Hydrometallurgy 144145 (2014) 3438

Contents lists available at ScienceDirect

Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

A novel process for silver recovery from a refractory AuAg ore in

cyanidation by pretreatment with sulfating leaching using pyrite
as reductant
Xian-yang Qiu, Zhen Hu, Bao-xu Song , Han-wen Li, Jian-jian Zou
Guangzhou Research Institute of Non-ferrous Metals, Guangzhou, Guangdong 510650, China

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

Article history: A novel process was developed to markedly increase silver cyanidation performance from a refractory goldsilver
Received 27 February 2013 ore in Beiya, Yunnan province, China. Before cyanidation, the process employs a pretreatment step that aims at
Received in revised form 19 November 2013 liberating the silver grains by destroying the crystal lattices of manganese minerals. The pretreatment step
Accepted 2 January 2014
could be described as a reductive sulfating leaching technology to preferentially dissolve the manganese min-
Available online 30 January 2014
erals, with silver remaining in the leaching residue for subsequent cyanidation, and the most important nding
Keywords:
of the study is that pyrite could be used as a reductant through the process. The result indicates that the recovery
Manganesesilver ore of silver has a remarkable 43.92% increase compared to a direct cyanidation process without pretreatment step.
Reductive leaching 2014 Elsevier B.V. All rights reserved.
Cyanidation
Refractory gold ore

1. Introduction
Gold- and silver-bearing ores are typically classied as either free
milling or refractory based on their metallurgical response to cyanide
leaching. As free milling gold- and silver-bearing mineral resources
are rapidly depleted, one of the most pressing problems facing the
gold and silver industry is to develop efcient and effective processes
to extract these precious metals from their refractory ores.
The refractoriness of silver-bearing ores results primarily from such
inherent mineralogical features as silver inter-locking with sulphide,
complete inclusions or isomorphism in the bearing minerals, and from
reactive gangue mineralogy (e.g. preg-robbing carbonaceous constitu-
ents). To effectively extract silver from silver-bearing refractory ores,
pretreatment of these ores prior to cyanide leaching is necessary to ren-
der the silver contained therein readily amenable to cyanidation.
Among all the silver refractory ores, the silvermanganese type is
perhaps the most common because the silver grains are very nely dis-
seminated as isomorphism in the crystal lattices of manganese minerals.
Silver cyanidation from the refractory silvermanganese ore is always
unsatisfactory either by mechanical beneciation methods or by
conventional cyanidation. Given the importance of refractory manga-
nesesilver ores as highly valued mineral resources for both silver and
manganese, there has been a great deal of research interest in develop-
ing efcient cyanidation process for these ores.
As the silver grains are very nely disseminated as isomorphism in the
crystal lattices of manganese minerals, destroying the lattice structures of
Corresponding author at: No. 363 (Guangzhou Institute of Non-Ferrous Metals),
Changxing Road, Tianhe district, Guangzhou city, Guangdong Province, 510650, China.
the manganese minerals is essential to liberate silver grains and, thus, en-
hance silver cyanidation effectiveness. One of the routes is to reduce the
MnO2 to Mn2+, which can be accomplished through pyro- or hydro-
metallurgical process. Compared with pyro metallurgical process which
requires high energy consumption and produces severe environmental
pollution, hydrometallurgical process has always been the dominant
and effective method. The reported hydrometallurgical processes for sil-
vermanganese ores can be classied into one-step and two-step pro-
cesses (Gupta and Ehrlich, 1989). The one-step process involves the
simultaneous leaching of manganese and silver, which has been proved
to only be effective for the manganesesilver ores with high silver
content, and the two-step process employs a reductive sulfating leaching
process to dissolve manganese minerals before cyanidation, which has
been widely applied in manganesesilver ore treatment.
At present, most of the reported researches have focused on the re-
ductants employed in the reductive leaching pretreatment process.
These reductants include sulfur dioxide, sodium sulte (Tian et al.,
2012), organic reductor (Pankratova et al., 2001) (Sahoo et al., 2001),
metallic iron powder (Bafghi et al., 2008), ferrous sulfate (Shen et al.,
2006) and so on (Lan, 2004; Zhang et al., 2006). The reduction of the
manganese oxides by above-mentioned reductants in acidic systems
can be summarized by the following reactions:
SO2 MnO2 MnSO4 1
Na2 SO3 H2 SO4 MnO2 Na2 SO4 MnSO4 H2 O 2
Cx Hy Oz MnO2 H2 SO4 MnSO4 CO2 H2 O 3
3MnO2 6H2 SO4 2Fe Fe2 SO4 3 3MnSO4 6H2 O 4

