%
*+/8*-6 ? -1-$, 2"$%/&+ 0+21.+0" 1: $51(- kI 4+02+%- /3
$2*/+.+& 9/-* $51(- IJ 4+02+%- 0+)1.$, 0+$,/C+& /% +$2* 1: -*+
:1(0 3-0/44/%8 3-$8+36

YE4+0/)+%-3 :10 2"$%/&+ 0+2"2,/%8 5" $/0 3-0/44/%8 $- -*+

=%3-/-(-+ 1: N+2*%1,18" 1: @$,-/,,1 4/,1- 4,$%- /%2,(&+&
$2/&/:/2$-/1% 1: -*+ 2"$%/&+ 31,(-/1% 5" 5(55,/%8 @\H 8$3 -1
-*+ HUX 4' 0$%8+ :10 'FQ>8A :10)$-/1% $%& 3-0/44/%8 9/-* $/0
/% $ H;/%2* &/$)+-+0 ?@' (%/-6 F*+)/2$, $%$,"3/3 :10 2"$%/&+
/% -*+ +::,(+%- 3-0+$)3 9$3 $221)4,/3*+& 9/-* $ 0+:,(E
&/3-/,,$-/1% )+-*1&6 =)410-$%- $34+2-3 1: -*+ &/3-/,,$-/1% 3-+4
$0+ -*+ +,/)/%$-/1% 1: /%-+0:+0+%2+3 $%& -*+ &+21)413/-/1% 1:
3-$5,+ )+-$,;2"$%/&+ 21)4,+E+36 N*+ 21,,+2-+& 2"$%/&+ 9$3
G($%-/:/+& 5" -/-0$-/1% 9/-* 3/,.+0 %/-0$-+ 3-$%&$0& 31,(-/1%
$%&B10 -*+ /1%;3+,+2-/.+ +,+2-01&+
`(0/%8 -*+ +E4+0/)+%-3 -91 3-0+$)3 *$& -1 5+ &+,/.+0+& -1
-*+ ?@'^ -*+ 2"$%/&+ 31,(-/1% $%& -*+ $/06 F"$%/&+ 31,(-/1%
9$3 401./&+& 5" $ 3()4 4()4 )1(%-+& 1% $ TJJ ,/-+0 0+-+%-/1%
-$%M6 N*+ 2"$%/&+ 31,(-/1% :,19 0$-+ 9$3 $&O(3-+& (3/%8 $
0+8(,$-+& 0+-(0% :,19 -1 -*+ -$%M6 a3/%8 $% $/0 21)40+3310<
$/0:,19 9$3 +.+%," &/3-0/5(-+& 5+-9++% -*+ (44+0 $%& ,19+0
3+2-/1%3 1: ?@' $%& $,, 4$0-3 9+0+ 3+$,+& 9/-* 8$3M+-36
F"$%/&+ 31,(-/1% $2/&/:/+& -1 4' ] HUX /% -*+ -$%M 9$3 :+& $&/::+0+%- :,19 0$-+3 -1 -*+ -14 1: -*+ ?@'6 N*+ +E/- 4/4+ 9$3
,12$-+& $- -*+ 51--1) 1: -*+ 2,13+& 0+8+%+0$-+& 2"$%/&+ -$%M
-1 40+.+%- 0+,+$3+ 1: 'FQ>8A6 N*+ 'FQ;,$&+% $/0 9$3
21,,+2-+& /% -*+ $53105+0 9*+0+ 0+$2-/1% 9/-* 31&/()
*"&01E/&+ PJ L .B. 0+8+%+0$-+& -*+ Q$FQ $G(+1(3 31,(-/1%6
?/0 9$3 /% 2,13+& 2/02(/- $- 3,/8*-," 0+&(2+& 40+33(0+ :10
.1,$-/,/C$-/1% 1: *"&018+% 2"$%/&+ :01) -*+ $2/&/:/+& 9$3-+
$%& $53104-/1% 1: *"&018+% 2"$%/&+ /% $ 31,(-/1% 1: 31&/()
*"&01E/&+6 N*+ (3+ 1: $/0 /% 2,13+& 2/02(/- 40+.+%-3 /%-01&(2;
-/1% 1: $-)134*+0/2 2$051% &/1E/&+ 9*/2* 91(,& %+(-0$,/C+
,/)+ /% -*+ $53104-/1% 31,(-/1%6 \4+0$-103 9+0+ 401./&+& 9/-*
4+031%$, 'FQ 8$3 )1%/-10B$,$0) (%/-3 >`0u8+0@+%310v;
w@YF'FQ;fK Jk PIJ /3 $ -0$&+)$0M 1: -*+ `0u8+09+0M
?M-/+%8+3+,,32*$:-< 0+8/3-+0+& /% e+0)$%"A6

! HJJT _=VYg;hF' h+0,$8 e)5' i F16 je$?< _+/%*+/)

JkTJ;XIPfBJTBJZJZ;JT b PX6IJ[6IJBJ

<=99 '(>,)

F +&1<8;1 $"* G)1%<11),"

Free Cyanide (PPM)

1000
100
0.5 l/min of SO2
2 l/min of SO2

10

70
60
50
40
30

1
0.1

Air = 150 l/min.

20

Air = 130 l/min.

10
0
0

10

15
20
25
Time of distribution air (sec.)

30

35

?)2<.& B@ Y::+2- 1: -/)+ 1: $/0 &/3-0/5(-/1% 1% 2"$%/&+ 0+21.+0"6

Cyanide Regeneration, %

YE4+0/)+%-3 9+0+ 4+0:10)+& (3/%8 IJJ 44) 1: FQU

40+4$0+& :01) $ IJ 8BV 3-12M 31,(-/1% 1: $G(+1(3 31&/()
2"$%/&+ :01) 4,$%- /% $ TJJ ,/-+0 :/5+08,$33 .+33+, $- $)5/+%-+)4+0$-(0+ >HZ rFA6 q/86 T 40+3+%-3 -*+ +E4+0/)+%-$,
21%&/-/1%3 $%& -*+ 0+3(,-3 15-$/%+& 0+8$0&/%8 2"$%/&+ &+4,+;
-/1% 9/-* -*+ $2/&/:/2$-/1% 1: -*+ :++& 31,(-/1% 9/-* @\H>8A6
?,31< q/86 T 3*193 -*+ .$0/$-/1% 9/-* -/)+ 1: -*+ 2"$%/&+
21%2+%-0$-/1% :10 -*+ -91 :,19 0$-+3 1: @\H>8A6 ?3 )$" 5+ 3++%<
-*+ :10)$-/1% 1: .1,$-/,+ 'FQ>8A /3 $ :$3- 0+$2-/1% $%& 2*$%8+3
/% -*+ 21%2+%-0$-/1% 1: :0++ 2"$%/&+ $0+ $ :(%2-/1% 1: -*+
80$&($, $2/&/:/2$-/1% 1: -*+ 31,(-/1%6

Cyanide recovery (%)

80

0.01

85
75

Air flow rate = 210 l/min

65
55

pH=2

45

pH=5

35

pH=7

25
15
15

0.001

20

25

30

35

40

45

Solution Flow rate, l/min

0

5
10
15
Time Of Feed SO2(Minutes)

20

?)2<.& >@ h$0/$-/1% 9/-* -/)+ 1: -*+ 2"$%/&+ 21%2+%-0$-/1% :10 -91 :,19 0$-+3 1:
@\H>8A6

N"4/2$, 0+3(,-3 21,,+2-+& $- 4' H6J :10 2"$%/&+ 0+8+%+0$-/1%

$0+ 40+3+%-+& /% q/86 Z6 ?,, +E4+0/)+%-3 9+0+ )$&+ $- -*+ 3$)+
31,(-/1% :,19 0$-+ 1: HJ ,/-+03B)/%(-+ $%& -91 $/0 :,19 0$-+36
?,31< -*+ &$-$ /% q/86 Z 3*19 -*$- 2"$%/&+ 0+8+%+0$-/1%
/%20+$3+3 5+2$(3+ $/0 :,19 /3 0$-+;&+4+%&+%-6
?,31< $3 3++% /% q/86 I< -*+ 4' $%& 31,(-/1% :,19 0$-+
/%:,(+%2+ 2"$%/&+ 0+21.+0"6 N*(3< $- $ ,19 4' .$,(+ 9*+% -*+
21%2+%-0$-/1% 1: FQU /3 .+0" 3)$,,< $ */8* 0+21.+0" /3 $2*/+.+&
&(+ -1 -*+ +$3" .1,$-/,/C$-/1% 1: 'FQ>8A6 \% -*+ 1-*+0 *$%&< $4' ] I< -*+ 0+21.+0" /3 3/8%/:/2$%-," ,19+0 >IH L $- HJ ,/-+03B
)/%(-+A6 N*+3+ -+3-3 /%&/2$-+ -*$- 3-0/44/%8 1: .1,$-/,+ 'FQ>8A
9/-* $/0 $%& 0+8+%+0$-/1% 1: 2"$%/&+ 9/-* 31&/() *"&01E/&+ /3
4';&+4+%&+%-6

?)2<.& F@ F"$%/&+ 0+21.+0" $%& 0+8+%+0$-/1% 9/-* ?@'6

!$3+& 1% -*+3+ -+3- 0+3(,-3< $% /%/-/$, +21%1)/2 21)4$0/31%

9/-* 2(00+%- D/,,3;F019+ 4012+33+3 /3 3())$0/C+& /% N$56 H6
?,, 1: -*+3+ 4012+33+3 :10 2"$%/&+ 0+21.+0" $0+ 2(00+%.+03/1%3 1: -*+ 10/8/%$, D/,,3;F019+ 4012+33 RPH<PI<PfS6 _/-*
-91 3-$8+3< -*+ 2"$%/&+;/1% 21%2+%-0$-/1% 2$% 5+ 0+&(2+& -1
5+,19 J6H )8BV 9/-* 0+21.+0/+3 W -*$% kk L6
q/%$,,"< /% N$56 T< 5$3+& 1% -*+ 4/,1- 4,$%- 0+3(,-3< +3-/)$-+3
1: -*+ 213- 1: 2"$%/&+ 0+21.+0" *$.+ 5++% 40+4$0+& 4+0
M/,180$) 1: 2"$%/&+ 0+21.+0"< $%& -*+ 4+0:10)$%2+ 1: -*+
?@' 21)4$0+3 :$.10$5," -1 -*+ 4$2M+&;5+& 3-0/44/%8 -19+0
-+2*%1,18"6
N*+ $&.$%-$8+ 1: -*+ ?@' -+2*%1,18" 1.+0 4$2M+& -19+03
/3 -*+ 0+3/&+%2+ -/)+6 =% 4$2M+& -19+03< -*+ 0+3/&+%2+ -/)+ :10
3-0/44/%8 .$0/+3 :01) X -1 HJ )/%(-+3< 9*+0+$3 -*+ ?@'
14+0$-+3 9/-* $ 0+-+%-/1% -/)+ 1: 1%," Z 3+21%&3 RXS6

A$/8& =@ F1)4$0/31% 1: -*+ +E4+0/)+%-$, 0+3(,-3 9/-* 0+3(,-3 :01) -0$&/-/1%$, D/,,3;F019+ 14+0$-/1%3
RPH<PI<PfS6
D/%+

7+$2-10

?/0BV/G

L 7+26

FQ=Q

FQ\aN

@-0+$)3

q,/% q,1% D/%+

Z -19+03

IHP

kH

IfJ

ZZ

31,(-/1%

7+$, &+, D1%-+ >D+E6A

Z -19+03

TZJ

kT

HHJ

31,(-/1%

?h7 >F$%)+-A

H -19+03

TTJ

kI

TTJ

31,(-/1%

F6 76 d6 >N$3)$%/$A

kI

HJJ

31,(-/1%

F"$%/3105
>QY7F\ `+V$)$0< a@A

H -19+03

TJJ

kI

fJJ

TJ

3,(00"

?@' >!$2/3;DnE/21A

P ?@'

PJ

KJ

HIJ

IJ

31,(-/1%

?@' >!$2/3; DnE/21A

P ?@'

PJJ

kJ

HIJ

HI

3,(00"

! HJJT _=VYg;hF' h+0,$8 e)5' i F16 je$?< _+/%*+/)

JkTJ;XIPfBJTBJZJZ;JZ b PX6IJ[6IJBJ

25,6& 78*& +,358"9& :; >HJJTA Z

<=99 '(>,)
A$/8& >@ F1)4$0/31% 1: 213- $%& 4+0:10)$%2+
D/%+

F13>a@bBM8 FQA

7$-/1
?/0B31,(-/1%

L 7+21.+0"
@/%8,+ 3-$8+

7+)$0M3

7+$, &+, D1%-+

>4$2M+& -19+03A

P6JJ

HJJUTIJ

fZ

!(/,&;(4 8"43() $%&

2144+0 -*/12"$%$-+
40+2/4/-$-+3

!$2/3 D/%+
>?@'A

J6KI

HJUPJJ

KJ

q0++ 1: 40+2/4/-$-+3

H ',"%8<1),"1

+&K&.&"%&1

N*+ $44,/2$-/1% 1: -*+ 8$3;34$08+& *"&012"2,1%+ 0+$2-10 :10

2"$%/&+ 0+2"2,/%8 /3 $ %+9 $%& 41-+%-/$,," /%+E4+%3/.+
$4401$2* :10 2"$%/&+ 0+21.+0"6 N*+ ?@' 0+$2-10 *$3 5++%
-+3-+& /% 5+%2* $%& 4/,1-;4,$%- 32$,+ $44,/2$-/1%3 $%& *$3 5++%
401.+% +::+2-/.+ :10 -*+ 0+2"2,/%8 1: 2"$%/&+ /% 31,(-/1% $%&
3,(00/+36
YE4+0/)+%-3 4+0:10)+& 3*19 -*$- -*+ ?@' 0+$2-10 /3 .+0"
21)4+-/-/.+ 9/-* 1-*+0 -+2*%1,18/+3 $%& -*$- 3/%8,+;3-$8+
2"$%/&+ 0+21.+0" +E2++&/%8 KJ L 2$% 5+ $2*/+.+&6

3%I",J8&*2&D&";1

RPS
RHS
RTS
RZS
RIS

RfS
RXS
RKS
RkS

RPJS
RPPS
RPHS

N*+ $(-*103 9/3* -1 +E40+33 -*+/0 80$-/-(&+ -1 F\Q?FgN<

F\@QYN >XJP6kI;dA $%& e0(41 D/%+01 !$2/3 :10 :/%$%2/$,
3(4410- $%& 4+0)/33/1% -1 4(5,/3* -*+ 0+3(,-36 D$%" -*$%M3 81
-1 V$)$0 a%/.+03/-" :10 3(4410- $%& $33/3-$%2+6

RPTS
RPZS

7+2+/.+&^ l(," TP< HJJH RFYN PffKS

RPIS
RPfS

N6 D2Q(,-"< ?/8/8* ?(*& =LL9< @< HIf6

D6 =6 l+::0+"< =6 D6 7/-2*/+< !& 79,3A)"35,6& B"3& =LLL< CDEF THIX6
`6 D6 _*/-+< N6 ?6 d/,1%< F6 _11,$0&< G(A& %,#& =LLL< HD< HPJI6
e6 V6 D/,-C$0+M< F6 '6 @$)4$/1< l6 V6 F10-/%$< ?/8,)(9# 78*& =LL=< C@F XI6
l6 76 d$08$< '6 D+02$&1< d0+2/1(3 D+-$,3 YE-0$2-/1% 5" `/0+2\E/&$-/.+ d0+33(0+ F"$%/&$-/1% 1: !$2c3 F1%2+%-0$-+3< ')"3& %(80"9
I"90 <")=6< !+$.+0 F0++M 9MM>< HJk6
l6 `6 `+3$/< F6 7$)$M0/3*%$< d6 @6 d$-+,< l6 ?9$3-*,< 25,6& 78*& G")90
9MMN< HH< PPI6
l6 `6 D/,,+0< g+ g/< ?/8& ')"3& (80 7JA)(3A& ?,A(99& %,.& 9MNM< H< TJX6
`6 V+,/%3M/< 76 !1M1-M1< l6 '(4M$< l6 `6 D/,,+0< ?/8& ?,A(99& ')"3& 9MMH<
@< KX6
l6 `6 D/,,+0< `6 V+,/%3M/< l6 76 d$08$< q/%$, 7+410-;Fw KHTXPP< ?&.$%2+
d012+33 N+2*%1,18" :10 -*+ _$3-+4$4+0 7+2"2,/%8 d,$%-3 $%& d(,4B
d$4+0 d,$%-3< @1(-*9+3- F+%-+0 :10 Y%./01%)+%-$, 7+3+$02* $%& d1,/2"<
9MMH@
`6 q6 V$!0$%2*+< D6 76 F1,,/%3< G(A& 78./)"8& %,#& 9MMH< ;K< TZK6
_6 l6 d$0M+0< '6 `6 D1%-+/-*< 78./)"8& ')"*),## 9MMH< C@< XT6
@)/-*< N6 D(&&+0< +5, 25,6/#A)L (80 +),(A6,8A "M 2L(8/0(A/"8 G(#A,#<
D/%/%8 l1(0%$, !11M3 V-&6< V1%&1% 9MM9< HXX6
_6 '1+2M+0< `6 D(/0< %,#& -,.& /8 7JA)(3A/., ?,A(99=)*L 9MMH< @< Hk6
F6 _6 V$90< F"$%/&+ 7+8+%+0$-/1% $3 d0$2-/2+& 5" -*+ F1)4$xc$
!+%+:/2/$&10$ &+ d$2*(2$< D+E/21< N+2*%/2$, d(5,/2$-/1% ?=DY Q16 HJK
>JfA 9M=M< PUTX6
7+410- F1)4$xc$ D/%+0$ &+ 7+$, &+, D1%-+< d$2*(2$< D+E/21< d012+33
:10 -*+ 7+21.+0" 1: F"$%/&+< 9MMO< PUPT6
D6 !1-C< l6 @-+.+%31%< 78*& N ?/8/8* !& 9MMF< ;< ZZ6

3//.&-)$;),"1
?@' $/0;34$08+& *"&012"2,1%+
$G
$G(+1(3 4*$3+
8
8$3 4*$3+

yyyyyyyyyyyyyyyyyyyyyyy

25,6& 78*& +,358"9& :; >HJJTA Z<

! HJJT _=VYg;hF' h+0,$8 e)5' i F16 je$?< _+/%*+/)

JkTJ;XIPfBJTBJZJZ;JI b PX6IJ[6IJBJ

4
New Technology for Recovery of Gold
and Silver by Pressure Cyanidation
Leaching and Electrocoagulation
Jos R. Parga1, Jess L. Valenzuela2 and Jos A. Daz1
1Department

of Metallurgy and Materials Science Institute

Technology of Saltillo, Saltillo Coahuila
2Department of Chemical Engineering and Metallurgy
University of Sonora, Hermosillo, Sonora
Mxico

1. Introduction
The present chapter describes a new technology of pressure oxidation/cyanidation leaching
for the dissolution of gold and silver and the recovery of the precious metals by using the
electrochemical process of Electrocoagulation (EC). The novel method demonstrates that the
oxidation and dissolution of gold and silver in alkaline cyanide solution can be conducted
simultaneously in the same reactor in less than 90 minutes with a recovery that exceeds 96%.
Then, the pregnant cyanide solution with gold and silver is sent for recovery of precious
metals by using a very promising electrochemical technique (EC) that does not require high
concentrations of silver and gold in cyanide solutions.
Gold is classed as a noble metal because of its inertness to most chemical reactions under
ordinary conditions. At the present time, cyanidation has superseded all previous leaching
processes, particularly chlorination, because of its ability to effectively and economically
treat ores containing as little as 1-3 g/ton gold. Cyanidation processes are especially suitable
for treatment of gold/silver-bearing sulphidic materials. Gold cyanidation has been
reported to involve the chemical reactions shown in Eqs. (1) and (2). Silver is accomplished
in the same fashion (Senanayake, 2008; Parga et al., 2007).
2Au + 4NaCN+O2+2H2O
2Au + 4NaCN+H2O2

2 Na[Au(CN)2]+2NaOH+H2O2
2 Na[Au(CN)2]+2NaOH

(1)
(2)

The Equation (1) proposed by Elsner is stoichiometrically correct but does not describe the
cathodic reactions associated with the dissolution. The stoichiometry of the process shows
that 4 moles of cyanide are needed for each mole of oxygen used. At room temperature
and std. atmospheric pressure, approximately 8.2 mg of oxygen are present in one liter of
water. This corresponds to 0.27 x 10-3 mol/L. Accordingly, the sodium cyanide concentration
(molecular weight of NaCN = 49) should be equal to 4 x 0.27 x 10-3 x 49 = 0.05 g/L or
approximately 0.01%. This was confirmed in practice at room temperature by a very dilute

72

Noble Metals

solution of NaCN of 0.01% - 0.5% for ores, and for concentrates rich in gold and silver of
0.5 % -5 % (Parga et al., 2007). Details of this electrochemical reaction have received
considerable attention and under certain circumstances the reaction is limited by the
coupled diffusion of CN- and O2 to the gold surface. Lime or sodium hydroxide (caustic)
is added to keep the system at an alkaline pH of 10-11. This protective alkalinity is
required to counteract the generation of acid during cyanidation, thereby preventing
cyanide degradation and the formation of the deadly HCN gas.
Gold and silver ores are classified as refractory when a significant portion of the precious
metals cannot be extracted by the conventional cyanidation process. The refractoriness may
be of a physical or chemical nature. The former type is usually due to sub-microscopic
particles of gold being locked within mineral particles, for example in sulphides or silicates.
Refractory gold-silver ores contain precious metals locked up in a matrix of pyrite and/or
arsenopyrite (Parga et al., 2007). Such ores are not amenable to cyanidation. To liberate the
gold-silver from the sulfide matrix and render it accessible to cyanidation. It is a common
practice to subject them to a preoxidation in order to enhance the recovery of the precious
metals. Although effective, these techniques result in the production of large quantities of
environmental hazardous substances such as sulphur dioxide gas or sulfuric acid, which can
cause difficulties in compliance with environmental pollution regulations. After review of
the literature (Parga et al., 2007), it was shown that roasting is currently the most cost
effective means of oxidizing refractory pyrite and arsenopyrite concentrates to produce a
product amenable to the cyanidation process. However, the major drawback of roasting is
that it produces large quantities of SO2 gas which is released into atmosphere and this is not
acceptable. The sulphur dioxide must be collected, or an alternative technology used. One
such alternative process that has previously been used successfully around the world, is that
of pressure aqueous pre-oxidation of the sulphide minerals. Pressure oxidation has been the
most popular method for the treatment of refractory gold concentrates (see Table 1); This
process utilizes oxygen or air at high pressures and temperatures to oxidize an aqueous
slurry of the ore or concentrate to produce hematite, iron sulphates and considerable
quantities of free sulphuric acid. Because of this, before the cyanidation process excessive
lime or caustic soda must be used in order to the pH of the pulp to 10 or 11.
This process, which is used in many commercial plants around the world, involves the
recovery of the precious metals by oxidation pretreatment followed by traditional
cyanidation. By consequence the saving in time for the gold and silver dissolution from ore
or concentrates is limited by the conventional cyanidation leaching step, a process which
requires 48 to 72 hours. It should be remembered that the pressure aqueous pre-oxidation
technology is not used to leach the gold but only to make the cyanide ions accessible to the
gold in the host mineral.

