Minerals Engineering 108 (2017) 6770

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Short communication

Improvements in gold ore cyanidation by pre-oxidation with hydrogen

peroxide
Thiago Oliveira Nunan a, Isabella Lima Viana a, Guilherme C. Peixoto a, Herbert Ernesto a,
Daniel Martin Verster b, Jose Henrique Pereira c, Jose M. Bonfatti c, Luiz Alberto Cesar Teixeira c,d,
a
Minerao Serra Grande (Anglo Gold Ashanti), Brazil
b
Postnet Suite 250, Private Bag H607, Boschfontein, Heidelberg, Gauteng 1438, South Africa
c
Peroxidos do Brasil Ltda (Solvay Group), Brazil
d
Pontifcia Universidade Catlica do Rio de Janeiro, Departamento de Eng. Quimica e de Materiais, Rua Marques de Sao Vicente, 225 sala L 501,
CEP 22451-000 Rio de Janeiro, RJ, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: It is known that the presence of sulphidic minerals in the cyanidation of gold ores may cause significant
Received 29 September 2016 consumption of oxygen supplied in the injected air. This may result in dissolved oxygen starvation for the
Revised 5 January 2017 oxidative leaching of the gold, and ultimately it will reduce the maximum attainable recovery of gold
Accepted 17 January 2017
from the ore. In addition, the presence of sulphides leads to extra consumption of the cyanide-
leaching agent, NaCN, due to the formation of thiocyanate, therefore increasing costs. These types of gold
sulphidic ores may be pre-treated prior to cyanidation by means of an oxidation step, converting the sul-
Keywords:
phides into oxides or sulphates. This treatment leads to a reduction in the consumption of dissolved oxy-
Pre-oxidation in gold cyanidation
Gold recovery
gen and of cyanide in the cyanidation step and to an improvement in the metallurgical recovery. In the
Cyanide consumption current work we present the results of a five month full-scale trial carried out in a gold extraction plant in
Hydrogen peroxide Brazil, which normally operated with three tanks in series carrying out an alkaline pre-oxidation step
using compressed air only, followed by a train of fourteen aerated and mechanically-agitated tanks for
the cyanidation. The ore feeding the leaching circuit averages 1.70 g Au/t, with about 2.5% of pyrrhotite
(FeS) as the main sulphide constituent. The addition of 60 L/h of concentrated hydrogen peroxide, H2O2,
50% w/w (density = 1.19 g/mL) for pre-oxidation of a slurry of 60% solids at a rate of 150 t/h (dry ore)
resulted in a marked increase in dissolved oxygen (DO). This addition corresponds to a dosing rate of
0.24 kg 100% H2O2 per ton of dry ore and increased the dissolved oxygen level from an average of about
1.0 to 7.2 mg/L in the pre-oxidation tanks. It also led to an overall reduction of NaCN consumption from
an average of 0.52 to 0.40 kg/t of ore, and an increase in metallurgical Au recovery from an average of
91.3% to 92.5%.
2017 Elsevier Ltd. All rights reserved.

1. Introduction
For several years the performance of the hydrometallurgical cir-
cuit at AngloGold Ashantis Serra Grandes gold extraction plant in
the state of Gois, Brazil, indicated that improvements could occur
in the recovery of gold, associated with the leaching kinetics.
Corresponding author at: Pontifcia Universidade Catlica do Rio de Janeiro,
Departamento de Eng. Quimica e de Materiais, Rua Marques de Sao Vicente, 225
sala L 501, CEP 22451-000 Rio de Janeiro, RJ, Brazil.
E-mail addresses: TONunan@AngloGoldAshanti.com.br (T.O. Nunan), ILViana@
AngloGoldAshanti.com.br (I.L. Viana), GCPeixoto@AngloGoldAshanti.com.br
(G.C. Peixoto), HErnesto@AngloGoldAshanti.com.br (H. Ernesto), martin.verster01@
gmail.com (D.M. Verster), Jose-Henrique.Pereira@solvay.com (J.H. Pereira), Jose.
Bonfatti@solvay.com (J.M. Bonfatti), teixeira@puc-rio.br (L.A. Cesar Teixeira).
Additional tanks were installed in 2009 to expand the circuit. But
in some of the ores to be leached the residence time in the circuit
was not yet sufficiently long to recover all leachable gold from the
ore on a regular basis. In previous internal studies it was found that
up to 30% of gold reporting in the tailings was still leachable and
wasnt being recovered due to process kinetics, specifically due
to low concentration of dissolved oxygen in the slurry in the initial
tanks of the cyanidation train.
The leaching circuit comprises an initial three-tanks-in-series
alkaline pre-oxidation step using only compressed air and lime,
followed by a train of fourteen aerated and mechanically-
agitated tanks for cyanidation. The ore feeding the leaching circuit
averages 1.70 g Au/t and the main oxygen-consuming component
is the sulphide mineral pyrrhotite (FeS) at about 2.5% w/w.