0304-386X/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2014.01.016
 X. Qiu et al. / Hydrometallurgy 144145 (2014) 3438 35

MnO2 2FeSO4 2H2 SO4 MnSO4 Fe2 SO4 3 2H2 O 5 Table 2

0 Experimental conditions for reductive sulfating leaching and cyanidation of the ore.
MnO2 ZnS 2H2 SO4 MnSO4 ZnSO4 2H2 O S 6
Parameter Reductive sulfating leaching Cyanidation

It should be noted, however, that most of the reported reductants FeS2 concentration, mol/L 0.030.060.100.12
with the related reduction processes are still in the testing stage because H2SO4 concentration, mol/L 0.070.110.140.200.24
NaCN concentration, g/L 0.120.160.200.24
of the long reaction time and the high chemical consumption to effectu- Pulp density, (w/w), % 25 25
ate the liquid/solid reaction. Temperature, C 95 2 28 2
For some AuAg deposits, the level of manganese contained therein Leach time, hour 1.5 30
may not reach an economic value, but it is still an impurity affecting the Agitation, rpm 1700 1700
Particle size, d80: micron 20 m 20 m
silver cyanidation. Thus, in order to completely recover silver minerals,
pH (CaO) Not measured 9 0.3
a pretreatment process is also required to remove manganese before
cyanidation.
For the refractory goldsilver ores associated with manganese min-
the ores are magnetite, maghemite and limonite, which were subjected
erals, this study has developed a reductive sulfating leaching pretreat-
to the oxy-alteration action during the formation of the ore body. The
ment process to dissolve manganese minerals before goldsilver
major gangue minerals are quartz, calcite, and dolomite.
cyanidation, and pyrite has been proved that could be used as an effec-
To better establish the distribution of silver in the major minerals, a
tive reductant in the pretreatment step.
balanced distribution result below 36 m was calculated as shown in
Table 4. According to the result, most of the silver was born in limonite
2. Materials and methods and coronadite with a distribution of 49.33%, and free silver accounts for
only 38.49%.
The ores used in this study were from Beiya, Yunnan province, China. The selected SEM images of silver presence and association are
The ore sample was crushed down to 2 mm using roll crushers and shown in Fig. 1, and details are as follows: Silver grains have complex
rifed to obtain 1 kg representative sub-samples. These were then associations and disseminations, some occur as native silver existing
ground in a laboratory ball mill to the desired neness (80% passing in heavy minerals (Fig. 1-A), and some occur as irregular associations
size, d80 = 20 m) prior to the leaching tests. The elemental analysis with lead minerals (Fig. 1-B and C). It should also be noted that
of the sample was determined by wet chemical analysis methods
using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectros-
copy) and the result is shown in Table 1. As can been seen from the Table 3
The mineral composition of the ore sample.
Table, the ore sample contained 2.70 ppm Au and 41.20 ppm Ag.
Accurate characterization of an ore is essential to identify the mode Minerals Content/%
and occurrence of gold and silver minerals, and hence, a mineralogical Magnetite 10.905
examination of the ore sample was performed, during which various Maghemite 13.704
techniques including optical microscopy, scanning electron microscopy Limonite 38.152
(SEM) and mineral liberation analyzer (MLA) were used. Malachite 0.052
Chrysocolla 0.021
Based on the chemical and mineralogical analysis of the sample, a
Galena 0.009
comprehensive recovery process was developed: grinding was rst per- Cerussite 0.030
formed to obtain a xed neness of grind d80: 20 m, during which Pyrite 0.078
pyrite was added and its usage level was recorded. After grinding, a re- Sphalerite 0.005
Arsenopyrite 0.002
ductive sulfating leaching pretreatment process was performed in a
Molybdenite 0.001
water bath using a mechanical stirrer at constant rate of 1700 r/min Bismite 0.005
and a temperature of 95 C, during which the concentration of H2SO4 Coronadite 1.389
was recorded. Then the cyanide leaching tests (30 h) were performed Manganite 0.796
in a glass reactor equipped with a pitched-blade turbine impeller rotat- Plumbogummite 0.024
Jarosite 0.057
ing at 1700 r/min, during which the concentration of NaCN was record-
Quartz 11.452
ed. The effects of pyrite concentration (0.030.12 mol/L), sulfuric acid Feldspar 3.498
concentration (0.070.24 mol/L), and NaCN concentration (0.12 Sericite 0.164
0.24 mol/L) were investigated, respectively, and Table 2 summarizes Illite 0.620
Biotite 4.543
the study conditions of the reductive sulfating leaching and the
Chlorite 4.350
cyanidation processes. Tremolite 1.283
Andradite 0.134
3. Results and discussions Topaz 0.010
Talcum 0.401
Clay 1.646
3.1. Mineralogical characteristics of the ores Fluorite 0.078
Calcite 1.106
The mineral composition of the ores determined by mineral libera- Dolomite 4.940
Ilmenite 0.083
tion analyzer (MLA) was shown in Table 3, and the major minerals in
Rutile 0.089
Titanite 0.013
Table 1 Perovskite 0.001
Elemental composition of the ore sample. Apatite 0.015
Monazite 0.003
Elements Cu Pb Zn Fe As Mn
Zircon 0.006
Content/% 0.37 0.54 0.09 37.22 0.13 1.28 Cassiterite 0.002
Elements Au Ag S Sn Glactite 0.228
Content/ppm 2.70 41.20 490 200 Gbbsite 0.099
Compounds Al2O3 MgO CaO SiO2 Others 0.003
Content/% 3.35 1.84 2.68 25.48 Total 100.000
36 X. Qiu et al. / Hydrometallurgy 144145 (2014) 3438