2. Extraction of gold and silver from the argentopyrite / argentite ore

2.1 Pressure oxidation / cyanidation chemistry
The oxidation of gold and silver is a prerequisite for its dissolution in the alkaline cyanide
lixiviant. Pyrite along with arsenopyrite, argentopyrite, sphalerite and covellite are the most
common host minerals of gold, silver and electrum. It is important from a process
optimization standpoint to understand the behavior of each of these minerals during
alkaline pressure oxidation/cyanidation which leads to dissolution/destruction and

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

73

subsequent liberation of gold and silver which would then be available for the cyanide ions.
Pressure oxidation of pyrite and argentopyrite at low temperature (700C) and oxygen
pressure (60 lb/in2) involves reactions yielding ferrous ion, sulfate ion, and elemental sulfur
as products (Anderson and Nordwick, 1996; Chander and Briceo, 1987).
The primary reactions are:
2FeS2 + 7O2 + 2H2O

2Fe2+ + 4SO42- + 4H+

FeS2 + 2H+

Fe2+ + H2S + S0

(3)
(4)

Operation Data
Capacity
T/d
T ( C) P (psi) t (min)
McLaughlin, California USA
Ore
Acid
2700
180
401
90
So Bento Brazil
Concentrate
Acid
240
190
230
90
Barrick Mercur Utah, USA
Ore
Alkaline
790
225
473
70
Getchell USA
Ore
Acid
3000
210
420
130
Goldstrike Nevada, USA
Ore
Acid
1360
225
439
75
Goldstrike Nevada, USA
Ore
Acid
5450
225
400
75
Porgera, Papua New Guinea Concentrate
Acid
1350
190
258
180
Campbell Canada
Concentrate
Acid
70
195
305
120
Barrik USA
Ore
Acid
2000
220
450
100
Goldstrike Nevada, USA
Ore
Acid
11580
200
200
140
Santa Fe Pacific Gold
Ore
Acid
4000
225
460
50
Nevada, USA
Sunshine Mining & Co
Ore
Acid
1000
120
90
60
Idaho, USA
Porgera, Papua New Guinea Concentrate
Acid
2700
190
250
150
Plant
Location

Feed

Medium

Table 1. Commercial plants using pressure aqueous pre-oxidation (Adams M.D., 2005; Parga
et al. 2007).
Ferrous ions produced by reaction (3, 4) are subsequently oxidized to ferric ions.
2Fe2+ + 1/2O2 + 2H+

2Fe3+ + H2O

(5)

And contribute to the leaching of sulfides only as a source of ferric ions. The ferric ions can
also contribute to the oxidation of argentopyrite, argentite, pyrite, pyrrhotite, sphalerite and
chalcopyrite:
AgFe2S3 + Fe3+
Ag2S +

Ag+ + 3Fe2+ + 2S2- + S0

2Fe3+

FeS2 + 8Fe3+ + 4H2O

Fe7S8 + 32H2O + 62Fe3+
ZnS + 2Fe3+
CuFeS2 + 4Fe3+

2Ag+ +

2Fe2+

S0

9Fe2+ + 8H+ + S0 + SO4269Fe2+ + 64H+ + 8SO42Zn2+ + 2Fe2+ + S0

Cu2+ + 5Fe2+ + 2S0

(6)
(7)
(8)
(9)
(10)
(11)

74

Noble Metals

Of course silver has been shown to activate the oxidation and dissociation of chalcopyrite
because a porous sulfur layer is formed (Parga et al., 2007). Then, elemental sulfur may also
be further oxidized to sulfate by oxygen or by ferric sulfate:
2S0 + 3O2 + 2H2O
S0 + 6Fe3+ + 4H2O

4H+ + 2SO42-

(12)

6Fe2+ + 8H+ + SO42-

(13)

This results in the formation of a porous, but nonprotective, elemental sulfur layer, thus
allowing cyanide and dissolved oxygen to access to the previously locked gold, silver and
electrum. It was thought that by maintaining high concentrations of CN- ions in the
pressure leach reactor it would be possible to complex gold and silver (Eq. 14) as they
became liberated and thus achieve both objectives, i.e. decomposition of refractory
minerals and leaching the Au/Ag with the cyanide ions, simultaneously in a single stage.
Also, two of the main advantages of this cyanidation process are the selectivity of free
cyanide for gold and silver dissolution and the extremely high stability of the cyanide
complex as illustrated in Table 2.
Reaction
Au+ + 2CN =Au(CN
Au(CN = AuCN+CN
Au++2HS = Au(HS
Au++HS = Au(HS)
Au++2OH = Au(OH
Au++OH = Au(OH)
Au++OH +CN =
Au(OH)(CN)
Au++2CH3CN =
Au(CH3CN
Au2S = 2Au++S2
Ag++2CN = Ag(CN

K
1038.31039.3
10 7 a
1030.1 b
1024.5 b
1022.0 c
1020.6 c1010.2 d

Reaction
Ag2S = 2Ag++S2
H++S2 = HS
HS +H+ = H2S
2S+HS +OH = S2S2 +H2O
3S+HS +OH = S3S2 +H2O
4S+HS +OH = S4S2 +H2O

K
10 53.5*f
1017m
107
102.2
103.9
104.6

1023.3 e

5S+HS +OH = S5S2 +H2O

104.6

101.6 n

6S+HS +OH = S6S2 +H2O

102.3

Cu2++4CN = Cu(CN
Fe3++6CN = Fe(CN
3Ag++Fe(CN
=
Ag3Fe(CN)6(s)
Au++2S2
= Au(S2O3
Ag++S2
= AgS2O3

1025
1043.6

Ag++2S2

= Ag(S2O3

1013.7

Ag++3S2

= Ag(S2O3

1014.2

10 72.8*f
1020.1

Ag++3CN = Ag(CN

1021.41021.8

Ag++2OH = Ag(OH
Ag++OH = AgOH
Ag++OH +CN =
Ag(OH)(CN)
AgCN = Ag++CN

103.6104.2
102.3103.9
1012.81013.2
10

15.7*

1018.2
1026
108.80

Table 2. Equilibrium constants (Marsden and House, 1960).

For this argentopyrite concentrate, both gold and silver extractions achieved were in fact
greater than 96%.
Since silver in Mexican ores occurs as argentite the cyanidation and sulfide oxidation
reaction are as follows:

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

Ag2S + 2nCN-

2Ag(CN)(n-1) n + S2-

Ag2S + 4CN- + 0.5H2O + O2

2Ag(CN)2- + 0.5 S2O32- + OH

S2- + CN- + 1/2O2 + H2O

2S2- + 2O2 + H2O
S2O32- + 2OH- + 2O2

SCN- + 2OH

S2O32- + 2OH2SO42- + H2O

75
(14)
(15)
(16)
(17)
(18)

According to the above equations, sulfide ions are oxidized to thiosulphate and can
contribute with the dissolution of gold. Also Graham et al. (Graham and James, 1995)
showed that an alkaline or near neutral solution of thiosulphate dissolved gold metal slowly
in the presence of a mild oxidant. The dissolution of the gold can be written as in Equation
(19), where oxygen is the oxidant and thiosulphate is the ligand.
4 Au + 8S2O32- + O2 + 2H2O

4[Au(S2O3)2]3- + 4OH-

(19)

Fig. 1. Schematic mechanism of gold and silver leaching.

Better extractions of gold with thiosulphate are achieved when elevated temperatures (e.g.
65 C) are used (Wan et al.,1993). The proposed leaching reaction mechanism for gold and

76

Noble Metals

silver dissolution in relatively mildly operating conditions of 70 C and 60 psi oxygen

pressure is described in Figure 1. The role of oxygen gas is to dissolve the easily solubilized
sulphides in mildly oxidative pressure and temperature by forming sulphate and metals
(e.g. Fe2+ to Fe3+) to liberate gold occluded in the refractory matrix.
2.2 Experimental details
Mineralogical analysis indicates that the sulfide minerals for the Bacs Mining Co.
concentrate include pyrite, argentopyrite, pyrrhotite, arsenopyrite, chalcopyrite, covellite,
hematite and magnetite. The non-opaque minerals were quartz, calcite, apatite, gypsum,
fluorite and barite. Also, several photomicrographs indicate occlusion and/or
dissemination of micron-size gold, silver, electrum particles in the sulfide minerals such
as argentopyrite, pyrite, sphalerite, arsenopyrite and quartz (Figure 2). The compositions
are listed in Table 3.

Fig. 2. Photomicrograph, Native gold, size 5 m , Argentite (ARG) occluded in pyrite, size
60 m, Electrum (EL) occluded in pyrite, size 10 m.
gr./ton

Au

Ag

Pb

Zn

Cu

Fe

As

Concentrate

87.09

12320

2.6

3.8

0.5

29.2

0.15

32

Ore

4.12

289

0.5

0.4

0.04

3.67

0.1

3.7

Table 3. Analytical data for the composite samples.

2.2.1 Leaching experiments
Experiments were carried out in a four-liter Parr autoclave assembled with impeller,
thermowell, pressure gauge, gas inlet and outlet pipes were used for simultaneous oxidation
and cyanidation in the same autoclave. Samples were ground to 84% minus 40 m or finer,
pulped with fresh tap water. Depending on test requirements, variables such as NaCN,
reaction time, temperature, particle size, pH and pulp density were set and the leaching
experiments were undertaken.

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

77

2.3 Results and discussion

2.3.1 Ambient condition
Preliminary batch testing had indicated that at ambient conditions (25 C, 1atm.) direct
cyanide leaching of the concentrate with air gave poor silver and gold recoveries. The
results obtained are shown in Figures 3 and 4.
2.3.2 Effect of the autoclave retention time
Figure 5 shows that there is an optimum leach time to achieve both maximum gold and
silver extractions. The optimum leach time appears to lie close to 60 minutes at 80 C.

EXTRACTION, %

Increase in time beyond this value leads to chemical degradation of gold and silver
cyanocomplexes, due to the hydrogen ions produced by the sulfide oxidation. Also for
prolonged leaching time there is significant loss in cyanide, since the oxygen present
oxidizes the cyanide to cyanate and ultimately to ammonia and carbon dioxide.

100

Temp.= 80 o C
P= 80 psi

80

Temp.= 25
P= 1 atm

oC

60
CONDITIONS
%Solids = 20
pH= 11.0
rpm = 300

40
20
0
0

50

100

150

200

TIME (min)

250

300

350

Fig. 3. Comparison of silver extraction at ambient conditions and high pressure.

2.3.3 Effect of cyanide concentration
Concentrations of 0.6 - 1.1 wt. % sodium cyanide were used to leach the concentrate in the
autoclave. When the concentration of sodium cyanide was less than 0.6%, gold and silver
extraction could not be completed optimally in a single stage of autoclave leaching.
Increasing the cyanide concentration resulted in an increase in the gold and silver extraction.
The results obtained are shown in Figure 6.
2.3.4 Effect of temperature
The concentrate was leached as 20-wt.% solids slurry with 1 wt.% of NaCN for 60 minutes.
Temperature was varied from 60 to 200 C. As the temperature was increased, the gold and
silver extractions decreased, since at temperatures higher than 80 C, the oxidation of
cyanide ions is too rapid resulting in the formation of CO2 gas and ammonium ion. Cyanide
is then not available for complexetion with the gold and silver. See Figure 7.
CNO- + H2O + 2H+

CO2 + NH4+

(20)

78

Noble Metals

EXTRACTION, %

100

P= 80 psi
T= 80 oC

80
60

P= 1 atm
Temp.= 25 C

CONDITIONS
%Solids= 20
pH= 11.0
rpm= 300

40
20
0
0

30

60

90

120

150

180

TIME (min)

210

240

270

300

Fig. 4. Comparison of gold extraction at ambient conditions and high pressure.

EXTRACTION, %

100
GOLD

95
CONDITIONS
%Solids = 20
pH = 11
Pressure = 80psi
rpm = 300
Temp. = 80 oC

90

SILVER

85
15

30

45

60

75

90

105

120

AUTOCLAVE RETENTION TIME (minutes)

Fig. 5. Effect of autoclave retention time on gold and silver extraction.

EXTRACTION, %

100

GOLD

90
80
70

CONDITIONS
% Solids = 20
pH = 11

SILVER

Temp. = 80 C
Pressure = 80 psi
rpm = 300
leach time = 60 min.

60
50
0.4

0.6

0.8

CYANIDE CONCENTRATION, %
Fig. 6. Effect of the cyanide concentration on gold and silver extraction

1.2

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

79

Fig. 7. Effect of temperature on gold and silver extraction.

2.3.5 Effect of pH
A pH range of 10.5-13, was examinated for the extraction of gold and silver. In Figure 8, it
can be seen that at a pH of 11.5 or above, optimum extractions could not be maintained.
This behavior is because in alkaline-oxidizing medium the pyrite and pyrrhotite in the
concentrate competes with gold and silver for consumption of oxygen, and this mechanism
may be responsible for the decrease in extraction.
2FeS2 + 7O2 + 2H2O
FeS + 2O2

2Fe2+ + 4H+ + 4SO42Fe2+ + SO42-

(21)
(22)

Eventually the ferrous sulfate formed is converted to the stable, insoluble ferric hydroxide.
FeSO4 + Ca(OH)2

Fe(OH)2 + CaSO4

2Fe(OH)2 + 1/2O2 + H2O

2Fe(OH)3

(23)
(24)

The decrease in the extraction of gold and silver with increasing pH may also be due to a
decrease in the formation of ferric sulfate which is the reagent that contributes to the
oxidation of sulfide minerals which occlude gold and silver. Also Deitz (Deitz and Halpern,
1953) found that at high pH values between 12 to 13, the silver surface was coated with a
whitish film of CaO2 and thus the leaching process was retarded.
2.3.6 Effect of pulp density
The effect of varying the pulp density in the range of 15-30% solids is shown in Figure 9.
Gold and silver extractions gradually decreased as the pulp density increased apparently
due to the increased apparent viscosity of the slurry which impedes good oxygen dispersion
in the system, and also for the excessive acid generation.

80

Noble Metals

2.3.7 Plant operation

The optimum conditions as delineated in the laboratory study (Table 4) were used to study
the extraction of gold and silver during a continuous one-month plant campaign. A total of
600 tons of concentrate was processed. Recoveries for both gold and silver averaged
approximately 96%. These plant data are shown in Figure 10.
On the basis of the results described above the plant tests were in good agreement with the
results obtained in the laboratory autoclave and relative to any comparable process, low
temperature, low pressure and with these conditions cheaper autoclaves can be used.
Thomas shows (Thomas et al., 1992) that a 1400 t/d acid pressure oxidation circuit might
cost C$30 million while the corresponding non-acid circuit might cost only C$15 million.

Fig. 8. Effect of pH on gold and silver extraction.

Fig. 9. Effect of percent solids in the extraction of gold and silver.

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

Solid % = 20
Temperature = 80 C
Pressure = 5.6 kg./cm2 (psi)
rpm = 300

81

Cyanidation time = 60 min.

NaCN = 1%
pH = 10.7
PbO = 100gr./ton

Table 4. Optimum parameters for the autoclave

Fig. 10. Result from continuous plant operation.

3. Electrocoagulation process alternative for silver and gold recovery

After the extraction of gold and silver from the argentopyrite/argentite ore, the next step
is the recovery of the precious metals from the cyanidation process by which gold and
silver are recovered from their ores, and it is recognized that the Carbon in Pulp, the
Merrill-Crowe (Metal displacements), the Ion Exchange and Electrowinning processes are
used for concentration and purification of gold and silver from cyanide solutions. Each
recovery method has advantages and disadvantages. Process selection depends on the
specific conditions for a particular operation and the facilities already available. The
Merrill-Crowe method had been the preferred process for many years for recovery silver
and gold from high reach solutions. Only recently, in the past years, has the carbon
adsorption process become popular for recovering gold from large volumes of low grade
pregnant leach solutions that contain mainly gold. Other processes, Ion-Exchange Resins
and Solvent Extraction, have recently been reviewed as an alternative for gold and silver
recovery from alkaline cyanide solutions, (Aguayo et al., 2007). Commercially available
resins were unable to compete with activated carbon due to poor selectivity, mechanical
breakdown of the beads and the requirement for complex elution, generation of HCN and
regeneration process.
Among several available options for recovery of precious metals from cyanide solutions,
Electrocoagulation (EC) is a very promising electrochemical technique that does not require
high concentrations of silver and gold in cyanide solutions in order to recovery them. Also,
literature review showed that the potential of EC as an alternative to traditional treatment
recovery of precious metals (silver and gold cyanide) has not yet been exploited.
Advantages and disadvantages for the different processes are presented in Table 5, along
with those of the EC (Mollah et al., 2004; Parga et al., 2005). EC has been proposed since
before the turn of the 20th century. A plant was built in London in 1889

82

Noble Metals

Method

Merrill-Crowe

Advantages

Lower capital and operating

costs.
Handles solutions containing
high silver and gold content.
It is highly efficient (99.5%).
Also can treat high-grade
solutions produced by carbon
elution.
Alternative to Electrowinning.
Well known technology.

Adsorption with
Activated Carbon

Does not require pre-treatment

of pregnant solution.
Not dependent on the
concentration of metals.
Large specific surface.
The pulp needs no clarification.

Ion Exchange
Resins

Does not need: washing,

revitalization or heat treatment.
High abrasion resistance in
tanks of adsorption.
High selectivity.

Electrocoagulation

Low residence time (minutes).

Does not use chemicals.
Handles solutions containing
lower or high silver and gold
contents.
Energy costs per m3 of pregnant
solution are lower than
conventional treatment systems.

Disadvantages
The pregnant solution need
clarification and
deoxygenating.
Low concentrations of
metals, increases amount
of zinc
Depends on the pH and
concentration of the free
cyanide.
The precipitate contain
cyanides like copper and
arsenic.
The precipitate spend one
week in the filter press.
Fouled carbon needs to be
regenerated by heating.
Large carbon inventory.
The pregnant solution has
to go through 5 or 6
columns.
High operating costs.
High cost of the process.
Lower loading capacity.
Royalty payments.
The resin must be
regenerated in acid
medium.
Sacrificial anode must be
placed periodically.
Precise initial pH control.
New technology.
The product is high in iron.
The sludge need to be
leaching with sulfuric acid.

Table 5. Advantages and disadvantages of methods for recovery of gold and silver
(Emamjomeh et al. 2004; Mollah et al., 2009; Parga et al., 2007).
for the treatment of sewage mixing it with seawater and electrolyzing it. In 1906, EC was
first patented (Parga et al., 2005) and used to treat bilge water from ships. In 1909, in the
United States J.T. Harries received a patent for wastewater treatment by electrolysis using
sacrificial aluminum and iron anodes (Vik et al., 1984). Matteson (Matteson et al., 1995),
described a device of the 1940s, the electronic coagulator which electrochemically
dissolved aluminum (from the anode) into solution, reacting this with the hydroxyl ion
(from the cathode) to form aluminum hydroxide. The hydroxide flocculates and coagulates

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

83

the suspended solids and thereby purifies water. A similar process was used in Britain in
1956 in which iron electrodes were used to treat river water (Holt et al., 2005).
3.1 Electrocoagulation fundamentals
The electrochemical phenomenon of Electrocoagulation has been employed previously for
treating many types of wastewater with varying degrees of success. This electrochemical
method of contaminant removal requires smaller quantities of salt addition to increase the
conductivity of the solution (typically, an aqueous electrolye), and the maintenance and
operation of the EC cells are relatively simple. Electrocoagulation processes offer significant
potential for removing ionic species from solution, particularly heavy metals (Mollah et al.,
2004; Parga et al., 2007). Operating conditions are highly dependent on the chemical
composition and properties of the aqueous medium, specifically, conductivity and pH.
Other important process variables, such as particle size, type of electrodes and retention
time between electrodes, electrode spacing and chemical-constituent concentrations
influence the operating process-parameters (Parga et al., 2007). The fundamental operatingprinciple is that cations produced electrolytically from iron and/or aluminum anodes (by
oxidation) provide for the coagulation of contaminants contained in the aqueous electrolyte.
Thus, the (sacrificial) metal-anodes provide a continuous supply of polyvalent metal cations
in the vicinity of the anode. These cations participate in the coagulation process by
neutralizing the negatively-charged ions (anions) that are transported toward the anode by
electrophoresis. In a continuous-flow EC system, the production of polyvalent cations from
the oxidation of the sacrificial anodes (Fe and/or Al) and the evolution of electrolysis gases
(H2 at the cathode and O2 at the anode) are directly proportional to the current (charge)
supplied according to Faradays Law of Electrolysis. The evolved gases enhance the
flocculation of the coagulant species.
A schematic of the electrocoagulation process for recovery gold and silver is shown in
Figure 11. The gas bubbles produced by electrolysis convey the gold and silver species to the
top (free-surface) of the electrolyte where it is concentrated, collected and removed. The
removal mechanisms in EC may involve oxidation, reduction, decomposition, deposition,
coagulation, absorption, adsorption, precipitation and flotation.
However, it is the reaction involving the metal ions that enhance the formation of the
coagulant. The metal cations react with the OH- ions produced at the cathode during the
evolution of hydrogen, to yield both soluble and insoluble hydroxides that will react with or
adsorb pollutants, respectively, from the solution and also contribute to coagulation by
neutralizing the negatively charged colloidal particles that may be present at neutral or
alkaline pH. This enables the particles to approach closely and agglomerate under the
influence of Van der Waals attractive forces. Depending on the pH range, the electrode
reactions that have been proposed to describe EC mechanisms for the production of H2(g),
OH (cathode) and H+ and O2(g) (anode) are (Moreno et al., 2009):
i.

pH <4

Anode:
Fe2+ + 2e- = Fe0

(25)

84

Noble Metals

Fig. 11. An illustration of the EC mechanism (arrow indicate the migration of ions, the H2
evolution and the formation of green rust).
Cathode:
2H++ 2 eii.