http://dx.doi.org/10.1016/j.mineng.2017.01.006
0892-6875/ 2017 Elsevier Ltd. All rights reserved.
68 T.O. Nunan et al. / Minerals Engineering 108 (2017) 6770
Usually the kind of gold ores containing sulphidic minerals
depending on the sulphide content and mineralogy can be
pre-treated by oxidation steps prior to cyanidation, converting
the sulphides to oxides or sulphates, in some cases enhancing
the opening up of the ore. Experts in the field propose that pre-
oxidation is used for two reasons: (i) to oxidize and breakdown
sulphide minerals to expose encapsulated gold; and (ii) to passi-
vate the sulphide minerals by oxidizing the surface and thus mak-
ing them less reactive in the cyanidation process. Pre-oxidation
generally comprises the alternatives (Li et al., 2006): bio-oxidation
(Amankwah et al., 2005; Ubaldini et al., 2000; Muravyov and
Bulaev, 2013); chemical oxidation with O2 enriched air, high
pressure, and/or lead nitrate (Deschnes and Wallingford, 1995;
Deschnes et al., 2009); hydrogen peroxide (Karimi et al., 2010);
and high temperature roasting. Pre-treatment basically aims at
improving oxygenation along the cyanidation circuit, increasing
metallurgical recovery and reducing consumption of the cyanide-
leaching agent. Each of the pre-treatment process options has its
applicability, depending on the efficiency, capital investment and
operating costs.
Previous experience in other gold extraction plants indicated
the possibility of the use of hydrogen peroxide (H2O2) for the pur-
pose of pre-oxidation. AngloGold Ashantis Siguiri plant in Guinea
introduced oxygen supplementation via H2O2 injection in the
cyanidation circuit, and that resulted in an improvement in overall
plant gold recovery from
90% to
94% (Verster, 2016). In general,
the supplementation of dissolved O2 by injection of pure O2 could
also be considered for this type of situation. This was in fact ini-
tially tried in an industrial trial, but results were not as expected.
The strategy for developing the work began with preliminary
lab trials (not reported here) with the aim of determining the rate
of H2O2 consumption that would be necessary to meet the O2
uptake by the slurry. Once the feed rate of hydrogen peroxide to
the continuous process was established, the project moved ahead
to the stage of running an industrial scale trial. A dosing system
was assembled consisting of a centrifugal pump for delivering
hydrogen peroxide diluted with water on a 110 ratio, for fast
and efficient mixing of the oxidant into the slurry at each of the
three pre-oxidation tanks.
The present work describes the conditions employed and
reports the results obtained from the cyanidation, following the
pre-oxidation of the gold ore slurry with hydrogen peroxide.
1.1. Hydrogen peroxide for oxidative pre-treatment prior
to cyanidation
Hydrogen peroxide (H2O2) has been used for many years in gold
and silver extraction plants, mainly for: effluent detoxification/
neutralization of spent heaps (Botz et al., 2005; Breuer et al.,
2010; Kitis et al., 2005)/washing of residual NaCN from waste
big-bags; oxidation in intensive cyanidation (Longley et al.,
2003); and enhanced oxidation in conventional cyanidation.
H2O2 has the following relevant features:
(1) It is an aqueous liquid oxidant with a standard redox poten-
tial (Eoh = 1.8 V), higher than that of O2 (1.2 V).
(2) As an oxidant, it is able to oxidize sulphides to form oxides
or sulphates, as exemplified in reactions (1) and (2).
MS 4H2 O2 ! MO H2 SO4 3H2 O 1 hydrogen peroxide solution, diluted 10 times with water, into
MS 4H2 O2 ! MSO4 4H2 O
(3) It is a non-persistent chemical in water, wastewater and pro-
cess solutions it decomposes spontaneously into water and
oxygen:
H2 O2 ! H2 O 1=2O2 3
(4) Decomposition reaction (3) is catalysed by suspended solids
and/or aqueous transition metal ions, such as Fe or Cu.
(5) For the possible use on pre-oxidation of ore containing sul-
phides, both the direct oxidation of the sulphides and the
reaction driven by the O2 generated by decomposition of
H2O2 are useful possible mechanisms.
2. Methodology and pre-industrial trial results
2.1. Survey of process parameters before the H2O2 pre-oxidation trial
For a period of 5 days the ore that feeds the leaching circuit was
sampled and characterized for mineralogical composition and
tested for the determination of the oxygen uptake rate. In addition,
measurements of dissolved oxygen (DO) and free cyanide concen-
tration (as NaCN) along the cyanidation train were conducted, and
auditing of NaCN consumption was carried out as usual.
Analytical measurements before and during the trial were per-
formed as follows: DO was determined using a Metrohm dissolved
oxygen probe; pH was measured by a Hanna pH-meter; Oxygen
uptake measurements (for the calculation of the hydrogen perox-
ide equivalent doses) were carried out with a modified, portable
O2-uptake device assembled by Verster (2016); free cyanide in
solution was determined by a portable Mintek Cyanoprobe instru-
ment, as well as by titration with AgNO3; Au in solution was deter-
mined by atomic absorption spectroscopy using Perkin-Elmer
equipment. Probes and equipment were used along with ordinary
calibration procedures, according to the manufacturers specifica-
tions. It was observed that the addition of H2O2 to the pulp caused
only a slight reduction in pH at the end of the pre-oxidation time
(less than 0.3 pH units). In the industrial trial it was compensated
for by a slight increase in lime dosage, to ensure that the pH
remained at 10.5.
The results of these analyses led to setting the operating range
of the H2O2 feed.
2.2. Dissolved oxygen (DO) and [NaCN] profiles
During the five day monitoring of the cyanidation plant param-
eters, measurements of DO and of the concentration of free cyanide
(expressed as NaCN) in each of the tanks of the leaching train were
performed. Tanks 1, 2 and 3 are pre-oxidation only tanks, and tanks
414 are for cyanidation (with NaCN introduced only in Tank 4).
The results indicated that the DO profile could be described as
very low (fluctuating around 0.51.0 ppm in the pre-oxidation
tanks 13, and 1.4 ppm in the first cyanidation tank (Tank 4)).
The free NaCN profile was seen as normal (averaging 250
400 ppm in the first cyanidation tank of the train (Tank 4)). The
pH of the slurry in tanks 13 was controlled by the addition of lime
at around 10.5 0.3 pH units. The very low DO values in the pre-
oxidation tanks 1, 2 and 3 were all less than 1.0 ppm, well below
saturation, indicating insufficient oxidation in these tanks.
2.3. Industrial trial settings
The method of H2O2 supply consisted of pumping a 50%
the alkaline pre-oxidation tanks (tanks 1, 2 and 3), using a dosing
2 skid equipped with a centrifugal pump and a flow meter. Peroxide
dilution with water was carried out in the main feed pipe, and it
was split equally into the three in-series pre-oxidation tanks.
A schedule was set up for the monitoring of the following
parameters, for each shift: flow rate of hydrogen peroxide
 T.O. Nunan et al. / Minerals Engineering 108 (2017) 6770 69