Table 4 results revealed that the cyanidation of gold and silver occurred most
The distribution of silver in major minerals. extensively over a period of 130 h. Thereafter, the dissolution of gold
Minerals Content/% Grade of Distribution and silver appeared to be leveled off with little change. The highest
silver/ppm of silver/% cyanidation of silver was only 27.4%, indirectly conrming the refracto-
Free silver 38.49 riness of silver.
Magnetite and maghemite 24.609 12.19 7.28
Limonite and coronadite 40.337 50.39 49.33 3.3. Pretreatment-cyanidation tests
Gangue 34.508 5.85 4.90
Others 0.546
Total 100.00 36.12 100.00 Based on the mineralogical characteristics of the ore in Beiya, the sil-
ver grains mainly occur as complete inclusions or isomorphism hosting
in the crystal lattices of coronadite, which makes the silver minerals
hardly accessible to cyanide. Thus, how to destroy the above mentioned
49.33% of the silver shown in Table 4 mainly occur as complete inclu- crystal lattices of coronadite to liberate the silver grains before
sions or as isomorphism in limonite and coronadite (Fig. 1-D, E and F). cyanidation has been a tough issue.
MnO and MnO2 are the main chemical compositions of coronadite,
and both exhibit strong oxidation state in acidic solutions. In the acidic
3.2. Direct cyanidation tests solutions, the pyrite only reacts to the MnO2, but not to the silver and
gold. Using pyrite as reductant, MnO2 can be easily reduced to Mn2+
The direct cyanidation tests were rst conducted to recover gold and and dissolved completely in the acidic solution, then the silver
silver from the as-received ores, and the results are shown in Fig. 2. The and gold reserve in the residue and are much more accessible for