H2(g)

(26)

pH 4 <pH< 7:

Anode: as before, reactions (25) and (26). Furthermore, iron also undergoes hydrolysis:
Fe + 6H2O

Fe(H2O)4(OH)2 (aq) + 2H+ + 2e-

(27)

Fe + 6H2O

Fe(H2O)3(OH)3 (aq) + 3H+ + 3e-

(28)

Fe(III) hydroxide begins to precipitate as a floc with yellowish color.

Fe(H2O)3(OH)3 (aq)

Fe(H2O)3(OH)3(s)

(29)

Rust can also be formed.

2Fe(H2O)3(OH)3

Fe2O3 (H2O)6

(30)

H2(g)

(31)

Cathode:
2H++ 2 e-

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

85

Additional hydrogen evolution takes place, but [H+] now comes from iron hydrolysis.
iii. pH 6 <pH< 9:
Anode: reactions (25) and (26). Precipitation of Fe(III) hydroxide occurs according to
Reaction (30) simultaneous with Fe(II) hydroxide precipitation whereby a dark-green floc is
produced.
Fe(H2O)4(OH)2 (aq)

Fe(H2O)4(OH)2 (s)

(32)

The minimum solubility of iron hydroxides, Fex(OH)y, occurs in the pH range of 78. EC
flocs are formed due to the polymerization of iron oxyhydroxides. Formation of rust
(dehydrated hydroxides) occurs according to the following:
2Fe(OH)3

Fe2O3 + 3H2O (hematite, maghemite)

Fe(OH)2

2Fe(OH)3 + Fe(OH)2
Fe(OH)3

FeO + H2O
Fe3O4 + 4H2O (magnetite)

FeO(OH) + H2O (goethite, lepidocrocite)

(33)
(34)
(35)
(36)

The species hematite, maghemite, rust magnetite, lepidocrocite and goethite have been
identified as EC products by (Parga et al. 2005).
Cathode:
H2O + 2e- = H2(g) + OH-

(37)

Overall reactions are:

Fe + 6H2O
Fe + 6H2O

Fe(H2O)4(OH)2 (s) + H2(g)

(38)

Fe(H2O)3(OH)3 (s) +1 H2(g)

(39)

The concentrations of the various species within the cell are not uniform; in addition the
concentration of species such as iron and hydronium ion are also time dependent.
Typically, the EC process employs bipolar electrodes (Parga et. al. 2005). It has been
demonstrated that with this configuration where the electrodes are connected in series,
and consequently low current-densities are present, iron (or aluminum) coagulant is
produced more effectively, at higher rates and more economically compared to chemical
coagulation (Parga et. al. 2005).
Also, in the electrocoagulation cell for the high voltage we produce a very strongly
oxidizing environment around the anode and this is suitable for destroying strong
cyanide solutions (greater than 1000 ppm) and is a direct oxidation of the cyanide ion at
the anode to cyanate ion which is further decomposed to carbon dioxide and nitrogen,
ammonium, and carbonate or oxalate ions according to the pH (Hwang et. al., 1987). The
reactions are as follows:
In strong alkaline solution (pH=12):
CN- + 2OH-

CNO- + H2O + 2e

(40)

86

Noble Metals

CNO- + 2OH-

CO2 +1/2N2 +H2O + 3e

(41)

In neutral and weak alkaline solution (pH = 7.0-11.7):

C2N2

2CN
C2N2 + 2OH-

CNO- + CN- + H2O

CNO- + 2H2O

(42)
(43)

NH+4 + CO2-3

(44)

C2O2-4 + 2 NH+4

(45)

In weak acidic solution (pH = 5.2-6.8):

C2N2 + 4H2O
3.2 Experimental details
The EC experiments were performed with a Fisher magnetic stirrer and a 400ml beaker size
reactor equipped with two carbon steel electrodes (6 cm x 3 cm) that were 5 mm apart. As a
source of current and voltage a universal AC/DC adaptor was used. pH was measured with
a VWR scientific 8005 pH meter and electrodes were properly scrubbed and rinsed prior to
each experiments to ensure a clean surface free from passive oxide layers . Gold and silver
adsorption onto iron hydroxide species was investigated with pregnant cyanide solutions
provided by Bacis S.A. de C.V mining group (13.25 mg L-1 Au, 1357 mg L-1 Ag, 200 mg L-1
free CN- and 1400 mg L-1 total CN- and pH of 8). Analysis were performed by ICP/Atomic
Emission Spectrometry (Perkin Elmer 3100). The conductivity of pregnant solutions was
adjusted by adding one gram of NaCl per liter (Fisher, 99.8% A.C.S. Certified, lot
#995007).To identify and characterize the iron species in the solid products, formed during
the EC process for the removal of gold and silver using iron electrodes, X-ray diffraction
(XRD) (Phillips model X-PERT), FT-IR analysis were carried out by Thermonicolate FTIR
spectrometer and Scanning Electron Microscope (SEM / EDX) (FEI Quanta 2000, Oxford
Instruments) were used.
Analysis of Au and Ag were conducted to the Bacis solution, by AES. EC was run at 15 Volts
(DC) and the corresponding current was of 0.1 A. EC was run for five minutes, and a sample
was taken every minute in order to determinate the removal efficiency for Au and Ag.
Solutions and solids from the EC process were separated by filtration through cellulose filter
paper. The sludge from the EC was dried either in an oven or under vacuum at room
temperature and characterized. The experimental set-up is presented in Figure 12. The
current and voltage during the EC process were measured and recorded, using Cen-Tech
multimeters. The pH values of the solution before and after EC were measured with a VWR
scientific 8005 pH meter.
The resulting sludge of iron hydroxide gel precipitate with Au/Ag is filtered. Then, this
rich sludge is treated in an acid leach step with sulfuric acid under oxidizing conditions
caused by the addition of air. The conditions of this acid leach are such that the major
portion of iron and copper are leached into solution with gold and silver remaining in the
residue. The resultant residue from the filtration step is gold and silver, as well as little
iron (10 % Au, 80 % Ag and 5 % Fe) suitable for further refining by conventional
commercial method.

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

87

Fig. 12. Experimental set-up of the EC process for the removal of Ag and Au.
3.3 Results and discussion
With the optimal parameters for cell work of EC, they were tested for removal efficiency
of gold and silver, the table 6 shows the results when making treatment of the solution
containing gold and silver and also the removal efficiency of cyanide, as shown in Figure
13. A maximum in gold and silver recovery were achieved at 5 minutes of treatment and
as the arithmetic average of five replications; achieved an efficiency of 99.24% Au to
99.93% Ag for both, with a standard deviation of 0.26 in gold and 0.06 in silver. Also, this
studies shown a very efficient recovery in the range of 2 to 3 minutes for gold and 1 to 2
for silver, this occurs in the pH range from 9 to 11 approximately, which coincides with
the production of the magnetic iron, Fe3O4, which has magnetic properties that accelerates
the process of adsorption of metals, the adsorption rate is then physically, because it is
caused by the magnetic forces of the magnetite into gold and silver these forces without
altering their chemical composition. Also, it is likely that the electrocoagulation cell is
oxidizing the Au and Ag cyanide complexes and converting them to a less-soluble form
that is captured by the iron hydroxide gel. The high voltage in the EC cell around the
anode destroys some of the cyanide.
About the same studies, Figure 14 shows graphically the evolution of pH during the
operation time, there was an increase in pH of the solution which is attributed to the
evolution of hydrogen at the cathode which is accompanied by alkalinization of the aqueous
solution. The final effect is the oxidation suffered by the water coupled with the generation
of hydroxyl ions generated during EC.

88
EC
residence
time (min)
0
1
2
3
4
5

Noble Metals

Au
(mg L-1)

Recovery
(%)

Ag
(mg L-1)

Recovery
(%)

pH

13.25
12.50
10.50
1.00
0.50
0.10

0
5.66
20.37
92.45
96.22
99.24

1357.0
1240.0
219.5
9.0
7.0
0.9

0
8.62
83.82
99.33
99.48
99.93

8.0
9.2
9.5
10.7
11.2
11.5

Removal of Removal of
Cyanide
Cyanide
(mg L-1)
(%)
1400
0
1050
25
870
38
750
46
400
71
210
85

Table 6. Recovery of gold and silver by EC.

Fig. 13. Gold and silver recoveries from Bacis cyanide solutions.

Fig. 14. Variation of pH vs. EC residence time and Cyanide removal vs time.

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

89

This results shown that in the EC cell with the iron electrodes decompose the content of
cyanide in the pregnant reach solution of gold and silver from initial cyanide content of 1400 to
210 mg L-1. It was found that (Tamura et al., 1974) the anodic oxidation of cyanide is
proportional to the alkalinity of the electrolyte and consistent with the following mechanism:
CN- + 2OH
2CNO- + 4OH-

CNO- + H2O + 2e2CO2 + N2 + 2H2O + 6e

CNO- + 2H2O

NH4 + CO-3

(46)
(47)
(48)

3.3.1 Product characterization

X-ray Diffraction Analysis. Diffraction patterns of flocs collected from the experiment with
gold and silver, (the sample were ground to a fine powder and loaded into a sample holder)
were obtained with a diffracted X-PERT Phillips meters equipped with a vertical
goniometer, with a range of analysis 2 10 to 70 . The source of X-rays has a copper
anode, whose radiation is filtered with a graphite monochromator ( = 1.541838) with scan
rate of 0.02 and a duration of 10 seconds per count. The X-Ray Diffractometer is controlled
by a Gateway 2000 computer, by PC-APD 2.0 with software for Windows.
Figure 15 shows the ray diffraction pattern of the flocs recovered from the sample of gold
and silver, respectively 13.25 mg/L and 1357 mg/L, initial pH 8, 5 minutes of treatment, 0.1
amperes and 15 volts. The species identified were magnetite, lepidocrocite, goehtite, silver
and copper hexacyanoferrate.

Fig. 15. X-ray diffractogram of solids obtained in the recovery of gold and silver. C: Cu2Fe
(CN) 62H2O A: Silver, M: Magnetite and L: Lepidocrocite.
Fourier Transform Infrared Spectroscopy. FT-IR analysis were carried out by
Thermonicolate FTIR spectrometer and OMNIC software using potassium bromide pellets
(sample: KBr =1: 50). The spectra were usually recorded in the range of 4000-400 cm-1 with 2
cm-1 resolution. 64 scans were collected for each specimen. Figure 16 shows the FT-IR
spectrum of the by-product. Infrared analysis of iron electrode by-product showed OH

90

Noble Metals

stretching at 3738 and 3447 cm-1, hydroxyl bending and `(OH) water bending vibration or
overtones of hydroxyl bending around 1637 cm-1 . Bands for lepidocrocite phase showed up
at 1120, 1023, and 745 cm-1. Magnetite (Fe3O4 or Fe3-xO4) band at 575 cm-1and Fe-O vibration
band is seen at 469 cm-1. For details of FT-IR analysis see Table 7.
XRD analyses also confirmed the presence of these species detected by FT-IR.

Fig. 16. FT-IR spectrum of iron electrode by-product.

Electrode
Material

Type of Vibrations
OH stretching

Iron

Hydroxyl bending
`(OH) water bending
Overtones of hydroxyl
bending
Magnetite (Fe3O4 or Fe3xO4)
Fe-O
Lepidocrocite

Vibration
wavenumbers (cm-1)
3738
3447
1637
1637

Vibration Range
(cm-1)
3689-3787
3550-3000
1572-1813
1572-1813

1637

1572-1813

575

526-840

469
1120
1023
745

416-510
1090-1245
923-1057
730-790

Table 7. FT-IR vibrations and their corresponding wave numbers and region for the bands
observed for the EC-byproduct
Scanning Electron Microscopy (SEM/EDAX). Figure 17 shows SEM images and EDAX of
silver adsorbed on iron species. These SEM and EDAX results show that the surfaces of these
iron oxide/oxyhydroxide particles were coated with a layer of silver. It is worth clarifying that,
given the low concentration of gold it was impossible to locate any nanoparticle of it.

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

91

Transmission Mssbauer Spectroscopy. Figure 18 shows the spectrum obtained from the
EC silver, gold and iron solid product from 1350 mg/L of silver and 13 mg/L of gold
cyanide solutions at pH = 11.0, Mssbauer Spectra for each sample was obtained on a 15
mm/s velocity scale, which allows observation of wide magnetic hyperfine spectra expected
from iron oxide compounds. The spectrum consists of a doublet magnetic spectrum, which
is probably due to fine particles of iron oxides (non-stoichiometric magnetite) or iron
hydroxides (Lepidocrocite, Goethite, etc.).From the analysis of these techniques the in-situ
generated small fine particles of iron- oxide/oxyhydroxides in the EC process are: nonstoichiometric magnetite, goethite and iron hydroxide oxide.

Fig. 17. Chemical composition of solid product as determined by EDX, which shows the
presence of silver in the particle of iron.

Fig. 18. Mssbauer spectrum with silver and gold at pH=10.5, indicating the presence of
magnetite species.

92

Noble Metals

4. Conclusions
This study has been very valuable in identifying that, gold and silver values are
associated with argentopyrite, pyrite, sphalerite and chalcopyrite in the Bacs concentrate.
The kinetics of the direct pressure oxidation/cyanidation was found to be strongly
dependent on particle size, concentration of sodium cyanide, oxygen pressure,
temperature and pH. Single stage direct pressure oxidation/cyanidation, has proven to be
effective in treating argentopyrite refractory gold and silver concentrates from the Bacs
mining and processing operations, for both gold and silver it was found that the precious
metals recovery exceeded 95%.
Also in this process, because of the short leaching time the inventory of gold and silver is
reduced. The relatively mild operating conditions of 80 C and 80 psi oxygen pressure offer
distinct advantages. For example, low cost materials of construction can be utilized for the
autoclave. Finally the pressure oxidation cyanidation process is flexible and can accommodate
gold and silver ore of different mineralogical composition and origin.
In addition it has been shown that Eletrocoagulation is an interesting process for the
recovery of gold and silver from the cyanide leach solution that is yet to be fully realized. EC
comprises complex chemical and physical processes involving many surface and interfacial
phenomena. Also, the results of this study suggest that EC produces magnetic particles of
magnetite and amorphous iron oxyhydroxides, and that this process can be used to remove
gold and silver cyanide ions. The results of this study indicate that silver and gold can be
successfully adsorbed on iron species produced by the Electrocoagulation process. So EC
may be used to recover gold and silver from cyanide solutions.
The X-Ray Diffraction, FT-IR analysis and Scanning Electronic Microscopy techniques
demonstrate that the formed species are of magnetic type, like lepidocrocite and magnetite,
and amorphous iron oxyhydroxide which adsorbed the silver and gold particles on his
surface due to the electrostatic attraction between both metals.
The 99.5% of gold and silver were removed in the experimental EC reactor, and it was
achieved in 5 minutes or less with a current efficiency of 99.7%. Finally, the high voltage in
the EC cell around the anode destroys some of the cyanide and this process can be
accelerated in the presence of copper ions.

5. Acknowledgment
The author thanks the management of Bacs Mining Co., Williams Mining Co., CONACYT
and DEGEST for the support and permission to publish this chapter and appreciation is
extended to Professor Jan D. Miller of University of Utah and Gerard P. Martins of Colorado
School of Mines for their interest in this research.

6. References
Adams, M.D. (2005). "Advances in gold ore processing Elsevier Inc. 346-369, ISBN
9780444517302, Amsterdam Netherlands.

New Technology for Recovery of Gold

and Silver by Pressure Cyanidation Leaching and Electrocoagulation

93

Aguayo, S., Valenzuela, J.L., Parga, J.R. & Lewis, R.G. (2007). Continuous laboratory gold
solvent extraction from cyanide solutions using LIX79 reagent. Chem. Eng.
Technol., 30, 1532-1536.
Anderson, C.G. & Nordwick, S.M. (1996). "Pretreatment using alkaline sulfide leaching and
nitrogen species catalyzed pressure oxidation on a refractory gold concentrate".
EPD Congress the Mineral and Materials Society., 323-341.
Chander, S. & Briceo, A. (1987). "Kinetics of pyrite oxidation". Minerals and Metallurgical
Processing., 8, 170-176.
Deitz, G.A. & Halpern, J. (1953). "Reaction of silver with aqueous solutions of cyanide and
oxygen". Journal of Metals., 5, 1109-1116.
Emamjomeh, M.M. & Sivakumar, M. (2009). Review of pollutants removed by
electrocoagulation and electrocoagulation /flotation processes. Int. J. Environ.
Manage., 90, 1663-1679.
Graham, J.S. & James, T.W. (1995). "Cyanide and other lixiviant leaching systems for gold
with some practical applications". Mineral Processing and Extractive Metallurgy
Review, 14, 193-247.
Holt, P., Barton, G. & Mitchell, C. (2005). The future of EC as a localized water treatment
technology. Chemosphere 9, 13, 335-367.
Hwang, J. Y., Wang, Y. Y. & Wan, C.C., (1987). Electrolytic oxidation of cuprocyanide
electroplating wastewaters under different pH conditions, J. Appl. Electrochem, 17,
684-694.
Marsden J. O. & House, C.L. (2006). The chemistry of gold extraction, Second edition,
Society of Mining, Metallurgy and Exploration, 237-238, ISBN 9780873352406.
Littleton, Colorado, USA.
Matteson, M. & Dobson, R, (1995). Electrocoagulation and separation of aqueous
suspensions of ultrafine particles. Colloids and Surfaces A: Physicochemical and
Engineering Aspects, 104, 1, 101-109.
Mollah, M., Morkovsky, P., Gomez, J., Parga, J.R., & Cocke, D. (2004). Fundamentals,
present and future perspectives of electrocoagulation. J. Hazard. Mat., B1, 14, 199210.
Moreno, H., Cocke, D. L., Gomes, J. A. G., Morkovsky, P., Parga, J. R., Peterson, E. & Garcia,
C. (2009). Electrochemical reactions for electrocoagulation using iron electrodes.
Ind. Eng. Chem. Res., 48, 22752280.
Parga, J.R., Cocke, D.L., Valenzuela, J.L., Kesmez, M., Gomes, J.A.G. & Valverde, V. (2005).
As removal by EC technology in the Comarca Lagunera Mexico. Journal of
Hazardous Materials, 124, 1-3, 247-254.
Parga, J.R., Valenzuela, J.L & Cepeda, F. (2007). Pressure cyanide leaching for precious
metals recovery. Journal of Metals, 10, 43-47.
Senanayake, G. (2008). A Review of effects of silver, lead, sulfide and carbonaceous matter
on gold cyanidation and mechanistic interpretation, Journal Science Direct, 2008, 90,
46-73.
Tamura, H., Arikado, T., Yoneyama, H. & Matsuda, Y. (1974). Anodic oxidation of
potassium cyanide on platinum electrode, Electrochim.Acta, 19, 273.
Thomas, K.G, Burns, D. & Hill, A.R. (1992). "Autoclaving technology and barrick gold",
(Paper prepared for the International Precious Metals Institute, Reno, Nevada), 11.

94

Noble Metals

Vik, E.A., Carlson, D.A., Eikun, A.S. & Gjessing, E.T. (1984). Electrocoagulation of potable
water. Water Research, 18, 11, 1355-1360.
Wan, R.Y., Le Vier, M. & Miller, J.D. (1993). "Research and development activities for the
recovery of gold from non-cyanide solutions". Hydrometallurgy fundamentals,
Technology & Innovations. (Society for Mining, Metallurgy & Exploration), 415-436.