50% w/w (L/h); concentration of dissolved oxygen (ppm) in all After evaluating results and costs for the first 32 days of H2O2
tanks of the cyanidation train; concentration of free sodium injection at different rates, it was decided to fix the H2O2 50% w/w
cyanide (ppm); Au leach feed content (g Au/t); Au content of solid dosing rate at 60 L/h for the remainder of the trial this corresponds
tailings (g Au/t); consumption of sodium cyanide. to a dosing rate of 0.24 kg of 100% H2O2 per ton of dry ore, bearing in
mind that for future consolidated operations the best method for
3. Industrial trial results and discussion regulating the H2O2 injection would be using automatic control
based on the desired DO level on the pre-oxidation tanks.
3.1. Dissolved oxygen concentration
3.2. Consumption of NaCN
The industrial trial with peroxide injection began with an initial
feed of 45 L/h of peroxide solution, further diluted with water prior The hydrogen peroxide and the consequent higher level of dis-
to distribution into the three pre-oxidation tanks. During the entire solved oxygen in the alkaline pre-oxidation tanks promoted faster
length of the five month trial, injection of hydrogen peroxide solu- and more effective oxidation of cyanide-consuming sulphidic spe-
tion was carried out only into the three alkaline pre-oxidation cies. These species, which used cyanide as complexing agent, were
tanks. Variations of pre-oxidation conditions were restricted to inactivated in the first tanks of the circuit. As a consequence, the
the peroxide flow only, in an attempt to achieve the concentration NaCN specific consumption in the cyanidation circuit was consid-
of dissolved oxygen of more than 6 ppm previously established in erably reduced, reaching the lowest value by comparison to the
the preliminary laboratory trials. Peroxide flow rates were set previous 3 years. Considering the period before the trial, the aver-
according to Table 1. age consumption of sodium cyanide in the five-month period
Measurements of DO concentration were carried out every 2 h. before the industrial trial was 0.52 kg/t. In the five-month period
The DO measurements showed that with the injection of hydrogen of the peroxide pre-oxidation trial, the average consumption of
peroxide (up to 80 L/h of H2O2, 50% w/w) it was possible to NaCN fell to 0.40 kg/t a reduction of 23% (Fig. 1).
increase the average concentration of dissolved oxygen in the alka-
line pre-oxidation tanks up to 8 ppm. Before the trial, that was lim- Table 2
ited to less than 1 ppm, using only compressed air. Average ore feed Au grades and Au recoveries: months 15 before pre-oxidation with
H2O2; months 610, during pre-oxidation with H2O2 injection.
Table 1 Month % Au ore feed % Au leach residue Au recovery (%)
Hydrogen peroxide feed rate during industrial trial.
1 3.17 0.323 89.8
Period (days) H2O2 50% flow Average DO in Tanks 2 3.56 0.238 93.3
rate (L/h) 1, 2 and 3 (ppm) 3 3.09 0.273 91.2
4 3.01 0.277 90.8
Before H2O2 0 <1.0
5 3.54 0.297 91.6
pre-oxidation
6 3.27 0.258 92.1
115 45 2.9
7 3.34 0.276 91.7
1621 55 4.2
8 3.25 0.224 93.1
2232 80 8.0
9 3.61 0.275 92.4
33150 60 7.2
10 3.83 0.271 92.9