Informacin Tecnolgica
Uso
de Resina
de(2012)
Intercambio Aninico para la Recuperacin del Complejo Oro
Vol. 23(2),
53-60

Chaparro

doi: 10.4067/S0718-07642012000200007

Uso de Resina de Intercambio Aninico para la

Recuperacin del Complejo Oro Tiosulfato desde
Soluciones Acuosas
Miriam E. Chaparro(1), Jess L. Valenzuela(2), Guillermo T. Munive(2) y Jos R. Parga(3)
(1) Instituto de Ingeniera, Universidad Autnoma de Baja California, Blvd. Benito Jurez y Calle a
la Normal S/N, Col. Insurgente Este, Mexicali, B.C.-Mxico. (miriam_edith1981@hotmail.com).
(2) Departamento de Ingeniera Qumica y Metalurgia, Universidad de Sonora,
Rosales y Blvd. Luis Encinas, Col. Centro, Hermosillo, Sonora-Mxico. (jvalen@iq.uson.mx).
(3) Departamento de Metalurgia y Materiales, Instituto Tecnolgico de Saltillo, Blvd. Venustiano
Carranza # 2400, Saltillo, Coahuila-Mxico. (jrparga@its.mx).
Recibido Ago. 26, 2011; Aceptado Nov. 02, 2011; Versin Final recibida Dic. 26, 2011

Resumen
Se estudi la adsorcin de oro utilizando la resina AuRIX100 en medio tiosulfato de amonio,
evaluando algunas variables que afectan la cintica del proceso tales como: temperatura,
velocidad de agitacin, pH, concentracin de tiosulfato de amonio (NH4)2S2O3 y concentracin de
oro. El estudio se llev a cabo en un reactor batch y una columna de intercambio inico. Las
condiciones de operacin que presentaron mejores resultados de extraccin de oro a 25C,
fueron: pH=10.5, velocidad de agitacin=500 rpm, [Au]=1 mg/l, [(NH4)2S2O3]=0.04 M, 5 gramos de
resina. Los resultados indican que al aumentar [(NH4)2S2O3] favorece la adsorcin en un 99%
durante tres horas, siendo afectado notablemente por la presencia de amonio. Las condiciones
con mejores resultados en la columna a 25C fueron, pH= 10.5 y [Au] =1 mg/l.
Palabras clave: adsorcin oro, tiosulfato, resina AuRIX100, cintica

Use of Anion Exchange Resin for the Recovery of the

Complex Gold Thiosulfate from Aqueous Solutions
Abstract
The adsorption and elution of gold in thiosulfate-ammonia media were studied using the resin
AuRIX100, evaluating some variables that affect the kinetics of the process, such as:
temperature, stirring speed, pH, thiosulfate concentration (NH4)2S2O3 and gold concentration. The
study was carried out in a batch reactor and an ion exchange column. The operation conditions
that presented better results of gold extraction at 25C were: pH=10.5, stirring speed=500 rpm,
[Au]=1 mg/l, [(NH4)2S2O3]=0.04 M, and 5 grams of resin. The results indicate that by increasing
[(NH4)2S2O3] favors the adsorption by 99% during three hours, being noticeably affected by the
presence of ammonia. The conditions with results on the column at 25C were, pH= 10.5, [Au]=1
mg/l.
Keywords: gold adsorption, thiosulfate, AuRIX100 resin, kinetics
Informacin Tecnolgica Vol. 23 N 2 - 2012

53

Uso de Resina de Intercambio Aninico para la Recuperacin del Complejo Oro

Chaparro

INTRODUCCIN
La mayora de las plantas minero metalrgicas utilizan el proceso de cianuracin para la
extraccin de oro, pero el principal problema es su alta toxicidad, por lo que en recientes aos, se
han desarrollado mtodos alternativos para ello, como es el caso del tiosulfato de amonio y
tiourea, que son tan efectivos como el cianuro, pero que aun no han logrado aplicaciones
industriales ya que presenta dificultades inherentes a la qumica de la solucin y los mtodos para
su recuperacin han limitado su progreso (Aylmore et al, 2001). Adems, las disoluciones de
lixiviacin han sido realizadas por Adsorcin en carbn activado, extraccin por solventes,
precipitacin por el proceso Merrill-Crowe, electrodeposicin y resinas de intercambio inico.
Estudios recientes (Chaparro, 2008), demostraron la viabilidad de la extraccin del complejo oro
tiosulfato, tratndolo con guanidina sobre una resina de intercambio aninica. Por otro lado, la
lixiviacin de oro desde concentrados y/o minerales usando disoluciones de tiosulfato y amoniaco
han sido estudiadas como alternativas al proceso de cianuracin. Sin embargo, uno de los
problemas asociados al uso del tiosulfato es la recuperacin de oro desde las disoluciones
obtenidas ya que son catalizadas por cobre y amoniaco, presentando un posible mecanismo de
reaccin, como el observado en las ecuaciones 1 y 2.

Au + Cu(NH3 )24 + 4S2O32- Au(S2O3 )32- + Cu(S2O3 )32- + 4NH3

(1)

Cu(S2O3 )32- + O2 + 2H2O + 6NH3 4Cu(NH3 )24+ + 8S2O32- + 4OH-

(2)

Con respecto al uso de resinas para la recuperacin de oro desde disoluciones acuosas con
tiosulfato y amoniaco, existen estudios en literatura (Molleman et al, 2002), donde utilizan resinas
de base dbil y la especie estable que se adsorbe es el complejo oro-tiosulfato, existiendo aniones
en la disolucin acuosa, como sulfito, tritionato y tetrationato que son adsorbidos por la resina,
provocando una disminucin en el complejo Au(S 2 O 3 ) 32- . Del mismo modo, en investigaciones
realizadas (Aguayo, 2007) sobre la extraccin por solventes para Ag y Au en soluciones alcalinas
provenientes de cianuracin, se utiliz como extractante LIX 79 en base guanidina e igualmente
que AuRIX100 en soluciones de tiosulfato y como diluyente keroseno, determinando que el
complejo oro-cianuro, se extrae a 10.5 < pH < 11.2. Al agregar tridecanol 5% en volumen,
obteniendo como resultado una adecuada selectividad con 10% LIX 79. Lo anterior, fue generado
a partir de licores de lixiviacin en columna con minerales oxidados y sulfurados pero conteniendo
Ag y pequeas cantidades de Au, Cu y Zn. Sin embargo, es necesario realizar una exhaustiva
investigacin utilizando el complejo oro-tiosulfato. As mismo, en investigaciones de adsorcin de
Au (Navarro et al, 2006), utilizando resina Amberlita IRA-410 en medio tiosulfato-amoniaco, se
demostr que la adsorcin de Au es rpida, debido a la presencia de tiosulfato est desfavoreci
la adsorcin; sin embargo, este aspecto no queda muy claro. De tal manera, que estudios
realizados para evaluar la eficiencia de la resina AuRIX100 (Valenzuela et al, 2006), para la
recuperacin del complejo oro-cianuro a pH 10.7, se determino que al aumentar la relacin slidolquido la cantidad de Au por unidad de masa de resina aumenta proporcionalmente. Durante la
adsorcin de Au en carbn activado, se ha discutido que el complejo oro-tiosulfato no es
adsorbido eficientemente, pero no obstante a ello (Vargas et al, 2006), ha reportado que la
presencia de tiosulfato, amoniaco e impurezas (Cu, Zn), son perjudiciales para la adsorcin de Au
ya que la Ea= 9.13 kJ/mol; por lo contrario, el complejo oro-cianuro si es adsorbido por el carbn
activado. Por otro lado, se han evaluado materiales (Seob et al, 2010) para la adsorcin de Au
obteniendo 427.77 mg/g con resina AmberjetTM4400, 170.64 mg/g en carbn activado y 361.76
mg/g en medio biosorbente. Por otra parte (Munive et al, 2011), se realizaron estudios
comparativos de lixiviacin sobre un mineral refractario conteniendo cantidades de sulfuros, pirita
y pirrotita, en presencia de cianuro y tiosulfato, donde este ltimo permanece estable, pero con la
finalidad de recuperar Au y Ag durante 48 hrs y ajustando el pH menor a 9.6 con solucin de
NaOH y Ca(OH)2. Resultados obtenidos (Breuer et al, 2002), donde el tiosulfato disuelve al cobre
presente en el mineral, se muestra que favorece al proceso, ya que acta como oxidante,
provocando que la disolucin de Au y Ag disminuya, atribuido a la inestabilidad del complejo
cuprotetramina (Yen et al, 1998) a pH=9.5. De lo anterior, se puede observar que existe un gran
inters por proponer lixiviantes alternativos al cianuro para la adsorcin de Au, con compuestos
54

Informacin Tecnolgica Vol. 23 N 2 - 2012

Uso de Resina de Intercambio Aninico para la Recuperacin del Complejo Oro

Chaparro

menos txicos y buscando tcnicas viables que permitan obtener una mxima adsorcin de
metales precisos. En la Tabla 1. Se enlistan las condiciones de lixiviacin de diferentes minerales.
Observando que la resina AuRIX100 contiene el componente activo guanidina, utilizada para
soluciones de lixiviacin del complejo oro-tiosulfato de amonio, constituida por una red de macro
retculas de estireno y divinil-benceno que funcionalizada con grupos guanidina actan como
bases orgnicas fuertes.
Tabla 1. Comparacin de parmetros de lixiviacin en minerales y avances en procesos de
adsorcin de oro
Antecedentes
Yen et al, (1998)
Molleman et al, (2002)
Navarro et al, (2002)
Breuer et al, (2002)
Ficeriov et al, (2002)
Zhang et al, (2002)
Valenzuela et al, (2006)
Navarro et al, (2006)
Vargas et al, (2006)
Jeffrey et al, (2010)
Seob et al, (2010)
Munive et al, (2011)

Tipo de Mineral
Au-Cu-0.36% Cu,
Au: 7.2-7.9 g/ton
Concentrado de Pirita
Conc. de Au: 95 g/ton
Cu(II), Au
Conc. de CuPbZn
20 mg/l, Au: 2 g/ton
Au: 0.32,
Ag: 0.43,Cu: 6.2
Au: 8 mg/l
Au: 10 mg/l, 2.2 g/ton
10 mg/l
Au
Au: 3.15 g/ton

NH3
(M)

% de
Rec.

24

S 2 O 32(M)
0.5

95-97

10-11
9-10
8-9.4
6-7
11
8-10.7

6
10
2
24
3

0.05
0.3
0.2
0.5
0.1
-

0.4
0-0.6
0.2
-

83
94
99
80-90
98

9-11
9.5
9
1-6
9.5

3
4
24
2-3
48

0-0.5
0-0.50
0.25

0-0.5
1-4
5-100 nM
0.1
0.4

92-98
15-28
2.7
84-96
70-82

T
(C)

pH

Ret
(h)

10

35
25
30-50
25
23-25
25
25
25
25-60
252
25

Por lo anteriormente expuesto, en este trabajo se propone estudiar el proceso de adsorcin de Au,
mediante pruebas batch y en columna, evaluando la eficiencia de la resina de intercambio
aninico AuRIX100 para la adsorcin del complejo oro-tiosulfato en medio amoniaco-tiosulfato,
con el objetivo de obtener los parmetros cinticos que intervienen en la reaccin, evaluando el
contenido de Au a un tiempo determinado, dando seguimiento a la reaccin en las soluciones por
absorcin atmica con la finalidad de establecer un proceso como mtodo alternativo para el uso
de las resinas de intercambio inico.
METODOLOGA

El mtodo seguido para el desarrollo del presente estudio, consistente en la extraccin de oro
mediante el uso de guanidina, se utiliza como componente activo guanidina en la resina
AuRIX100, determinando adems la influencia de las variables que intervienen en la reaccin
durante la extraccin del metal.
Extraccin de oro utilizando una resina AuRIX100, pruebas batch
En un reactor batch Kettles marca Pyrex, capacidad 500 ml, con disolucin acuosa de 250 ml, con
parmetros experimentales: Tiempo de contacto= 3 h, temperatura= 25C, [Au]i= 1-8 mg/l, razn
resina/disolucin= 20000 mg/l, velocidad de agitacin= 200-800 rpm. Evaluando el porcentaje de
oro adsorbido en funcin del tiempo. Las variables se presentan en la Tabla 2. Agregando al
reactor la disolucin acuosa, [Au]i, [(NH4)2S2O3], ajustando la temperatura y pH, se agreg la
resina a la disolucin y se agit el sistema, se sacaron muestras de la fase acuosa de 10 ml cada
30 min para anlisis, se midi el pH, en 3 h se detuvo la agitacin, se separaba la resina de la
disolucin acuosa y para su anlisis por la tcnica de absorcin atmica en un espectrofotmetro
Perkin Elmer 3110 y la carga de oro en la resina se determin por balance de oro.
Extraccin de oro utilizando una resina AuRIX100, pruebas en columna
Las pruebas en columna de intercambio inico dividida en cuatro secciones conectadas en serie
separacin slido-lquido, con una suspensin acuosa y resina en cada etapa, cada seccin tiene
Informacin Tecnolgica Vol. 23 N 2 - 2012

55

Uso de Resina de Intercambio Aninico para la Recuperacin del Complejo Oro

Chaparro

una malla de alambre en la parte inferior y superior para retener la resina colocada en cada una
de las celdas. Las dimensiones de las celdas son de 2.5 x 7.7 cm de dimetro y altura (2.54 x
7.52 cm), para pasar la solucin conteniendo oro, a travs de la columna se us una bomba
peristltica en tres corridas experimentales, con 5 gramos de resina como fase fija a 25C, con
una velocidad de 0.50, 0.60, 0.70 rpm, con 7.43 ml/min, 15 ml/min, 23 ml/min, equivalente a 89276 BVH, fue necesario saber la relacin flujo de solucin/volumen de resina y tambin fueron
analizadas las isotermas de adsorcin.
Disolucin de oro y disolucin eluyente
La disolucin de oro se llevo a cabo utilizando agua destilada y deionizada y tiosulfato de amonio
(NH4)2S2O3 con pureza 99% marca Aldrich, la solucin de oro (10002 g/ml), se ajusto el pH con
NH4OH y en la elucin con hidrxido de sodio [NaOH], sulfato de cobre pentahidratado
[CuSO45H2O], perclorato de sodio [NaClO42H2O], sulfito de sodio [Na2SO3] y cloruro de sodio
[NaCl].
Pruebas de desorcin
Los experimentos de desorcin se realizaron en un reactor de 500 ml de capacidad con agitacin,
donde se mantuvieron constantes las siguientes condiciones experimentales: pH= 9.5-11.5,
concentracin de ClO-4 , concentracin de SO 32 - , concentracin de Cl- , concentracin de NaOH.
Caracterizacin de la resina AuRIX100
La caracterizacin se llev a cabo por anlisis difraccin de rayos-X, caracterizacin por anlisis
infrarrojo y microscopio electrnico de barrido (MEB).
Tabla 2: Variables y rangos de experimentacin en la etapa de adsorcin
Variable
pH
Concentracin de Aui
Concentracin de (NH4)2S2O3

Rango de experimentacin
9-10.50
1-8 mg/l
0.00674-0.04 M

RESULTADOS Y DISCUSIN

En las Fig. 1 a 3 se estudi el efecto de tiempo de contacto en la extraccin de oro, se ve el efecto

del cambio de concentraciones de 1 mg/l a 8 mg/l, al aumentar el pH se logr un aumento en
porcentaje extraccin, donde el pH mejor fue de 10.5, en 3 h. En la Fig. 4 se muestra el efecto de
la velocidad de agitacin en la extraccin de oro en resina AuRIX100.

Fig. 1: Extraccin de oro en resina AuRIX100.

Condiciones: [(NH4)2S2O3]= 0.04 M, [Au]i=1 mg/l,
AuRIX100= 5 g. y T= 25C

56

Fig. 2: Extraccin de oro en resina AuRIX100.

Condiciones: [(NH4)2S2O3]= 0.04 M, [Au]i= 2 mg/l,
AuRIX100= 5 g, velocidad= 500 rpm y T= 25C

Informacin Tecnolgica Vol. 23 N 2 - 2012

Uso de Resina de Intercambio Aninico para la Recuperacin del Complejo Oro

Fig. 3: Efecto de tiempo de contacto en la extraccin

de oro en resina AuRIX100.
Condiciones: [(NH4)2S2O3]= 0.04 M, [Au]i= 8 mg/l,
AuRIX100= 5 g, pH= 9-10.5 y T= 25C

Chaparro

Fig. 4: Efecto de velocidad de agitacin en la

extraccin de oro en resina AuRIX100. Condiciones:
[(NH4)2S2O3]= 0.04 M, [Au]i= 1 mg/l, AuRIX100= 5 g,
pH= 10.5, velocidad= 200, 500, 800 rpm

En la Fig. 5 se muestra el efecto de pH en la extraccin de oro en la resina. Se encontr que la

mayor extraccin de oro se realiz a pH= 10.5 y 120 minutos y en la Fig. 6 se observ el efecto de
la [(NH4)2S2O3] en la adsorcin de oro en la resina al trabajar a pH 10.5. Es evidente el efecto
positivo que produce el contenido de tiosulfato en la disolucin acuosa sobre el porcentaje de oro
adsorbido, en 3 h. En presencia de tiosulfato, la adsorcin de oro alcanz un 99% y con 0.00674
M de tiosulfato el comportamiento no fue estable, la adsorcin disminuy a 98%, 0.03 M de
tiosulfato la adsorcin disminuy a 98% y 0.04 M de tiosulfato la adsorcin aumento a 99%.

Fig. 5: Efecto de pH en extraccin de oro en resina

AuRIX100. Condiciones: [(NH4)2S2O3]= 0.04 M,
[Au]i= 1, 2, 8 mg/l, AuRIX100= 5 g, pH= 9-10.5 y
T= 25C

Fig. 6: Efecto de la concentracin de tiosulfato en

extraccin de oro en resina AuRIX100.
Condiciones: [(NH4)2S2O3]= 0.00674, 0.03, 0.04 M y
[Au]i= 1 mg/l, AuRIX100= 5 g, velocidad= 500 rpm y
T= 25C

Se realizaron tres corridas experimentales con 5 gramos de resina, con una velocidad de 0.50,
0.60, 0.70 rpm, con 7.43 ml/min, 15 ml/min, 23 ml/min, equivalente a 89, 180 y 276 BVH. Los
resultados se muestran en las Fig. 7 a 10.
En la Fig. 7 Muestra el perfil de la velocidad de adsorcin, en cada seccin de la columna,
observndose que el trabajo en la ltima es inapreciable, pero en la primer seccin es ms rpida,
por lo que esta ser la primera que llegue a saturacin, se observ que con el paso del tiempo la
concentracin que sale de cada seccin va en aumento, en el momento que la concentracin que
entre sea igual a la que sale.

Informacin Tecnolgica Vol. 23 N 2 - 2012

57

Uso de Resina de Intercambio Aninico para la Recuperacin del Complejo Oro

Chaparro

Fig. 7: Perfil en la extraccin de oro al utilizar resina

AuRIX100, en las secciones de la columna con
velocidad de 0.50, con flujo de 7.43 ml/min,
equivalente a 89 BVH

Fig. 8: Perfil de la concentracin de oro, en las

secciones de la columna con velocidad de 0.60, con
flujo de 15 ml/min, equivalente a 180 BVH

Fig. 9: Comportamiento en la extraccin de oro al

utilizar resina AuRIX100 en las secciones de la
columna a 0.70, con flujo de 23 ml/min, equivalente a
276 BVH

Fig. 10: Perfil de la concentracin en la extraccin de

oro al utilizar resina AuRIX100 de la primera
seccin de la columna manejando diferentes flujos

Para 180 BVH. se compararon las secciones se observ que se incrementa la velocidad de
adsorcin en cada seccin con respecto a la velocidad mostrada en la Fig. 7 a 89 BVH. Se
observ que la concentracin de salida en cada seccin se incrementa un poco con respecto a la
de salida mostrada en la Fig. 7. Al aumentar el flujo aumenta la concentracin de salida de la
solucin, esto indica que a mayor flujo el tiempo para alcanzar la concentracin de saturacin de
la resina es menor y en caso de manejar flujos mayores sera necesario una quinta seccin en la
columna, para lograr la recuperacin total del in intercambiado.
CONCLUSIONES

En base a los resultados obtenidos del estudio de adsorcin de oro, se puede concluir que: Al
aumentar la concentracin de tiosulfato de amonio de 0.00674, 0.03, 0.04 Molar se favoreci la
extraccin de oro, debido a una mayor presencia de tiosulfato libre. Cuando aumenta el valor de

58

Informacin Tecnolgica Vol. 23 N 2 - 2012

Uso de Resina de Intercambio Aninico para la Recuperacin del Complejo Oro

Chaparro

pH por encima de 11, los iones hidroxilo promueven la degradacin de iones tiosulfato, causando
la precipitacin de oro.
Se encontr que la presencia de tiosulfato favorece la adsorcin de oro. Con tiosulfato, se obtuvo
en 0.04 M, se obtuvo un 99% de adsorcin mientras que con 0.03 M de tiosulfato, la adsorcin
disminuy al 98%, el proceso de adsorcin fue ms inestable y con 0.00674 M la adsorcin
disminuy al 98%, pero las condiciones de adsorcin fueron demasiado inestables.
La velocidad de agitacin del sistema es una variable muy importante porque permite la
suspensin de las partculas en movimiento y eso facilita la transferencia de masa. Las
concentraciones de oro como afectan de 1, 2, y 8 mg/l, los porcentajes de recuperacin
respectivamente fueron similares de 99, 93 y 95.75% de recuperacin de oro.
La resina AuRIX100 tiene las ventajas de trabajar a pH altos tpicos de las soluciones industriales
(9-11.5), dando como resultado el pH mejor 10.5 y en pH 9 disminuye la disolucin de oro con
tiosulfato de amonio, lo cual es atribuido a la inestabilidad en la disolucin de oro.
AGRADECIMIENTOS

Los autores expresan sus agradecimientos a la Universidad de Sonora por brindar su apoyo
durante la investigacin, al Departamento de Ingeniera Qumica y Metalurgia, al Laboratorio de
Servicios de Metalurgia, CONACyT, empresa COGNIS, a CESUES, a M.C. Juan Arvalo
Amezcua, por su valiosa colaboracin en la elaboracin del proyecto.
REFERENCIAS

Aguayo, S., J.L. Valenzuela, J.R. Parga y M. Cruz, Continuous Laboratory Gold Solvent Extraction
from Cyanide Solutions using LIX 79 Reagent, Chemical Engineering & Technology 30(11), 14571599 (2007).
Aylmore, M.G. y D.M Muir, Thiosulfate leaching of gold-a review, Minerals Engineering 14, 135174 (2001).
Breuer, P.L. y M.I. Jeffrey, Electrochemical study of gold leaching in thiosulphate solutions
containing ammonia and copper, Hydrometallurgy 65, 145-157 (2002).
Chaparro, M., Extraccin del complejo oro tiosulfato utilizando guanidina en una resina de
intercambio aninico, Tesis de Maestra, Dpto. de Ing. Qumica y Metalurgia, Univ. de Sonora,
Sonora, Mxico (2008).
Ficeriov, J., P. Bal., E. Boldiarov y J. Stanislav, Thiosulfate leaching of gold from a
mechanically activated CuPbZn concentrate, Hydrometallurgy 67(5), 37-43 (2002).
Jeffrey, M.I., D.M. Hewitt, X. Dai y S.D. Brunt, Ion exchange adsorption and elution for recovering
gold thiosulfate from leach solutions, Hydrometallurgy 100, 136-143 (2010).
Molleman, E. y D. Dreisinger, The treatment of copper-gold ores by ammonium thiosulfate
leaching, Hydrometallurgy 66, 1-21 (2002).
Munive, T.G., M. Encinas, A. Valenzuela, Valenzuela J.L. y J.R. Parga, Estudio comparativo de la
lixiviacin de un mineral refractario con cianuro de sodio y tiosulfato de sodio para la recuperacin
de oro y plata, GEOMIMET 291, 12-24 (2011).
Navarro, P., C. Vargas, A. Villarroel y F.J. Alguacil, On the use of ammoniacal/ammonium
thiosulphate for gold extraction from a concentrate, Hydrometallurgy 65, 37-42 (2002).

Informacin Tecnolgica Vol. 23 N 2 - 2012

59

Uso de Resina de Intercambio Aninico para la Recuperacin del Complejo Oro

Chaparro

Navarro, P., C. Vargas, V. Reveco y J. Orellana, Recuperacin desde un medio amoniacotiosulfato con resina de intercambio inico Amberlita IRA-410, Revista de Metalurgia 42(5), 354366 (2006).
Seob, I. y otros siete autores, Sequential process of sorption and incineration for recovery of gold
from cyanide solutions: Comparison of ion exchange resin, activated carbon and biosorbent,
Chemical Engineering Journal: 165, 440-446 (2010).
Valenzuela A., J.L. Valenzuela, S. Aguayo y J.R. Parga, Estudio de la resina AuRIX100 de
intercambio inico para recuperar oro en las soluciones cianuradas, GEOMIMET (268), 26-38
(2006).
Vargas, C., P. Navarro, E. Araya, F. Pavez y F.J. Alguacil, Recuperacin de oro a partir de
disoluciones de amoniaco y tiosulfato utilizando carbn activado, Revista de Metalurgia 42 (3),
222-233 (2006).
Yen, W.T., M. Aghamirian, G. Deschenes y S. Theben, Gold extraction from mild refractory ore
using ammonium thiosulfate. Proceedings of the International Symposium on Gold Recovery,
Montreal May 3-6 CIM (1998).
Zhang, H. y D.B. Dreisinger, The adsorption of gold and copper onto ion-exchange resins from
ammoniacal thiosulfate solutions, Hydrometallurgy 66, 67-76 (2002).

60

Informacin Tecnolgica Vol. 23 N 2 - 2012

REVISTA DE METALURGIA, 48 (3)

MAYO-JUNIO, 165-174, 2012
ISSN: 0034-8570
eISSN: 1988-4222
doi: 10.3989/revmetalm.1102

Tostacin de un concentrado refractario de oro y plata()

J. H. Coronado*, M. A. Encinas*, J. C. Leyva*, J. L. Valenzuela*, A. Valenzuela* y G.T. Munive*
Resumen

En el procesamiento de minerales de metales preciosos con altos contenidos de pirita, se obtienen concentrados
refractarios difciles de procesar. En este estudio se lixivi un concentrado refractario de oro y plata con cianuro de
sodio, obtenindose extracciones de 34 % para oro y 40 % para plata. Se utiliz el mtodo de tostacin para oxidar
el concentrado, hacindolo ms susceptible a la cianuracin, y extraer ms eficientemente el oro y la plata. Las
variables analizadas fueron: temperatura de tostacin y tiempos de tostacin y cianuracin. Adems, la calcina caliente
se agreg a la solucin lixiviante a temperatura ambiente para analizar el efecto en el tamao de partcula y recuperacin.
Los mejores resultados, aunque no del todo satisfactorios (50 % oro y 61 % plata), se obtuvieron mediante tostacin
del concentrado durante 4 h a temperaturas de 600 C, seguido de una cianuracin de 20 h. El consumo de cal para
elevar el pH a 11,3, se increment notablemente hasta 25 kg/m.

Palabras clave

Tostacin; Minerales refractarios; Cianuracin.

Roasting of refractory gold and silver concentrate

Abstract

In processing of precious metal ores with high pyrite content, refractory concentrates are obtained, which are
difficult to process. A refractory gold and silver concentrate was leached with sodium cyanide. Results show low
extraction percentages, being 34 % of gold and 40 % of silver. A roasting method to oxidize the concentrate was
used, making it more susceptible to cyanidation, hence a more efficient way to extract precious metals. The
variables include roasting temperature and roasting and cyanidation time. In addition, the hot calcine was added
to the leaching solution at room temperature to analyze the effect on particle size and recovery. The best results,
although not entirely satisfactory (50 % of gold and 61 % of silver) were obtained by roasting the concentrate for
4 h at 600 C, followed by cyanidation for 20 h. The lime consumption to raise the pH to about 11.3 was increased
markedly to 25 kg/m.

Keywords

Roasting; Refractory minerals; Cyanidation.

1. INTRODUCCIN
En Mxico existen muchas menas de baja ley, as
como otras en las que el oro y la plata se encuentran
ocluidos o asociados a minerales de hierro, arsnico,
manganeso y silicio, los cuales se clasifican como
depsitos refractarios aurferos y argentferos. La
mayora de las veces, la cianuracin de estos minerales
requiere largos periodos de lixiviacin y, desafortunadamente, bajas recuperaciones de oro[1-5]. La tostacin de minerales y concentrados refractarios de
oro, antes de la lixiviacin con cianuro, es un mtodo
alternativo que se ha empleado durante dcadas. El
principal objetivo de la tostacin es liberar el oro
ntimamente asociado a los minerales sulfurosos y

telurosos, para aumentar la extraccin del oro durante

la lixiviacin con cianuro. Esto se realiza oxidando
los sulfuros a xidos o sulfatos, o reduciendo los silicatos y xidos a un estado metlico crudo, con el propsito de cambiar los compuestos metlicos insolubles
en otros que sean solubles en el agente lixiviante; as
como para volatilizar ciertas impurezas solubles que
pudieran contaminar la solucin cargada. Tambin
es til para volver porosos los compuestos metlicos,
y hacerlos de esta forma ms fcilmente accesibles al
disolvente de la lixiviacin[6].
Como la tostacin es una operacin relativamente
costosa, solo puede aplicarse a materiales de alta ley
que puedan justificar los altos costos de este tratamiento. Sin embargo, puede obtenerse el efecto de

() Trabajo recibido el da 13 de enero de 2011 y aceptado en su forma final el da 20 de febrero de 2012.

*Departamento de Ingeniera Qumica y Metalurgia, Universidad de Sonora. Rosales y Blvd. Luis Encinas S/N, Hermosillo, Sonora, 83000,
Mxico. E-mail:(jhcoronado@iq.uson.mx.

165

J. H. CORONADO, M. A. ENCINAS, J. C. LEYVA, J. L. VALENZUELA, A. VALENZUELA Y G.T. MUNIVE

una tostacin oxidante o sulfatizante de minerales

sulfurosos de baja ley, mediante su intemperizacin
natural experimentada durante un periodo prolongado de tiempo.
La mineralizacin de los materiales refractarios
de oro no se ha establecido detalladamente para
todos los depsitos; no obstante, en muchos depsitos, la resistencia a la cianuracin directa se atribuye al oro extremadamente fino encapsulado en
pirita y ciertos minerales de la ganga, como cuarzo.
La presencia de materia carbonosa, arcillas, cianicidas, pelculas pasivantes, teluros y otros muchos
factores pueden tambin propiciar la refractariedad
de una mena[7]. En algunos depsitos se ha observado
que el oro incrustado en pirita se presenta en una
forma no metlica asociada a zonas ricas de arsenopiritas. Una explicacin es que los tomos de oro
han substituido al arsnico o a los posibles tomos
de hierro, dando lugar a una adecuada substitucin
intersticial. Metalrgicamente esto podra ser significativo, y puede explicar el porqu en una oxidacin se proyecta solamente la oxidacin parcial
de los sulfuros[8].
La qumica bsica de una oxidacin por tostacin
para minerales concentrados piritosos y arsenopiritosos de oro, es relativamente sencilla; los sulfuros
metlicos son convertidos a xidos metlicos y dixido de azufre (SO2), este ltimo liberndose como
gas. Las reacciones se desarrollan generalmente entre
600 y 700 C.
La tostacin de la pirita (FeS2) en una atmsfera
altamente oxidante, produce la hematita (Fe2O3)
segn lo mostrado en la reaccin (1):
4 FeS2 + 11 O2 ! 2 Fe2O3 + 8 SO2

(1)

Cuando la atmsfera de la tostacin es menos oxidante, la magnetita (Fe3O4), ser producida segn lo
mostrado en la reaccin (2):
3 FeS2 + 8 O2 ! Fe3O4 + 6 SO2

(2)

Para la extraccin ms favorable del oro, un producto que contiene aproximadamente 75 a 85 % de

hematita, y el resto magnetita, es generalmente el
ms deseable. Se puede formar durante la tostacin
un poco de sulfato de hierro (FeSO4), el cual es generalmente indeseable, los ferrocianuros se forman fcilmente con FeSO4 [9].
La arsenopirita (FeAsS) es oxidada a dixido de
azufre (SO2), hematita (Fe3O4) y trixido de arsnico
(As2O3).
166

La oxidacin de la arsenopirita es algo ms compleja

que la de la pirita. La reaccin (3) ocurrir si la arsenopirita se tuesta en una atmsfera altamente oxidante.
FeAsS + 3 O2 ! FeAsO4 + SO2

(3)

Esta es una reaccin indeseable puesto que se

forma el arseniato frrico (FeAsO4), que inhibir la
extraccin del oro durante la lixiviacin con cianuro.
Las reacciones deseables son mostradas en las reacciones (4 y 5); la reaccin (4) convierte el arseniato
a trixido de arsnico voltil (As2O3), en una atmsfera menos oxidante a una temperatura relativamente
ms baja (500 C y 80 % de O2).
La reaccin (5) se desarrolla a una temperatura y
a una atmsfera altamente oxidante.
12 Fe As S + 29O2 !
6As2 O3 + 4Fe3O4 + 12SO2

(4)

4Fe3O4 + O2 ! 6Fe2 O3

(5)

Para lograr estas reacciones se requiere una tostacin en 2 etapas. La etapa 1 debe ser a bajas temperaturas y poco aire para producir As2O3 y evitar la
formacin de FeAsO4. La etapa 2 debe ser a una temperatura alta y con exceso de aire para producir la
hematita porosa (As2O3 es durante la tostacin).
La reaccin (6) muestra que el carbn orgnico
elemental (C) se oxida a dixido de carbono (CO2).
C + O2 ! CO2

(6)

Esta reaccin depende del tipo de carbn presente

y de la temperatura de tostacin. El carbn orgnico
con una temperatura de ignicin bastante baja se oxidar fcilmente a CO2, mientras que los carbonos de
tipo grafticos con altas temperaturas de ignicin pueden no reaccionar durante la tostacin. Los carbonatos de magnesio y calcio (MgCO3, CaCO3), se calcinan parcialmente a xidos; sin embargo, las temperaturas de tostacin son demasiado bajas para la
calcinacin completa[6].
La reaccin (7) muestra la descomposicin de los
carbonatos de calcio y magnesio a xidos de calcio
y magnesio (CaO/MgO).
CaCO3 /MgCO3 ! CaO/MgO + CO2

(7)

Rev. metal. 48 (3), MAYO-JUNIO, 165-174, 2012, ISSN: 0034-8570, eISSN: 1988-4222, doi: 10.3989/revmetalm.1102

TOSTACIN DE UN CONCENTRADO REFRACTARIO DE ORO Y PLATA

ROASTING OF REFRACTORY GOLD AND SILVER CONCENTRATE

Tabla I. Anlisis qumico del concentrado

Esta reaccin depende del tipo de carbonatos presentes y de la temperatura. El carbonato de magnesio
se descompone a una temperatura mucho ms baja
que el carbonato de calcio (350 C frente a 825 C,
dependiendo de los minerales). La descomposicin
del dixido de azufre descomponindose a sulfato o
sulfito (SO3=) es a menudo una reaccin deseable,
porque reduce la cantidad de SO2 que se debe lavar
en los gases de salida. La desventaja de la formacin
de sulfato de calcio (CaSO4) es que pueden alterarse
las caractersticas de la calcina e inhibir la disolucin
del oro.
La reaccin (8) muestra la reaccin entre CaO o
MgO, generado en la reaccin (7), y el SO2 durante
la tostacin.
CaO/MgO + SO2 + O2 ! CaSO4/MgSO4 (8)
Esta reaccin es generalmente deseable, sin
embargo, con algunos minerales concentrados, la formacin de sulfato de calcio inhibir la extraccin del
oro durante la lixiviacin con cianuro (el oro se encapsula en el sulfato de calcio). Esta reaccin se refiere
a la fijacin del SO2. Una tostacin ideal formar la
hematita porosa; la temperatura excesiva de tostacin
(sobre tostacin o sinterizacin del mineral), inhibir
la formacin de la hematita y reducir seriamente la
extraccin del oro. La tostacin generalmente es perjudicial para la plata en las extracciones por lixiviacin; cuanto ms alta es la temperatura de tostacin,
ms baja es la extraccin de plata. Las variables de
proceso ms importantes que deben ser consideradas
en la tostacin son: cantidad de alimentacin, temperatura, tiempo de tostacin, adicin de oxgeno,
oxidacin del azufre y del carbn orgnico elemental,
fijacin del dixido de azufre, entre otras[5, 10 y 11].

2. MTODO EXPERIMENTAL
El anlisis qumico del concentrado mineral utilizado
en este estudio se muestra en la tabla I. Las pruebas
de tostacin se llevaron a cabo utilizando un horno
elctrico marca Lindberg/Blue M., modelo 55345.
Para hacer los anlisis del tamao de partcula, se utiliz un analizador de partculas marca Coulter 100 Q.
Para evaluar los resultados obtenidos en la tostacin
del concentrado se utiliz una lixiviacin agitada con
cianuro de sodio (NaCN), en un reactor de vidrio
Pyrex de 100 ml con acceso para la toma de muestra,
y un sistema de agitacin marca STIR-PAK de
25-2.300 rpm, equipado con flecha y propela. Los
reactivos utilizados en la lixiviacin fueron cianuro

Table I. Chemical analysis of concentrate

Elemento

Composicin (%)

Au
Ag
Fe
Cu
Zn
As
S

60(*)
10,200(*)
36,38
0,50
4,72
0,15
33,34

pH
(*)

6,05

g/t.

de sodio, hidrxido de calcio y nitrato de plata, todos

ellos de grado reactivo y disueltos en agua destilada.
Para el anlisis de la solucin lixiviada, se utiliz un
espectrofotmetro de absorcin atmica, marca Perkin
Elmer modelo 3110 con lmpara de ctodo hueco a
una longitud de onda de 242,8 nm para el oro; para
la plata se aplic una llama de oxgeno-acetileno y
una longitud de 328,1 nm.
En cada prueba experimental, primero se ajust el
horno tostador a temperatura de trabajo, posteriormente se pesaron 12 g de concentrado, los cuales se
colocaron en un recipiente de porcelana; la muestra
de concentrado se introdujo en el interior del horno
tostador por un tiempo programado. Al finalizar la
etapa de tostacin, la muestra se retir del horno,
transfirindose a un reactor con el agente lixiviante,
midiendo inmediatamente el valor de pH.
Seguidamente se adicion cal hasta alcanzar un valor
de pH entre 10,5 y 11,0, para posteriormente agregar
el cianuro de sodio, tomando este paso como el inicio
de la etapa de lixiviacin y mantenindola durante
el intervalo de tiempo determinado. Se tomaron muestras de solucin a intervalos de tiempo predeterminados para analizar las concentraciones de oro y plata
en la solucin. La cantidad de NaCN en la solucin,
se obtuvo por titulacin con nitrato de plata.

3. RESULTADOS Y DISCUSIN
En la figura 1 a) se presenta el anlisis de tamao de
partcula del concentrado sin tostar. Podemos observar que la media del tamao de partcula se encuentra
alrededor de 23,56 micras, y la moda alcanza un valor
de 23,81 micras.

Rev. metal. 48 (3), MAYO-JUNIO, 165-174, 2012, ISSN: 0034-8570, eISSN: 1988-4222, doi: 10.3989/revmetalm.1102

167

J. H. CORONADO, M. A. ENCINAS, J. C. LEYVA, J. L. VALENZUELA, A. VALENZUELA Y G.T. MUNIVE

Figura 1. Resultados del analizador de partculas del concentrado: 1 a) sin tostar; 1 b) concentrado tostado, t = 1 h, T = 500 C; 1 c) concentrado tostado, posteriormente la calcina caliente
se agreg inmediatamente a la solucin lixiviante, t = 1 h, T = 500 C.
Figure 1. Particle size analyses of the concentrate: 1 a) unroasted concentrate; b) roasted
concentrate, t = 1 h, T = 500 C; 1 c) roasted concentrate, after roasting the hot calcine was
added immediately to the leaching solution, t = 1 h, T = 500 C.
Analizando de forma general, podemos concluir
que el concentrado obtenido del proceso de flotacin
contiene partculas finas, con tamaos menores de
33 micras. En la figura 1 b) se presenta el anlisis de
tamao de partcula obtenido del concentrado calcinado por un tiempo de 1 h a una temperatura de
500 oC, con el objetivo de observar el cambio de
tamao de partculas al someterse al proceso de tostacin. En esta figura se observa que existe un aumento
considerable en el tamao de la partcula despus del
proceso de tostacin, ya que el valor medio en este
caso result ser de 95,18 micras, con una moda de
127,6 micras. Por lo anterior se concluye que existe
un aumento en el tamao de las partculas del concentrado al estar expuesto a este tratamiento trmico,
el cual posiblemente se deba a una expansin de las
partculas, generada por la salida de elementos en forma
de gases, los cuales tienen su punto de ebullicin menor
a 500 oC. En la figura 1 c), se presenta el anlisis de
tamao de partcula del concentrado que fue sometido
a un proceso de tostacin a una temperatura de 500 oC
durante una hora, y posteriormente la calcina caliente
se agreg inmediatamente a la solucin lixiviante, que
se encontraba a temperatura ambiente, para lograr con
esto, un cambio rpido de temperatura en el sistema;
con el objetivo de determinar si la partcula caliente,
por efecto del cambio trmico sufre algn tipo de fragmentacin en su tamao, lo cual podra ayudar a la
liberacin de los valores. Sin embargo, comparando
estos resultados con los de la figura 1 b), observamos
diferencias poco significativas en el tamao de partcula; stas se consideran no significativas para deter168

minar que exista algn cambio apreciable en el tamao

de la partcula. La tabla II, presenta el anlisis de los
parmetros estadsticos antes mencionados.
Tabla II. Anlisis estadstico del analizador
de partculas
Table II. Statistical analysis of particle
size analyzer
Volumen estadstico (aritmtico) 100%

Media
Mediana
Moda
D.S.
C.V.
%<
10
25
50
75
90

23,56
17,38
23,81
21,10
89,5(*)

95,14
78,14
127,6
77,26
81,2(*)

106,3
94,47
127,6
75,35
70,9(*)

2,498
7,405
17,38
33,03
56,98

10,29
31,86
78,14
140,5
207,6

17,40
46,12
94,49
151,8
212,7

Clculo de partculas de 0,375 a 948 m.