Fig. 1. NaCN consumption before (months 15) and during (months 610) pre-oxidation with H2O2 injection.
70 T.O. Nunan et al. / Minerals Engineering 108 (2017) 6770
Fig. 2. Metallurgical recovery of Au before (months 15) and during (months 610) pre-oxidation with H2O2 injection.
3.3. Au metallurgical recovery
Table 2 shows the monthly average values of ore feed Au grade,
Au grade in the cyanidation residue, and the calculated metallurgi-
cal Au recovery for each of the five previous months and the other
subsequent months of the pre-oxidation trial. The graph in Fig. 2
compares the values of Au metallurgical recovery before (months
15) and after (months 610) pre-oxidation with H2O2 injection.
In spite of the inevitable variations in metal recovery that may
be attributed partly to the changes in the lithology of the ore fed
into the plant, the average recovery increased from 91.3% to
92.5%, a satisfactory net gain for the inclusion of peroxide as a
chemical in the leaching process, considering that the cost of add-
ing the peroxide is more than offset by the reduction in the con-
sumption of NaCN. Diagnostic intensive re-cyanidation of tailings
also indicated a reduction in Au content amenable to cyanidation
from an average of 0.144 g/t (in months 15) to 0.107 g/t (with
peroxide in months 610).
4. Conclusions
The injection of 60 L/h of hydrogen peroxide (H2O2 50% w/w,
density = 1.19 g/mL) in a slurry (60% w/w solids) of gold ore
containing sulphides (2.5% w/w FeS), for the purpose of pre-
oxidation in a cyanidation circuit processing a feed of 150 t/h
(dry ore), corresponding to a dosing rate of 0.24 kg 100% H2O2/t
of dry ore, had the following effects:
(1) Increase of the average concentration of dissolved oxygen in
the three tanks of pre-oxidation from 1 to 7.2 ppm.
(2) Reduced consumption of NaCN in the cyanidation circuit
from an average of 0.52 kg/t to 0.40 kg/t of dry ore.
(3) Increase in the metallurgical recovery of Au from an average
of 91.3 to 92.5%
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