Tamao en micras, (*) %

Rev. metal. 48 (3), MAYO-JUNIO, 165-174, 2012, ISSN: 0034-8570, eISSN: 1988-4222, doi: 10.3989/revmetalm.1102

TOSTACIN DE UN CONCENTRADO REFRACTARIO DE ORO Y PLATA

ROASTING OF REFRACTORY GOLD AND SILVER CONCENTRATE

La figura 2 presenta los resultados obtenidos en

la recuperacin de oro y plata durante la lixiviacin
del concentrado, por un periodo de 25 h sin ningn
tratamiento de tostacin.
En esta figura se muestra que a las 2,5 h, el oro
tiene un porcentaje de recuperacin del 24,16 %,
posteriormente a las 5 h se incrementa hasta un
28,89 %, alcanzando un mximo del 34,16 % a las
25 h. La plata tiene un comportamiento ligeramente
superior, con porcentajes de recuperacin de 31,36 %
en las primeras 2,5 h, hasta llegar a 40,19 % despus
de 25 h de lixiviacin. El consumo de cianuro para
este tipo de concentrado sin tostar alcanza los
3,6 kg/m3. Se puede apreciar tanto para el oro como
para la plata, que las recuperaciones por el mtodo
de cianuracin de estos concentrados son demasiado
bajas, por lo que se considera al concentrado como
refractario, siendo necesario utilizar un mtodo complementario y/o alternativo para su tratamiento, con
el fin de aumentar la recuperacin de los valores de
oro y plata.
En la figura 3 se observan los resultados obtenidos
en las prdidas de peso, azufre y arsnico del concentrado calcinado a diferentes temperaturas, de los 350
a 800 C con un tiempo de tostacin de 1 h.
A temperaturas menores de 350 C existe una
prdida de peso no mayor del 0,94 %; al aumentar la

temperatura a 400 C el incremento en la prdida

de peso aumenta notablemente alcanzando un
13,42 %, siguiendo este aumento hasta un 18,68 %
a una temperatura de 450 C. A partir de esa temperatura, la velocidad de prdida de peso disminuye,
alcanzando un mximo de 19,6 % a una temperatura
de 800 C. Podemos pensar que a temperaturas alrededor de 450 C la prdida de peso se relaciona con
la prdida de azufre presente en el concentrado, entre
otros elementos voltiles.
En el caso del azufre, a temperaturas menores de
350 C, la eliminacin por volatilizacin del contenido total es bajo, con un 1,14 %. Entre 350 y 450 C
la prdida de azufre se incrementa rpidamente hasta
un 76,3 % y a 500 C alcanza un 84,55 %. A partir
de esta ltima temperatura, la velocidad de prdida
se hace ms lenta hasta alcanzar un 93,16 % a 700 C.
Observamos en la grfica, que los resultados obtenidos
coinciden con los esperados, ya que el punto de ebullicin del azufre (444,6 C), est dentro de los intervalos de temperaturas manejadas.
El porcentaje de prdida de arsnico a 350 C es
aproximadamente del 12 %, al ir incrementando la
temperatura, se aprecia que el porcentaje aumenta
de tal manera que a una temperatura de 700 C la
prdida es del 40 %. Sin embargo, la ley del arsnico
en el concentrado es baja, 0,15 %; analizando estos

Figura 2. Recuperacin de oro y plata y consumo de cianuro del concentrado sin tratamiento de tostacin. t = 25 h, peso de muestra = 12 g.
Figure 2. Recovery of gold and silver, and cyanide consumption from the
concentrate without a roasting threatment, t = 25 h, sample weight = 12 g.
Rev. metal. 48 (3), MAYO-JUNIO, 165-174, 2012, ISSN: 0034-8570, eISSN: 1988-4222, doi: 10.3989/revmetalm.1102

169

J. H. CORONADO, M. A. ENCINAS, J. C. LEYVA, J. L. VALENZUELA, A. VALENZUELA Y G.T. MUNIVE

Figura 3. Efecto de la temperatura de tostacin, en la prdida de peso,

azufre y arsnico del concentrado, t = 1 h, peso de muestra = 12 g,
T = 500 C.
Figure 3. Effect of roasting temperature, in weight loss of sulfur and arsernic
from the concentrate, t = 1 h, sample weight t = 12 g, T = 500 C.
resultados se puede pensar que el intervalo de temperatura de tostacin no afecta de forma general en
el contenido de arsnico, por lo que posiblemente
ste se encuentra asociado con alguna especie que
no permite su completa eliminacin.
En la figura 4 se muestran los resultados del comportamiento en la recuperacin de oro y plata de concentrado tostado y lixiviado durante 1 h. La recuperacin del oro a temperaturas de tostacin de 450 C
es del 32,16 %; al aumentar la temperatura a 500 C
existe una disminucin drstica en los porcentajes
de recuperacin del oro de 10,83 %, hasta llegar a
6,58 % a 700 C. Los porcentajes de lixiviacin de
la plata se encuentran alrededor del 10,68 % a 450
C, manteniendo valores casi similares hasta la temperatura de 700 C. El consumo de cianuro de sodio
es de alrededor de los 0,5 kg/m3 a 400 C, generndose un aumento paulatino hasta llegar alrededor de
los 0,8 kg/m3 a 700 C.
Puede observarse, que tanto las recuperaciones
de plata como las de oro son muy bajas; posiblemente
los tiempos de tostacin y lixiviacin no son los adecuados. La calcina que se obtiene en la tostacin es
de color gris-negruzco, indicndonos que hay presencia de una mayor cantidad de magnetita, lo cual no
favorece a la lixiviacin, coincidiendo con lo observado en otros estudios, donde un color de calcina
170

caf-chocolate indica una mayor presencia de hematita ( 75-80 %), siendo el resto de magnetita, donde
se obtienen las mejores recuperaciones[9].
La figura 5 presenta los resultados obtenidos en
la recuperacin de oro y plata del concentrado tostado
y lixiviado con un tiempo de 4 h de tostacin y 20 h
de lixiviacin respectivamente.
En esta figura puede observase que el oro se recupera aproximadamente en un 27 % a una temperatura
de tostacin entre 400 y 500 C. Al aumentar la temperatura a 600 C hay un aumento en la recuperacin
de oro casi del 50 %, y al tostar a 700 C la recuperacin disminuye drsticamente hasta un 20,66 %.
Respecto a la plata, sta sigue una tendencia parecida
al oro, pero con una mayor recuperacin, as podemos
observar, que al tostar el concentrado a 400 C, la
recuperacin es del 31,32 %, alcanzando un mximo
de 61,27 % a 600 C. Al incrementar la temperatura
a 700 C existe una cada en la recuperacin de plata
al 51 %. La prdida de la recuperacin del oro y plata
a altas temperaturas, posiblemente se deba a la sinterizacin de la partcula de concentrado.
El consumo de cianuro a 400 C, es de 0,8 kg/ton
y disminuye hasta un 0,2 kg/m3 a 700 C.
En la figura 6 se presentan los resultados obtenidos
en la recuperacin de oro y plata, cuando se agreg
inmediatamente el concentrado tostado (calcina),

Rev. metal. 48 (3), MAYO-JUNIO, 165-174, 2012, ISSN: 0034-8570, eISSN: 1988-4222, doi: 10.3989/revmetalm.1102

TOSTACIN DE UN CONCENTRADO REFRACTARIO DE ORO Y PLATA

ROASTING OF REFRACTORY GOLD AND SILVER CONCENTRATE

Figura 4. Resultados en la recuperacin de oro, plata y consumo de cianuro

del concentrado tostado y lixiviado, t = 1 h, peso de muestra = 12 g.
Figure 4. Recovery of gold and silver, and cyanide consumption from
the concentrate roasted and leached, t = 1 h, sample weight = 12 g.

Figura 5. Resultados en la recuperacin de oro, plata y consumo de

cianuro del concentrado tostado y lixiviado, tostacin t = 4 h, lixiviacin
t = 20 h, peso de muestra = 12 g.
Figure 5. Recovery of gold and silver, and cyanide consumption from
the concentrate roasted and leached roasting treatment, t = 4 h, leaching
t = 20 h, sample weight = 12 g.
Rev. metal. 48 (3), MAYO-JUNIO, 165-174, 2012, ISSN: 0034-8570, eISSN: 1988-4222, doi: 10.3989/revmetalm.1102

171

J. H. CORONADO, M. A. ENCINAS, J. C. LEYVA, J. L. VALENZUELA, A. VALENZUELA Y G.T. MUNIVE

Figura 6. Resultados en la recuperacin de oro, plata y consumo de

cianuro del concentrado tostado y lixiviado, tostacin t = 4 h, lixiviacin
a una temperatura inicial de 40 C, t = 20 h, peso de muestra = 12 g.
Figure 6. Recovery of gold and silver, and cyanide consumption of the
concentrate roasted and leached roasting treatment, t = 4 h, leaching
at initial temperature of 40 C, t = 20 h, sample weight = 12 g.
desde el horno a la solucin lixiviante, que se encontraba a 40 C, con el objetivo de observar el comportamiento en los porcentajes de recuperacin del
oro y plata al efectuar un cambio brusco en la temperatura de la calcina caliente. La recuperacin del
oro a la temperatura de 400 C se encuentra alrededor
del 13 %; al aumentar la temperatura disminuye la
extraccin de tal manera que a 500 C es aproximadamente 7 %, hasta llegar a un 3 % en 700 C. Por
otro lado, la recuperacin de plata se encuentra en
11 % a 400 C, empezando a subir a 15 % en 500 C,
para alcanzar un 26 % a 700 C.
Estas recuperaciones de oro y plata son demasiado
bajas, ya que la recuperacin del oro cae hasta un
3 %, y aunque la plata sube, en general es muy poco.
Se observa que a diferencia de las pruebas anteriores
el comportamiento es muy diferente, posiblemente
el cambio de temperatura de forma rpida afecta a la
superficie de la partcula, lo cual impide la penetracin de la solucin lixiviante para la extraccin de
los valores. Existe un aumento de la temperatura en
la solucin de 2 a 3 C, lo cual no provoca beneficio
alguno para la etapa de lixiviacin en este caso. El
consumo de cianuro oscila en un promedio de
0,9 kg/m3.
172

En la figura 7 se presentan los resultados de la

recuperacin de oro y plata cuando la calcina caliente
se pone en contacto con la solucin lixiviante que
se encuentra a una temperatura de 50 C. Los valores
obtenidos son casi similares a los obtenidos en la grfica anterior (Fig. 6), ya que el porcentaje de recuperacin de oro se encuentra alrededor del 24 % a
una temperatura de tostacin de 400 C, y disminuye
hasta un 1,5 % a 700 C. La recuperacin de plata a
400 C es del 10 % y sufre un incremento hasta un
32 % a 700 C. Con lo anterior se constata que al
agregar la calcina caliente directamente del horno a
la solucin lixiviante, no existe una mejora en la
recuperacin del oro, sino que la perjudica notablemente, ya que las recuperaciones son demasiado bajas.
Por otro lado, aunque la recuperacin de plata se
incrementa, estos resultados no son del todo satisfactorios. El consumo de cianuro se encuentra alrededor de 0,8 kg/m3.
En la figura 8 se presenta el consumo de cal para
elevar el pH del concentrado lixiviado en 24 h, alrededor de 1,3 kg/m3 para subir el pH a 11,4. Tambin
se presenta el consumo de cal de la lixiviacin del
concentrado tostado a 500 C. Al inicio el pH de la
solucin oscila alrededor de 3,0; al agregar el equi-

Rev. metal. 48 (3), MAYO-JUNIO, 165-174, 2012, ISSN: 0034-8570, eISSN: 1988-4222, doi: 10.3989/revmetalm.1102

TOSTACIN DE UN CONCENTRADO REFRACTARIO DE ORO Y PLATA

ROASTING OF REFRACTORY GOLD AND SILVER CONCENTRATE

Figura 7. Resultados en la recuperacin de oro, plata y consumo de

cianuro del concentrado tostado y lixiviado, tostacin t = 4 h, lixiviacin
a una temperatura inicial de 50 C, t = 20 h, peso de muestra = 12 g.
Figure 7. Recovery of gold and silver, and cyanide consumption of the
concentrate roasting and leached roasting t = 4 h, leaching at initial
temperature of 50 C, t = 20 h, sample weight = 12 g.

Figura 8. Consumo de cal del concentrado lixiviado y tostado. Lixiviacin

t = 20 h, tostacin t = 4 h, peso de muestra = 12 g.
Figure 8. Consumption of limestone from the concentrate leached and
roasted. Leaching t = 20 h, roasting t = 4 h, , sample weight = 12 g.
Rev. metal. 48 (3), MAYO-JUNIO, 165-174, 2012, ISSN: 0034-8570, eISSN: 1988-4222, doi: 10.3989/revmetalm.1102

173

J. H. CORONADO, M. A. ENCINAS, J. C. LEYVA, J. L. VALENZUELA, A. VALENZUELA Y G.T. MUNIVE

valente a 7 kg/m3 de cal el pH es de 3,2; al aumentar

la cal a 17 kg/m3 el pH es de 6,1, siendo necesario
agregar otros 7 kg de cal (suman ya 23 kg/m) para
llegar a un pH mayor de 11. Si comparamos el consumo de cal para elevar el pH alrededor de 10,5 con
respecto a un mineral oxidado, ste requiere aproximadamente 1 kg/m3, por lo que concluimos que es
demasiada la cal necesaria para obtener el pH adecuado para la lixiviacin.

caf-chocolate, nos indica que se efecta una oxidacin de los sulfuros a hematita (75-80 %) y
magnetita (20-25 %) lo cual favorece a la lixiviacin, coincidiendo con lo observado en otros
estudios[9], donde reportan buenas recuperaciones
del mineral de oro y plata. Se recomienda hacer
otras pruebas con otros lixiviantes, para comparar
recuperaciones, y/o utilizar otro mtodo alternativo en lugar de tostacin.

CONCLUSIONES

REFERENCIAS

El concentrado presenta una ley de oro de 60 g/t

y de plata de 10,200 kg/t, un 36,38 % de hierro
y 33,34 % de azufre. El azufre se elimina hasta un
60 % a una temperatura de tostacin inicial de
400 C, hasta alcanzar un 93 % a una temperatura
de 700 C.
Al tostar el concentrado se detect un incremento en el tamao de partcula, debido posiblemente a la eliminacin del azufre en forma de
gas. La lixiviacin del concentrado por 24 h,
alcanza un porcentaje de recuperacin del oro
del 34 % y del 40 % para la plata, confirmndose
la clasificacin de mineral como refractario.
A una temperatura de tostacin de 600 C y despus de lixiviar con cianuro de sodio se obtiene
un porcentaje de recuperacin mxima del oro
del 50 % y 61 % para la plata. Al aumentar la
temperatura a 700 C, las recuperaciones disminuyen, posiblemente debido a una sinterizacin
de la partcula. Al someter la calcina caliente, a
la solucin lixiviante, existe un aumento de la
solucin de 2 a 3 C, resultando en porcentajes
de recuperacin de oro y plata muy bajos.
El consumo de cal para elevar el pH a las condiciones de lixiviacin con cianuro (pH > 10),
oscila alrededor de 25 kg/m. El color de la calcina

[1] E. Salinas, I. Rivera, F. R. Carrillo, F. Patio, J.

Hernndez y L. E. Hernndez. Rev. Soc. Qum.
Mx. 48 (2004) 315-320.
[2] J. R. Parga y F. R. Carrillo. Rev. Metal. Madrid,
32 (1996) 254-261.
[3] V. Arias-Arce, R. Coronado-Falcn, L. Puente
Santibez y D. Lovera-Dvila. Revista del
Instituto de Investigacin FIGMMG, 8 (2005)
5-16.
[4] O. Celep, I. Alp, H. Deveci y M. Vicil. Met.
China 19 (2009) 707-713.
[5] J. H. Coronado, Tesis de Maestra, Departamento
de Ingeniera Qumica y Metalurgia, Universidad
de Sonora, 1997.
[6] J. R. Goode. TMS, EPD Congress, 1993, pp.
291-317.
[7] J. C. Yannopoulus. The extractive metallurgy
of gold, Van Nostrand Reinhold, 1991 pp.
79-98.
[8] D. C. Harris. Mineral. Deposita 25 (1990) 3-7.
[9] R. B. Coleman. Proceedings of Gold. Symposum,
1990, pp. 381-388.
[10] A. Vladimir, R. C. Falcon, L. Puente y D. Lovera.
Rev. Inst. Inv. FIGMMG, 16 (2005) 5-7.
[11] P. R. Taylor, Z. B. Yin y R. W. Barlett. Gold 90,
SME, 1990, pp. 411-419.

174

Rev. metal. 48 (3), MAYO-JUNIO, 165-174, 2012, ISSN: 0034-8570, eISSN: 1988-4222, doi: 10.3989/revmetalm.1102

Advances in Chemical Engineering and Science, 2012, 2, 342-349

doi:10.4236/aces.2012.23040 Published Online July 2012 (http://www.SciRP.org/journal/aces)

Kinetic Aspects of Gold and Silver Recovery in

Cementation with Zinc Power and Electrocoagulation
Iron Process
Gabriela V. Figueroa Martinez1, Jos R. Parga Torres1, Jess L. Valenzuela Garca2,
Guillermo C. Tiburcio Munive2, Gregorio Gonzlez Zamarripa1
1

Department of Metallurgy and Materials Science, Institute of Technology of Saltillo, Saltillo, Mxico
2
Department of Chemical Engineering and Metallurgy, University of Sonora, Hermosillo, Mxico
Email: jrparga@its.mx
Received February 11, 2012; revised March 16, 2012; accepted March 29, 2012

ABSTRACT
The Merrill-Crowe or Cementation process is used for concentration and purification of gold and silver from cyanide
solutions. Among other available options for recovery of precious metals from cyanide solutions, Electrocoagulation
(EC) is a very promising electrochemical technique for the recovery of this precious metals. In this work first, an introduction to the fundamentals of the Merrill Crowe and EC process are given, then Kinetic aspects conditions and results
of the both process, for the removal of gold and silver from cyanide solutions are presented, and finally the characterization of the solid products formed during the EC process with X-ray Diffraction and SEM are shown. Results suggests
that The cementation of both gold and silver by suspended zinc particles conforms to well-behaved fist order kinetics
and for the EC process the results show that is an excellent option to remove Au and Ag from cyanide solution by using
iron electrodes. Finally, 99.5% of gold and silver were removed in the experimental EC reactor, and it was achieved in
5 minutes or less.
Keywords: Cyanidation; Merrill Crowe; Electrocoagulation; Kinetics

1. Introduction
Cyanide leaching processes have been used by the mining industry for over 150 years in the extraction of noble
metals, the popularity of cyanidation is based mostly on
the simplicity of the process. Elsner in Germany in 1846
studied the dissolution of gold in cyanide aqueous solution and noted that atmospheric oxygen played an important role during dissolution of gold [1]. Also, sodium
cyanide in an alkaline solution is a strong solvent for
gold and silver, most mill operators use it to dissolve fine
gold particles with a practical maximum size is no greater
than 50 microns. In most cyanidation operations, the gold
particles require 24 to 72 hrs for complete dissolution in
slurry or pulp of about 50 percent solids. Extremely large
leaching reactors known as Pachuca tank in with the
finely ground ore was agitated with the alkaline cyanide
leaching agent and equipped with compressed air injection in the pulp had been designed to dissolve the gold
and silver. It is widely accepted that the gold cyanidation
process can be represented by the classic Elsners Equation (1). The mechanism and kinetics have been discussed in several papers and reviews [1,2].
Copyright 2012 SciRes.

4Au 8CN

O2

2H 2 O

4Au CN

4OH

(1)

Silver, similarly, dissolves readily in dilute cyanide solutions in the presence of oxygen. However, since silver
in Mexicans ores occurs as argentite the cyanidation and
sulphide oxidation reaction are as follows:
Ag 2S 4CN

2Ag CN

S2

(2)

1
O 2 H 2 O CNS 2OH
(3)
2
The cyanide concentration determines the rate of anodic gold dissolution while the oxygen reduction rate is
dependent on the concentration of dissolved oxygen. In
the cyanidation process, free cyanide ions in solution can
be provided only at pH > 9.3. The pH of the pulp can be
increased with the additions of alkali hydroxides (NaOH,
KOH, Ca(OH)2 etc.), known as proactive alkalis. Also,
details of this electrochemical reaction have received
considerable attention and under certain circumstances
the reaction is limited by the coupled diffusion of CN
and O2 to the gold surface.
Lixiviation of undesirable base metals, such as copper,
S2

CN

ACES

343

G. V. F. MTZ ET AL.

iron and arsenic, reduces the efficiency of the process by

consuming additional reagents, and necessitates further
processing to remove these contaminants [3].
Actually, the two conventional processes for gold and
silver recovery from cyanide leach solution are: the Merrill Crowe zinc dust cementation and the carbon adsorption process. In the first process, the efficiency of the
reaction is significantly improved by removing dissolved
oxygen from the system prior to zinc addition, using a
vacuum deaeration technique. This reaction of cementation is sensitive to suspend solids in the leach solution
and thus requires solution clarification before cementation. In the activated carbon process, the precious metals
are absorbed onto granules of carbon and after loading,
they are then stripped of the loaded gold by a hot causticcyanide solution. Then, the cathodes from the carbon
adsorption process or the precipitates from the Merrill
Crowe process (metal displacements) are then melted in
crucible furnaces along with fluxing materials such as
borax, niter and silica. The resultant product from smelting is Dore bullion of precious metals typically analyzing
more than 95 percent of precious metals.
Each recovery method has advantages and disadvantages. Process selection depends on the specific conditions for particular operation and the facilities already
available. Another new process is the Electrocoagulation
(EC) technology and has recently been reviewed as an
alternative for gold and silver recovery from alkaline
cyanide solutions [3]. The EC process is a very promising technique for the recovery of precious metals such as
silver and gold: EC needs no chemical reagents, does not
generate toxic materials requiring special disposal and
this also make it an ecologically viable technique. Literature reviewing showed that the potential of EC as an
alternative to traditional treatment recovery of precious
metals (silver and gold cyanide) has not yet been exploited.

1.1. The Merrill Crowe Process or Cementation

Technology
The term cementation comes from a Spanish word meaning precipitation. This term was first used in 1500 to
describe a process for the recovery of copper from aqueous solutions at Rio Tinto in Spain. However, cementation of a noble metal from solution by means of more
base, or electronegative, metal has been practiced since
ancient times [4]. Near the beginning of the fourth century, Zosimos stated that, when iron is immersed in a
solution of a copper salt, it acquires a coating of copper.
In the sixteenth century, Paracelsus precipitated silver
from silver nitrate by inserting a plate of copper in the
solution, and he noted that the copper dissolved. Bergman, in this De Precipitates Metallics, in the midCopyright 2012 SciRes.

eighteenth century, observed that the metals precipitate

one on another after a certain order of nobility: zinc, iron,
lead, tin, copper, silver and gold.
Then, cementation reactions, variously know as metaldisplacement reactions or contact-reduction reactions, are
processes in which a metal ion in a solution is reduced to
the elemental metallic state with the concurrent oxidation
of a more electronegative metal placed into the same
solution. This process is one of the most ancient, yet
economical and efficient, hydrometallurgical processes
known and has been used for the recovery of dissolved
metal values from leach solutions, as well as for the purification of electrolytes. Cementation has been extensively applied for the recovery of gold and silver from
cyanide solutions, typically followed by the production
of Dore metal, which is known as the Merrill-Crowe
process. Although cementation of precious metals is
widely used in the metallurgy industry, most of the articles published on cementation of gold and silver until
about 1980 dealt only with plant practice. Scientific detailed laboratory investigations of the cementation reaction have only been reported during the past three decades. Studies of gold and silver have mostly been confined to the kinetics of gold and silver cementation on
rotating discs or cylinders [5].
In spite of this research effort, the mechanistic details
of the reactions taking place during cementation and the
role of various species in solution in promoting or inhibiting the recovery of precious metals have received little
attention and are still somewhat unclear. For example, it
is generally accepted that cementation is sensitive both to
the alkalinity and to the free cyanide concentration in
solution. However, suitable experimental data are not
available to describe plant practice in any detail. Only a
few fundamental studies have been carried out in the
recent past and also, until now, no detailed research has
been reported regarding the morphological influence of
the deposit structure on the cementation rate.

1.2. Review of Cementation Phenomena

In cementation reactions the metal to be reduced from
aqueous solutions is more noble, having a greater electron affinity, than the precipitating metal. For example,
the recovery or metallic silver by cementation with zinc
dust is an electrochemical process involving the oxidation of zinc and the reduction of the silver cyanidation.
The overall stoichiometry for the reaction in the case of
silver is as follows:
2Ag CN

Zn

2Ag Zn CN

(4)

A similar reaction can be written for gold precipitation.

Silver is deposited at cathodic surface sites while zinc
dissolves from anodic sites, and electrons are conducted
ACES

344

G. V. F. MTZ ET AL.

between the two metallic phases as shown in Figure 1.

1.3. Cementations Kinetics

Considerable research has been reported on the characteristic features and mechanistic details of cementation
reactions and this literature has been reviewed in terms of
electrochemical theory and transport phenomena on several occasions [6].
In most cases, the cementation reactions follow firstorder reaction kinetics and generally are limited by diffusion of the noble metal ion through the mass-transfer
boundary layer. In some cases the structure and morphology of the reaction product can have a significant
effect on passivating the surface in other cases.
Most of the cementation reactions are found to be firstorder diffusion processes [7] with respect to the noble
metal ion, and the reaction velocity constant, k, for such
a reaction may be computed from the general first-order
rate equation:

dc
dt

kAC
V

(5)

If k is not concentration dependent and the area is unchanging, Equation (5) may be integrated resulting in the
integrated first-order expression,
C
log
Co

kAt
2.3V

(6)

where C and Co are the noble metal concentrations at tine

t and the initial concentration at time t = 0, respectively;

k is the reaction velocity constant (cm/sec); A is reaction

surface area (cm2); and V is the solution volume rate
(cm3). In Equation (5), it can be seen that the cementation
rate is a function of the reaction area A. it has been
shown by many investigators that in almost all cementation systems the initial exposed geometric area of the
precipitant metal can be used in the analysis of initial rate
data. However, in a more general sense, the area term is
not always that simple to evaluate due to the changing
nature of the noble metal deposit which grows on the
active metal during the course of the reaction.
Experimental investigations [7] indicate that most cementation reactions are controlled by a mass transfer
process, film diffusion, as indicated by the results presented in Table 1.
Notice in Table 1, that for almost all the cementation
systems the apparent activation energy is in the range 2 6 kcal/mole which would suggest that the cementation
reactions are limited by mass transfer in the aqueous
phase, with some exceptions (Pb2+/Fe and Pb2+/Cu). Also
the reaction velocity constants are of the order 102
cm/sec which also supports the position that these cementation reactions are mass transfer controlled.

1.4. The Electrocoagulation Technology

Electrocoagulation (EC) has been known as an electrochemical phenomenon since the last century. It has been
employed previously for treating many types of wasteTable 1. Data for selected cementation aqueous systems at
25C [7].
System

Eo , V

Ag+/Cu

2.0 - 5.0

2.5 - 6.0 102

1.83

3.7 - 5.8

1.5 102

Ag /Fe (Cl )

1.29

3.0

2.2 102

Ag+/Zn (CN)

0.95

5.5

5.5 102

Ag+/Zn

1.56

2.0 - 6.0

2.6 - 5.2 102

3+

As /Cd

0.65

3.1 1.3

7 103

Au+/Zn(CN)

0.61

3.1

1.7 102

Bi /Fe

0.76

4.5 - 7.6

2.9 102

Cd2+/Zn

0.36

4.0 - 4.7

0.54 - 1.1 102

2+

Cu /Fe

0.75

3.1 - 5.1

0.6 - 0.9 102

Cu2+/In

0.83

2.3

5.9 102

2+

Cu /Ni

0.57

2.7 - 3.7 (14.2 - 19.0)

0.25 - 1.0 102

Cu2+/Zn

1.10

3.1

1.6 - 2.1 102

Ni2+/Fe

1.4 104

3+

Copyright 2012 SciRes.

Reaction Velocity
Constant, cm/sec

0.46

Ag+/Cu (CN)

Figure 1. Electrochemical reaction of cementation of silver

on zinc particle.

Activation Energy,
Kcal/mole

0.21

7.0

2+

Pb /Fe

0.31

12.0

Pb2+/Zn

0.64

Pb2+/Cu

0.49

9.5 - 7.4

0.64 102
0.36 - 2.3 102

ACES

345

G. V. F. MTZ ET AL.

water with varying degrees of success [8-10]. The EC

process can be considered as an acelerated corrosion
process was green rust (GR) is an intermediate product
that is responsible for the removal of contaminants (suspended and dissolved solids, metals, organic compounds,
etc). EC mechanisms may involve oxidation, reduction,
decomposition, deposition, coagulation, absorption, adsorption, precipitation and flotation. EC operates on the
principle that hidrolized cations produced electrolytically
from iron and/or aluminum anodes enhance the coagulation of contaminants from an aqueous medium.
The sacrificial metal anodes are used to continuously
produce polyvalent metal cations in the vicinity of the
anode. These cations facilitate coagulation by neutralizing the negatively charged particles that are carried toward the anodes by electrophoretic motion. Generally in
the EC process bipolar electrodes are used [9-11]. It has
been reported that cells with bipolar electrodes connected
in series operating at relatively low current densities produced iron or aluminum coagulant more effectively. In
the EC technique, the production of polyvalent cations
from the oxidation of the sacrificial anodes (Al or Fe)
and the production of electrolysis gases (O2 and/or H2)
are directly proportional to the amount of current applied
(Faradays law). The electrolysis gases enhance the flotation of the coagulant material. A schematic representation of the EC process, using iron electrodes, is shown in
Figure 2. As mentioned above, the gas bubbles produced
by electrolysis carry the gold and silver along with the
sludge to the top of the solution where it is collected and
removed.
However, it is the reactions of the metal ions that enhance the formation of the coagulant. The metal cations
are hydrolyzed, releasing hydrogen ions that result in
hydrogen evolution at the cathode, to yield both soluble
and insoluble hydroxides that will react with or adsorb
gold and silver from the cyanide solution and also contribute to coagulation by neutralizing the negatively
charged colloidal particles that may be present at neutral

Figure 2. An illustration of the EC mechanism (arrow indicate the migration of ions, the H2 evolution and the formation of green rust).
Copyright 2012 SciRes.

or alkaline pH.
This enables the particles to approach closely and agglomerate under the influence of Van der Waals attractive forces. The chemical reactions that have been proposed to describe EC mechanism [12] when using iron
electrodes are:
Fe
2

Fe OH

Fe+3 + 3e

H2O

2H+ + 2e
Fe OH
Fe OH

1
2

2 aq

Fe OH

1
3

Fe OH

(7)
1

(8)

H2(g)

(9)

Fe OH

2 aq

H2O

Fe OH

Fe OH

3 aq

(10)
(11)

(12)

Overall reaction
6Fe

12 x H 2 O

1
12 x H 2 g
2
xFe OH 3 6 x Fe OH

(13)
2 s

The pH of the medium usually rises as a result of this

electrochemical process and the Green Rust formed
[xFe(OH)3 (6 x)Fe(OH)2(s)] remains in the aqueous
stream as a gelatinous suspension, which can remove the
gold and silver from pregnant cyanide rich solutions,
either by complexation or by electrostatic attraction of
magnetic nanoparticles followed by coagulation and flotation. Generally, in the EC process, bipolar electrodes
are used [8]. It has been reported that cells with bipolar
electrodes, connected in series operating at relatively low
current densities, produce iron or aluminum coagulant
more effectively, more rapidly and more economically
when compared to chemical coagulation.

2. Experimental Procedures
2.1. Suspended Zinc Particle Experiments
The bath reactor experiments were done in four-necked,
one liter glass reaction cells supported in a constant temperature bath. A condenser, stirrer, nitrogen dispersion
tube, and sampling derive were placed into a reactor
through the openings in the lid. The Teflon stirrer was
attached through the center port by means of a Chesapeak stirrer connection. In all studies purified nitrogen
was passed through the solution, via a dispersion tube,
before and during the experiment to maintain an oxygenfree environment. Tyler sieves were used to prepare
monosize fractions of zinc in the range from 70 to 400
mesh.
The specific surface area of the zinc dust was measured using two techniques, the BET technique (QuanACES

346

G. V. F. MTZ ET AL.

tasorb Model 0S10, made by Quantachrome Corporation),

surface area 255 cm2/gr, and the air permametry technique (Permaran made by Outokumpu), surface area 216
cm2/gr. The stirring speed was adjusted manually (1000
RPM) and was checked with a stroboscope. The particulate sample of zinc was washed with acetone and cleaned
with acid to remove the surface oxide film before being
introduced into the reaction flash. For most of the experiments, one gram of 270 400 mesh (d50 = 45 m)
particles of zinc were introduced through one of the
cover ports, and the reaction was initiated. In order to
follow the course of cementation reaction, solution aliquots of 2 ml were taken periodically and analyzed for
silver and gold with a DCP (Direct-Current Plasma)
Spectrophotometer manufactured by Beckman Instruments.

2.2. Experimental Electrocoagulation Details

The EC experiments were performed in a 400 ml beaker
size reactor equipped with two carbon steel electrodes (6
cm 3 cm) that were 5 mm apart. As a source of current
and voltage a universal AC/DC adaptor was used. pH
was measured with a VWR scientific 8005 pH meter.
Gold and silver adsorption onto iron species was investigated with pregnant cyanide solutions provided by Bacis
S. A. de C. V. mining group (13.25 ppm Au and 1357
ppm Ag and pH of 8). Analyses were performed by ICP/
Atomic Emission Spectrometry. The conductivity of
pregnant solutions was adjusted by adding one gram of
NaCl per liter (Fisher, 99.8% A. C. S. Certified, lot
#995007).
To identify and characterize the iron species in the
solid products, formed during the EC process for the removal of gold and silver using iron electrodes, X-ray
diffraction (XRD) and Scanning Electron Microscope
(SEM/EDX) were used. Analysis of Au and Ag were
conducted to the Bacis solution, by AES. EC was run at
15 Volts (DC) and the corresponding current was of 0.1
. EC was run for five minutes, and a sample was taken
every minute in order to determinate the removal efficiency for Au and Ag. Solutions and solids from the EC
process were separated by filtration through cellulose
filter paper. The sludge from the EC was dried either in
an oven or under vacuum at room temperature and characterized.

3. Results and Discussion

3.1. Zinc Dust Particle Size Results
As was shown by Equation (5), the rate of cementation
reaction is expected to be a function of the surface area
and the concentration of the reacting noble metal ion
(gold or silver in the present case). To examine the traditional first order rate expression, the cementation reaction kinetics were studied using monosize zinc particles.
Two experiments were conducted at 10 ppm (5 105 M)
gold and 100 ppm (9 104) silver in order to study the
reaction kinetics at these concentrations. The equilibrium
concentration profiles (on logarithmic scale), the results
were found to conform to the first-order rate process for
over 99% removal as shown in Figure 3 (Au/Zn(CN)
system) and (Ag/Zn(CN) system). From these data it is
evident that the cementation of both gold and silver by
zinc conforms to well-behaved fist order kinetics. Also,
from these figure, the micrograph of reacted zinc particles can be seen. This micrograph reveals the nature of
the silver and gold deposits. The effect of the gold and
silver deposits on the rate of cementation reaction product showed that the gold and silver formed uniforms,
apparently porous layer around the zinc particle. Table 2
lists the values of the reaction velocity constant for the
cementation of gold (10 ppm) and silver (100 ppm) on
zinc dust.

3.2. Electrocoagulation Results

Running the EC process for gold and silver removal on
iron electrodes, gave the results shown in Table 3 and in
Figure 4, shows the equilibrium concentration profile of
gold and silver removal efficiency and final pHs values
vs. Time. The obtained results show that EC is an excellent option to remove Au and Ag from cyanide pregnant
solution by using iron electrodes. Also, under these conditions, the results show that, when residence time increases from 1 to 3 minutes the silver and gold removal
increase to 92% and 99% respectively, this variation occurs at pH values from 9 to 10.7, approximately; these
values coincide with the production of magnetic iron,
Fe3O4 (green rust). Also, it is apparent that the uptake
percents of gold/silver increased by increasing the pH
value.
The mechanism of the EC process for gold and silver

Table 2. Comparison of experimental reaction velocity constants with calculated mass-transfer coefficients for suspended
particles. NaCN = 102 M, pH = 10.5, Stirring speed = 1000 rpm, Au = 10 ppm (5 105 M), Ag = 100 ppm (9 104 M).
System

Particle size, mesh

Experimental reaction velocity constant, cm/sec

Calculated mass-transfer coefficient

Au/Zn(CN)

400 270

1.9 102

2.35 102

Ag/Zn(CN)

400 270

1.62 102

3.2 102

Copyright 2012 SciRes.

ACES

G. V. F. MTZ ET AL.

347

Figure 3. First-order plots showing removal of gold and silver from cyanide solution.
Table 3. Recovery of gold and silver by EC.
EC residence
time (min)

Au
(mgL1)

Recovery
(%)

Ag
(mgL1)

Recovery
pH
(%)

13.25

1357.0

12.50

5.66

940.0

30.72

9.2

10.50

20.37

219.5

83.82

9.5

1.00

92.45

9.0

99.33

10.7

0.50

96.22

7.0

99.48

11.2

0.10

99.24

0.9

99.93

11.5

8.0

recovery is then physical and chemical adsorption, caused

by the highly reactive species and adsorption properties
of green rust. These processes do not alter their chemical
composition. Figure 4, also shows graphically the pH
during the EC the process for gold and silver removal,
the pH increment in the solution from 8 to a pH final of
11 is attributed to the hydrogen evolution at the cathode
which is then accompanied by alkalinization of the
aqueous solution.

3.3. Product Characterization

X-ray Diffraction Analysis. Diffraction patterns of flocs
collected from the experiment with gold and silver, (the
sample were ground to a fine powder and loaded into a
Copyright 2012 SciRes.

sample holder) were obtained with a diffracted X-PERT

Phillips meters equipped with a vertical goniometer, with
a range of analysis 2 10 to 70. The source of X-rays
has a copper anode, whose radiation is filtered with a
graphite monochromator ( = 1.541838 ) with scan rate
of 0.02 and a duration of 10 seconds per count. The
X-Ray Diffractometer is controlled by a Gatawey 2000
computer, by PC-APD 2.0 with software for Windows.
Figure 5 shows the ray diffraction pattern of the flocs
recovered from the sample of gold and silver, respectively 13.25 mg/L and 1357 mg/L, initial pH 8, 5 minutes
of treatment, 0.1 amperes and 15 volts. The species identified were magnetite, lepidocrocite, goehtite, silver and
copper hexacyanoferrate. Scanning Electron Microscopy (SEM/EDAX). Figure 6 shows SEM images and
EDAX of silver adsorbed on iron species. These SEM
and EDAX results show that the surfaces of these iron
oxide/oxyhydroxide particles were coated with a layer of
silver. It is worth clarifying that, given the low concentration of gold it was impossible to locate any nanoparticle of it.

4. Conclusion
The cementation of both gold and silver by suspended
zinc particles conforms to well-behaved fist order kinetACES

348

G. V. F. MTZ ET AL.

Figure 4. Gold and silver recoveries from Bacis cyanide solutions and pH vs. EC residence time.

Figure 5. X-ray diffractogram of solids obtained in the recovery of gold and silver C: Cu2Fe(CN)62H2O, A: Silver, M:
Magnetite and L: Lepidocrocite.

ics. The effect of the gold and silver deposits on the rate
of cementation reaction product showed that the gold and
silver formed uniforms, apparently porous layer around
the zinc particle. The experimental reaction velocity constants correspond to the expected magnitude of the limiting mass-transfer coefficients and support the hypothesis
that the cementation reactions under these conditions are
mass-transfer limited reactions with recoveries of gold
and silver of 99.8%. The obtained results show that EC
process is an excellent option to remove Au and Ag from
cyanide pregnant solution by using iron electrodes. The
X-Ray Diffraction, Scanning Electronic Microscopy, techniques demonstrate that the formed species are of magnetic type, like lepidocrocite and magnetite, and amorphous iron oxyhydroxide which adsorbed the silver and
gold particles on his surface due to the electrostatic attraction between both metals. The 99.5% of gold and
silver were removed in the experimental EC reactor, and
it was achieved in 5 minutes or less with a current efficiency of 99.7%.
Copyright 2012 SciRes.

(a)

(b)

Figure 6. Chemical composition of solid product as determined by EDX, which shows the presence of silver in the
particle of iron.
ACES

G. V. F. MTZ ET AL.

5. Acknowledgements
The authors wish to acknowledge support of this project
to the National Council of Science and Technology
(CONACYT) and to Direccin General de Educacin
Superior Tecnolgica (DGEST) from Mexico.

Mines Geological Bulletin, No. 59, 1967, pp. 1-42.

[7]

S. Gamini, The Cyanidation of Silver Metal: Review of

Kinetics and Reaction Mechanism, Hydrometallurgy,
Vol. 81, No. 2, 2006, pp. 75-85.

[8]

J. R. Parga, D. L. Cocke, J. L. Valenzuela, H. Moreno,

and M. Weir, Arsenic Removal via Electrocoagulation
from Heavy Metal Contaminated Groundwater in La Comarca Lagunera Mexico, Journal of Hazardous Materials, Vol. 124, No. 1-3, 2005, pp. 247-254.
doi:10.1016/j.jhazmat.2005.05.017

[9]

M. Mollah, P. Morkovsky, J. Gomez, J. R. Parga and D.

Cocke, Fundamentals, Present and Future Perspectives
of Electrocoagulation, Journal of Hazardous Materials,
Vol. 114, No. 1-3, 2004, pp. 199-210.
doi:10.1016/j.jhazmat.2004.08.009

REFERENCES
[1]

[2]

F. Habashi, A short History of Hydrometallurgy, Hydrometallurgy, Vol. 79, No. 1-2, 2005, pp. 15-22.
doi:10.1016/j.hydromet.2004.01.008
J. R. Parga, G. Gonzalez, H. Moreno and J. L. Valenzuela,
Thermodynamic Studies or the Strontium Adsoption on
Iron Species Generated by Electrocoagulation, Desalination and Water Treatment, Vol. 37, No. 1-3, 2012, pp.
244-252.

[3]

J. R. Parga, J. L. Valenzuela, H. Moreno and J. E. Perez,

Copper and Cyanide Recovery in Cyanidation Effuents,
Advances in Chemical Engineering and Science, Vol. 1,
No. 4, 2011, pp. 191-197. doi:10.4236/aces.2011.14028

[4]

R. Woods, Extracting Metals from Sulfide Ores, 2010.

http://electrochem.cwru.edu/encycl/art-m02-metals.htm

[5]

W. Wai, L. Eugene and A. S. Mujumdar, Gold Extraction and Recovery Processes, 2009.
http://www.eng.nus.edu.sg/m3tc/M3TC_Technical_Repo
rts/Gold%20Extraction%20and%20Recovery%20Process
es.pdf

[6]

F. Habashi, Kinetics and Mechanism of Gold and Silver

Dissolution in Cyanide Solution, Montana Bureau of

Copyright 2012 SciRes.

349

[10] M. M. Emamjomeh and M. Sivakumar, Review of Pollutants Removed by Electrocoagulation and Electrocoagulation/Flotation Processes, Journal of Environmental
Management, Vol. 90, No. 5, 2009, pp. 1663-1679.
doi:10.1016/j.jenvman.2008.12.011
[11] X. Zhao, B. Zhang, H. Liu and J. Qu, Removal of Arsenite by Simultaneous Electro-Oxidation and ElectroCoagulation Process, Journal of Environmental Management, Vol. 184, No. 1-3, 2010, pp. 472-476.
doi:10.1016/j.jhazmat.2010.08.058
[12] H. Moreno, D. L. Cocke, J. A. G. Gomes, P. Morkovsky,
J. R. Parga, E. Peterson and C. Garcia, Electrochemical
Reactions for Electrocoagulation Using Iron Electrodes,
Industrial & Engineering Chemistry Research, Vol. 48,
No. 4, 2009, pp. 2275-2282. doi:10.1021/ie8013007

ACES

GMPR #601483, VOL 33, ISS 5

RECOVERY OF SILVER AND GOLD FROM CYANIDE

SOLUTION BY MAGNETIC SPECIES FORMED IN THE
ELECTROCOAGULATION PROCESS
J. R. Parga, M. Rodrguez, V. Vazquez, J. L. Valenzuela, and
H. Moreno, H. Moreno
QUERY SHEET
This page lists questions we have about your paper. The numbers displayed at left can be
found in the text of the paper for reference. In addition, please review your paper as a whole
for correctness.
Q1: Au: Please provide complete reference for citation Moreno Casillas 2009 or delete
citation.
Q2: Au: Please provide volume no. in ref. Mollah et al. 2004.
Q3: Au: Please cite ref. Parga et al. 2009 in the text or delete ref.
Q4: Au: Please provide location of publisher in reference Valenzuela et al. 2003.

TABLE OF CONTENTS LISTING

The table of contents for the journal will list your paper exactly as it appears below:

Recovery of Silver and Gold From Cyanide Solution by Magnetic Species

Formed in the Electrocoagulation Process
J. R. Parga, M. Rodrguez, V. Vazquez, J. L. Valenzuela, and H. Moreno

3b2 Version Number

File path
Date and Time

:
:
:

7.51c/W (Jun 11 2001)

p:/Santype/Journals/TandF_Production/Gmpr/v33n5/GMPR601483/GMPR601483.3d
14/04/12 and 12:22

Mineral Processing & Extractive Metall. Rev., 33: 111, 2012

Copyright # Taylor & Francis Group, LLC
ISSN: 0882-7508 print=1547-7401 online
DOI: 10.1080/08827508.2011.601483

RECOVERY OF SILVER AND GOLD FROM CYANIDE

SOLUTION BY MAGNETIC SPECIES FORMED IN THE
ELECTROCOAGULATION PROCESS
J. R. Parga1, M. Rodrguez1, V. Vazquez1, J. L. Valenzuela2,
and H. Moreno3

Department of Metallurgy and Materials Science, Saltillo Institute of

Technology, Saltillo, Coahuila, Mexico
2
Department of Chemical Engineering and Metallurgy, University of Sonora,
Hermosillo, Sonora, Mexico
3
Department of Chemical Engineering, La Laguna Institute of Technology,
Torreon, Coahuila, Mexico
Cyanidation is the predominant process by which gold and silver are recovered from
their ores in metallurgical operations, and it is recognized that the Carbon in Pulp, the
MerrillCrowe, the Ion Exchange, and Solvent Extraction processes are used for concentration and purification of gold and silver from cyanide solutions. Among other available
options for recovery of precious metals from cyanide solutions, Electrocoagulation (EC)
is a very promising water and wastewater electrochemical technique that does not require
high concentrations of silver and gold in cyanide solutions to yield excellent results. In this
work, an introduction to the fundamentals of the EC process is given, followed by the conditions and results of the EC test run for removal of precious metals from cyanide solutions,
and finally the characterization of the solid products formed during the EC process with
X-ray Diffraction, SEM, and Transmission Mossbauer Spectroscopy. Results suggest that
magnetite particles and amorphous iron oxyhydroxides are present (Lepidocrocite and
Gohetite). With the EC process, the achieved removal efficiency of silver and gold from
cyanide solutions, within 5 min, exceeded 99%.

10

15

20

25

Keywords: electrocoagulation, gohetite, green rust, lepidocrocite

INTRODUCTION
Cyanidation processes are especially suitable for treating gold=silver-bearing
sulfidic materials. Modern hydrometallurgy technology of precious metals is based
on the application of cyanide leaching for the dissolution of gold and silver. Gold
cyanidation are reported to involve the chemical reactions shown in Eqs. (1) and
(2). Silver follows a similar process.
!
"
2Au 4NaCN O2 2H2 O ! 2Na AuCN2 2NaOH H2 O2

Address correspondence to J. R. Parga, Department of Metallurgy and Materials Science, Saltillo

Institute of Technology, V. Carranza 2400, Saltillo, Coahuila 25000, Mexico. E-mail: jrparga@its.mx
1

30

J. R. PARGA ET AL.

!
"
2Au 4NaCN H2 O2 ! 2Na AuCN2 2NaOH

2
35

Q1

The equation proposed by Elsner is stoichiometrically correct but does not

describe the cathodic reactions associated with the dissolution. The stoichiometry
of the process shows that 4 mol of cyanide are needed for each mole of oxygen present
in solution. At room temperature and standard atmospheric pressure, approximately
8.2 mg of oxygen are present in 1 L of water. This corresponds to 0.27 $ 10%3 mol=L.
Accordingly, the sodium cyanide concentration (molecular weight of NaCN 49)
should be equal to 4 $ 0.27 $ 10%3 $ 49 0.05 g=L or approximately 0.01%. This
was confirmed at room temperature by a very dilute solution of NaCN of
0.010.5% for ores, and for concentrates rich in gold and silver of 0.55% (Parga,
Valenzuela, and Cepeda 2007). Details of this electrochemical reaction have received
considerable attention and under certain circumstances the reaction is limited by the
coupled diffusion of CN and O2 to the gold surface. Lime or sodium hydroxide
(caustic) is added to keep the system at an alkaline pH beteween 10 and 11. This protective alkalinity is required to counteract the generation of acid during cyanidation,
to prevent cyanide degradation, and the formation of the deadly HCN gas.
The two conventional processes for gold and silver recovery from cyanide leach
solution are: The Carbon Adsorption Process and the MerrillCrowe zinc dust
cementation process. In the Carbon Adsorption Process, the precious metals are
absorbed onto granules of activated carbon. After loading, they are then stripped
of the loaded gold by a hot caustic-cyanide solution. This solution is then fed to electrowinning cells where gold and silver are electrolytically deposited onto steel wool
cathodes. In the MerrillCrowe process, the product is filtered zinc dust precipitate.
The cathodes from the carbon adsorption process or the precipitates from the MerrillCrowe process (metal displacements) are then melted in crucible furnaces along
with fluxing materials such as borax, niter, and silica. The resultant product from
smelting is Dore bullion of precious metals typically analyzed with more than 97%
of precious metals.
Each recovery method has advantages and disadvantages. Process selection
depends on the specific conditions for a particular operation and the facilities already
available. Traditionally, The MerrillCrowe method was the preferred process for
many years. In just the past 40 years, the carbon adsorption process has become
popular for recovering gold from large volumes of low grade pregnant leach solutions that contain mainly gold.
The Ion Exchange Resins and Solvent Extraction process has recently been
reviewed as an alternative for gold and silver recovery from alkaline cyanide solutions (Valenzuela et al. 2003; Aguayo et al. 2007). Another method that has been
tried for the recovery of gold and silver uses adsorption on a chemically modified
chitosan with magnetic properties (Donia, Atia, and Elwakeel 2007).
The alternative processes are compared in Table 1 along with those of the EC
(Parga et al. 2005; Moreno Casillas 2009). The EC process is seen to be a very promising technique for the recovery of precious metals such as silver and gold: EC needs
no chemical reagents, and does not generate toxic materials requiring special disposal making it an ecologically viable technique. Literature review shows the potential of EC as an alternative to traditional treatment recovery of precious metals
(silver and gold cyanide) yet to be exploited.

40

45

50

55

60

65

70

75

80

RECOVERY OF SILVER AND GOLD FROM CYANIDE SOLUTION

Table 1 Advantages and disadvantages of methods for recovery of gold and silver (Mollah et al. 2004;
Parga, Valenzuela, and Cepeda 2007; Emamjomeh and Sivakumar 2009)
Method
MerrillCrowe

Adsorption with
Activated Carbon

Ion Exchange Resins

Solvent Extraction

Electrocoagulation

Advantages

Disadvantages

. Lower capital and operating

costs.
. Handles solutions containing
high silver and gold content.
. It is highly efficient (99.5%).
. Also can treat high-grade
solutions produced by carbon
elution.
. Alternative to electrowinning.
. Does not require pretreatment of
pregnant solution.
. Not dependent on the concentration of metals.
. Large specific surface.
. The pulp needs no clarification.
. Does not need: washing,
revitalization, or heat treatment.
. High abrasion resistance in tanks
of adsorption.
. High selectivity.
. High selectivity.
. Does not need: washing, revitalization, or heat treatment.
. Low residence time (minutes).
. Does not use chemicals.
. Handles solutions containing
lower or high silver and gold
contents.
. Energy costs per m3 of pregnant
solution are lower than conventional treatment systems.

. The pregnant solution needs

clarification and deoxygenating.
. Low concentrations of metals
increases amount of zinc.
. Depends on the pH and concentration of the free cyanide.
. The precipitate contains cyanides
like copper and arsenic.
. Fouled carbon needs to be
regenerated by heating.
. Large carbon inventory.
. The pregnant solution has to go
through 5 or 6 columns.
. High operating costs.
. High cost of the process.
. Lower loading capacity.
. Royalty payments.
. The resin must be regenerated in
acid medium.
. High cost of the process.
. New technology.
. Stripping Difficult.
. Sacrificial anode must be
replaced periodically.
. Precise initial pH control.
. New technology.
. The product is high in iron.

ELECTROCOAGULATION CHARACTERISTIC
Electrocoagulation (EC) has been known as an electrochemical phenomenon
for more than 70 years. EC has been employed previously to treat many types of
wastewater with varying degrees of success (Mollah et al. 2004; Parga et al. 2005;
Emamjomeh and Sivakumar 2009).
85
The EC process can be considered as an accelerated corrosion process where
green rust (GR) is an intermediate product responsible for the removal of contaminants (suspended and dissolved solids, metals, organic compounds, etc). EC mechanisms may involve oxidation, reduction, decomposition, deposition, coagulation,
absorption, adsorption, precipitation, and flotation. EC operates on the principle 90
that hidrolized cations produced electrolytically from iron and=or aluminum anodes
enhance the coagulation of contaminants from an aqueous medium. The sacrificial
metal anodes are used to continuously produce polyvalent metal cations in the vicinity of the anode. These cations facilitate coagulation by neutralizing the negatively
charged particles that are carried toward the anodes by electrophoretic motion. 95

J. R. PARGA ET AL.

Figure 1 An illustration of the EC mechanism to remove gold and silver (arrows indicate the migration of
electrolysis gases O2 and H2).

Bipolar electrodes are generally used in the EC process (Mollah et al. 2004;
Emamjomeh and Sivakumar 2009; Zhao et al. 2010). It is reported that cells with
bipolar electrodes connected in series operating at relatively low current densities
produced iron or aluminum coagulant more effectively. In the EC technique, the
production of polyvalent cations from the oxidation of the sacrificial anodes (Al
or Fe) and the production of electrolysis gases (O2 and=or H2) are directly proportional to the amount of current applied (Faradays law). The electrolysis gases
enhance the flotation of the coagulant material. A schematic representation of the
EC process, using iron electrodes, is shown in Figure 1. Aforementioned, the gas
bubbles produced by electrolysis carry the gold and silver along with the sludge to
the top of the solution where it is collected and removed.
It is the reactions of the metal ions that enhance the formation of the coagulant. The metal cations are hydrolyzed, releasing hydrogen ions that result in hydrogen evolution at the cathode. This process yields both soluble and insoluble
hydroxides which react with or adsorb gold and silver from the cyanide solution
and contribute to coagulation by neutralizing the negatively charged colloidal particles if present in a neutral or alkaline pH. This enables the particles to closely
approach and agglomerate under the influence of Van der Waals attractive forces.
The EC mechanism and chemical reactions (Moreno et al. 2009) when using iron
electrodes are:
Fe $ Fe3 3e%

FeOH2 H2 O ! FeOH1
2 H

2H 2e% ! H2g "

100

105

110

115

RECOVERY OF SILVER AND GOLD FROM CYANIDE SOLUTION

%
FeOH1
2 e ! FeOH2aq

FeOH2aq H2 O ! FeOH%1
3 H

%
FeOH%1
3 ! FeOH3aq e

Overall reaction
6Fe 12 xH2 O ! 1=212 % xH2g " xFeOH3 ' 6 % XFeOH2s

9
125

The pH of the medium usually rises as a result of this electrochemical process

and the GR formed [xFe(OH)3' (6 X) Fe(OH)2 (s)] remains in the aqueous stream
as a gelatinous suspension, which can remove the gold and silver from pregnant
cyanide rich solutions, either by complexation or by electrostatic attraction followed
by coagulation and flotation.
130
Formation of rust (dehydrated hydroxides) occurs after the following
processes:
2FeOH3 $ Fe2 O3 3H2 O hematite; maghemite

10

FeOH2 $ FeO H2 O

11

2FeOH3 FeOH2 $ Fe3 O4 4H2 O magnetite

12

FeOH3 $ FeOOH H2 O goethite; lepidocrocite

13

Due to the high voltage in the EC cell, a very strongly oxidizing environment is
produced around the anode suitable for destroying strong cyanide solutions (greater
than 1000 ppm). This represents a direct oxidation of the cyanide ion at the anode to 140
cyanate ion which is further decomposed to carbon dioxide and nitrogen,
ammonium, and carbonate or oxalate ions according to the pH (Hwang, Wang,
and Wan 1987). The reactions are as follows:
In strong alkaline solution (pH 12)
CN% 2OH% ! CNO% H2 O 2e

14

CNO% 2OH% ! CO2 1=2N2 H2 O 3e

15

In neutral and weak alkaline solution (pH 7.011.7)

2CN ! C2 N2

16

C2 N2 2OH% ! CNO% CN% H2 O

17

2%
CNO% 2H2 O ! NH
4 CO3

18

J. R. PARGA ET AL.

In weak acidic solution (pH 5.26.8)

C2 N2 4H2 O ! C2 O2%
4 2NH4

19
155

Tamura et al. (1974) determined that the anodic oxidation of cyanide is proportional to the alkalinity of the electrolyte consistent with the following mechanism:
CN% 2OH ! CNO% H2 O 2e%

20

2CNO% 4OH% ! 2CO2 N2 2H2 O 6e%

21

CNO% 2H2 O ! NH4 CO%

3

22

EXPERIMENTAL DETAILS
EC experiments were performed with a Fisher magnetic stirrer and a 400 mL
beaker size reactor equipped with two carbon steel electrodes (6 $ 3 cm) 5 mm apart.
The electrodes were properly scrubbed and rinsed prior to each experiment trial run
to ensure a clean surface free of passive oxide layers. A universal AC=DC adaptor
was used as a source of current and voltage. The pH was measured with a VWR
scientific 8005 pH meter. Gold and silver adsorption onto iron hydroxide species
was investigated with pregnant cyanide solutions provided by Bacis S.A. de C.V.
mining group (13.25 mg=L Au, 1357 mg=L Ag, 200 mg=L free CNand 1400 mg=L
total CNand pH of 8). Analyses were performed with ICP=Atomic Emission Spectrometry (Perkin Elmer 3100). The conductivity of pregnant solutions was adjusted
by adding 1 g of NaCl per liter (Fisher, 99.8% A.C.S. Certified, lot #995007). To
identify and characterize the iron species in the solid products, formed during the
EC process for the removal of gold and silver using iron electrodes, X-ray diffraction
(XRD Phillips model X-PERT) and Scanning Electron Microscope (SEM=EDX,
FEI Quanta 2000, Oxford Instruments) were used.
Analyses of Au and Ag were conducted with the Bacis solution by AES. EC
was run at 15 V (DC) and the corresponding current was of 0.1 A.
EC was performed on five replicates for 5 min each with a sample taken every
minute in order to determinate the removal efficiency for Au and Ag. Solutions and
solids (shown in Figure 2) from the EC process were separated by filtration through
cellulose filter paper. The sludge from the EC was dried either in an oven or under
vacuum at room temperature and characterized.
The resulting sludge of iron hydroxide gel precipitate with Au=Ag is filtered.
This rich sludge is treated in an acid leach step with sulfuric acid under oxidizing
conditions caused by the addition of air. The conditions of this acid leach are such
that the major portion of iron is leached into solution with gold and silver remaining
in the residue. The resultant residue from the filtration step is gold, silver, and some
iron (10% Au, 80% Ag, and 5% Fe) suitable for further refining by conventional
commercial method.

165

170

175

180

185

190

RECOVERY OF SILVER AND GOLD FROM CYANIDE SOLUTION

Figure 2 Picture of the EC process for the removal of Au and Ag, showing GR.

RESULTS AND DISCUSSION

The EC process, gave the results shown in Table 2, values of concentration come
from the arithmetic average of five replications. As shown in Figure 3, the maximum
values for gold and silver recovery achieved within 5 min of treatment are of 99.24%
for Au and of 99.93% for Ag with a standard deviation of 0.26 for gold and 0.06 for
silver. This study showed very good recovery values within 23 min for gold and
12 min for silver. These results occur with pH ranging from 9 to 11, which coincides
with the production of magnetite (Fe3O4). Magnetites magnetic properties accelerate
the process of metal adsorption. The adsorption rate is physically determined by the
magnetic forces of the magnetite into gold and silver without altering their chemical
composition. The high voltage in the EC cell around the anode destroys some of the
cyanide. It is likely that the EC cell oxidize Au and Ag cyanide complexes, thus converting them to a less soluble form that might be captured by the iron hydroxide gel.
Figure 4 graphically displays the evolution of pH during the operation time.
There is an increase in pH of the bulk solution, which is attributed to the hydrogen
evolution at the cathode that accompanied the generation of hydroxyl ions during EC.
Figure 4 also shows cyanide concentration vs. time. In the EC cell, with iron
electrodes, cyanides decompose in the gold and silver pregnant solution, and the concentration changes from the original cyanide content of 1400 to 210 mg=L.

Table 2 Recovery of gold and silver by EC

EC residence time
(min)
0
1
2
3
4
5

Au (mg=L)

Recovery
(%)

Ag (mg=L)

Recovery
(%)

pH

Cyanide
(mg=L)

Cyanide
removal

13.25
12.50
10.50
1.00
0.50
0.10

0
5.66
20.37
92.45
96.22
99.24

1357.0
1240.0
219.5
9.0
7.0
0.9

0
8.62
83.82
99.33
99.48
99.93

8.0
9.2
9.5
10.7
11.2
11.5

1400
1050
870
750
400
210

0
25
38
46
71
85

195

200

205

210

J. R. PARGA ET AL.

Figure 3 Gold and silver recoveries from Bacis cyanide solutions.

PRODUCT CHARACTERIZATION
X-Ray Diffraction Analysis
Diffraction patterns of experimentally collected flocs with gold and silver (samples were ground to a fine powder and loaded into a sample holder) were obtained
with a diffracted X-PERT Phillips meters equipped with a vertical goniometer with a 215
2h analysis range of 10( 70( . The X-ray source is a copper anode, whose radiation is
) with scan rate of 0.02( and
filtered with a graphite monochromator (k 1.541838 A
a duration of 10 s per count. The X-Ray Diffractometer is controlled using a
Gateway 2000 computer by PC-APD 2.0 with software for Windows.
Figure 5 shows the ray diffraction pattern of flocs recovered from the sample of 220
gold and silver, respectively, 13.25 mg=L and 1357 mg=L, initial pH 8, 5 min of treatment, 0.1 A and 15 V. The species identified were magnetite, lepidocrocite, goehtite,
silver, and copper hexacyanoferrate.

Figure 4 pH vs. EC residence time and Cyanide removal vs. time.

RECOVERY OF SILVER AND GOLD FROM CYANIDE SOLUTION

Figure 5 X-ray diffractogram of solids obtained in the recovery of gold and silver C: Cu2Fe (CN)62H2O
A: Silver, M: Magnetite, and L: Lepidocrocite.

Scanning Electron Microscopy (SEM/EDAX)

Figure 6 shows SEM images and EDAX of silver adsorbed on iron species.
These SEM and EDAX results show that the surfaces of these iron oxide=oxyhydroxyhydroxide particles were coated with a layer of silver. Given the low concentration of gold, it was impossible to locate any nanoparticle of it.

225

Transmission Mossbauer Spectroscopy

Figure 7 shows the spectrum obtained from the EC silver, gold, and iron solid 230
product from 1350 mg=L of silver and 13 mg=L of gold cyanide solutions at

Figure 6 Chemical composition of solid product as determined by EDX, which shows the presence of
silver in the particle of iron.

10

J. R. PARGA ET AL.

Figure 7 Mossbauer spectrum with silver and gold at pH 10.5, indicating the presence of magnetite
species.

pH 11.0. Mossbauer Spectra for each sample was obtained on a )15 mm=s velocity
scale, which allows observation of wide magnetic hyperfine spectra expected from
iron oxide compounds. The spectrum consists of a doublet magnetic spectrum, which
is probably due to fine particles of iron oxides (nonstoichiometric magnetite) or iron 235
hydroxides (Lepidocrocite, Goethite, etc.).
From the analysis of these techniques, the in situ generated small fine particles
of iron- oxide=oxyhydroxides in the EC process are: nonstoichiometric magnetite,
goethite, and iron hydroxide oxide.

CONCLUSIONS

240

The results of this study indicate that silver and gold can be successfully
adsorbed on iron species produced by the EC process. EC may be a viable method
to recover gold and silver from cyanide solutions.
The X-Ray Diffraction, Scanning Electronic Microscopy, and Transmission
Mossbauer Spectroscopy techniques demonstrate that the formed species are 245
magnetic (e.g., lepidocrocite and magnetite and amorphous iron oxyhydroxide),
which adsorb the silver and gold particles on the surface by electrostatic
attraction.
Yields of 99.93% gold and 99.24% silver were efficiently removed in the experimental EC reactor within 5 min and a current efficiency of 99.7%.
250
Aditionally, the high voltage in the EC cell around the anode destroys some of
the cyanide.

RECOVERY OF SILVER AND GOLD FROM CYANIDE SOLUTION

11

ACKNOWLEDGMENTS
The authors wish to acknowledge support of this project to the National Council of Science and Technology (CONACYT) and to Direccion General de Educacion
Superior Tecnologica (DGEST) from Mexico.

255

REFERENCES

Q2

Q3

Q4

Aguayo, S., Valenzuela, J. L., Parga, J. R., and Lewis, R. G., 2007, Continuous laboratory
gold solvent extraction from cyanide solutions using LIX 79 reagent. Chemical Engineering and Technology, 30, pp. 15321536.
Donia, A. M., Atia, A. A., and Elwakeel, K. Z., 2007, Recovery of gold(III) and silver(I) on a
chemically modified chitosan with magnetic properties. Hydrometallurgy, 87, pp. 197206.
Emamjomeh, M. M. and Sivakumar, M., 2009, Review of pollutants removed by electrocoagulation and electrocoagulation=flotation processes. International Journal of Environmental Management, 90, pp. 16631679.
Hwang, J. Y., Wang, Y. Y., and Wan, C. C., 1987, Electrolytic oxidation of cuprocyanide
electroplating wastewaters under different pH conditions. Journal of Applied Electrochemistry, 17, pp. 684694.
Mollah, M., Morkovsky, P., Gomez, J., Parga, J. R., and Cocke, D., 2004, Fundamentals,
present and future perspectives of electrocoagulation. Journal of Hazardous Materials,
199210.
Moreno, H., Cocke, D. L., Gomes, J. A. G., Morkovsky, P., Parga, J. R., Peterson, E., and
Garcia, C., 2009, Electrochemical reactions for electrocoagulation using iron electrodes. Industrial and Engineering Chemistry Research, 48, pp. 22752228.
Parga, J. R., Casillas, H., Vazquez, V., and Valenzuela, J. L., 2009, Cyanide detoxification of
mining wastewaters with TiO2 nanoparticles and its recovery by electrocoagulation.
Chemical Engineering and Technology, 32, pp. 19011908.
Parga, J. R., Cocke, D. L., Valenzuela, J. L., Moreno, H., and Weir, M., 2005, Arsenic
removal via electrocoagulation from heavy metal contaminated groundwater in La
comarca lagunera, mexico. Journal of Hazardous Materials, B124, pp. 247254.
Parga, J. R., Valenzuela, J. L., and Cepeda, F., 2007, Pressure cyanide leaching for precious
metals recovery. Journal of Metals, 10, pp. 4347.
Tamura, H., Arikado, T., Yoneyama, H., and Matsuda, Y., 1974, Anodic oxidation of
potassium cyanide on platinum electrode. Electrochimica Acta, 19, p. 273.
Valenzuela, J. L., Aguayo, S., Parga, J. R., and Lewis, R. G., 2003, Gold solvent extraction
from alkaline cyanide solutions using LIX 79 extractant. In Hydrometallurgy, Fifth
International Conference, Vol. 1 (C. A. Young, A. M. Alfantazi, C. G. Anderson, D.
Dressinger, B. Harris, and A. James Eds.), TMS, pp. 881889.
Zhao, X., Zhang, B., Liu, H., and Qu, J., 2010, Removal of arsenite by simultaneous
electro-oxidation and electro-coagulation process. Journal of Hazardous materials,
184, pp. 472476.

260

265

270

275

280

285

290