Fig. 1. Selected presence and association of gold and silver in ore under ore microscopy and scanning electron microscopy (SEM).
 X. Qiu et al. / Hydrometallurgy 144145 (2014) 3438
Fig. 2. Direct cyanidation (0.2 g/L NaCN) of gold and silver from the as-received ores over a
period of 50 h, particle size d80: 20 m.
subsequent cyanidation. The overall reactions in the reductive sulfating
leaching process are as follows:
363k
2FeS2 s 14H2 SO4 15MnO2 s Fe2 SO4 3 15MnSO4
14H2 O
363k
MnO H2 SO4 MnSO4 H2 O
After the reductive sulfating leaching step under different condi-
tions, cyanidation was performed to its residue, and Figs. 3 and 4 sum-
marize the subsequent goldsilver cyanidation efciency. Compared
with a direct cyanidation without reductive pretreatment, it is rather
apparent that silver cyanidation is enhanced. Data in Fig. 3 also shows
that increasing the FeS2 concentration increases the silver cyanidation
efciency, with cyanidation rate peaking at 0.12 mol/L. Likewise, data
in Fig. 4 indicate that increasing the H2SO4 concentration increases
the silver cyanidation recovery, with cyanidation rate peaking at
Fig. 3. The effect of FeS2 concentration on the subsequent goldsilver cyanidation process
(0.14 mol/L H2SO4, 0.2 g/L NaCN; pH 9; leach time: 30 h; particle size (d80) 20 m).
37
Fig. 4. The effect of H2SO4 concentration on the subsequent goldsilver cyanidation
process (0.12 mol/L FeS2, 0.2 g/L NaCN; pH 9; leach time: 30 h; particle size (d80) 20 m).
0.14 mol/L. Thus, 0.12 mol/L FeS2 and 0.14 mol/L H2SO4 are selected
for the subsequent cyanide cyanidation of gold and silver.
A comparison between direct cyanidation and pretreatment-
cyanidation is presented in Fig. 5, and the concentration of NaCN has
been investigated. As can be seen from the result, at 0.2 g/L NaCN con-
7
centration, the gold and silver recoveries both reach the steady values,
and pretreatment-cyanidation has a remarkable increase of silver
recovery.
Finally, under the optimal conditions, the stable tests of direct
8
cyanidation and pretreatment-cyanidation were conducted, respective-
ly, and the comparison is shown in Table 5. After the direct cyanidation
process, the nal residue assays 0.36 ppm Au, and 29.91 ppm Ag, which
indicates a very low silver recovery of 27.40%. While after the
pretreatment-cyanidation process, the nal residue assays 0.18 ppm
Au and 11.82 ppm Ag, and the silver recovery has a remarkable
43.92% increase, reaching 71.32%. The result indicates that the effect is
somewhat more pronounced with the silver cyanidation than with the
gold cyanidation, and the reductive sulfating leaching pretreatment
also appeared to have a positive effect on gold cyanidation.
Fig. 5. The effect of NaCN concentration on direct cyanidation and pretreatment-
cyanidation for gold and silver recovery (0.12 mol/L FeS2 and 0.14 mol/L H2SO4; pH 9;
leach time: 30 h; particle size (d80) 20 m).
38 X. Qiu et al. / Hydrometallurgy 144145 (2014) 3438

Table 5 minerals, which have weak magnetism. Therefore, the emphasis of fu-
The comparison between direct cyanidation and pretreatment-cyanidation stable tests. ture research is how to introduce magnetic separation operation for
Schemes Grade of Leaching pre-concentration of the refractory silver and manganese minerals be-
residue/ppm recovery/% fore leaching, and the latest cost of the reagents has been reduced to
Au Ag Au Ag 9 dollars per ton.
Direct cyanidation 0.36 29.91 85.00 27.40
Pretreatment-cyanidation 0.18 11.82 93.34 71.32 Acknowledgment

4. Conclusions Sincere thanks and appreciation go to the Yunnan Gold Mining

The refractoriness of silver-bearing ores results primarily from in-
herent mineralogical features, and manganese has always been an im-
purity because the silver grains always occur as isomorphism hosting
in the crystal lattices of manganese minerals, making silver minerals
hardly accessible to the cyanide leaching. For these silvermanganese
ores, destroying the lattice structures of the manganese minerals is
essential to enhance silver cyanidation. In this study, a novel process
of reductive sulfating leaching using pyrite as a reductant has been
developed and shown to be an effective pretreatment process step.
The result shows that the cyanidation of silver has a remarkable
43.92% increase, and the recommended process also has a positive effect
on gold cyanidation.
The reagents of the whole process cost approximately 17 dollars per
ton, and sulfuric acid occupies more than 50%. Although the chemical
cost is a little high, there is still a new output of 23 dollars per ton by in-
creasing the silver recovery. For future works, how to reduce the
reagents cost still has a lot of work to do, and we have noticed that
the refractory silver minerals are mainly disseminated in manganese
Group for nancial support and kindly providing the samples.
References
Bafghi, Monhammad Sh., Zakeri, Alireza, Ghasemi, Zahra, Adeli, Mandana, 2008. Reduc-
tive dissolution of manganese ore in sulfuric acid in the presence of iron metal.
Hydrometallurgy 90, 207212.
Gupta, Asha, Ehrlich, Henry L., 1989. Selective and non-selective bioleaching of manga-
nese from a manganese-containing silver ore. Biotechnology 9 (4), 287304.
Lan, Y.Z., 2004. Laboratory study: simultaneous leaching silver-bearing low-grade manga-
nese ore and sphalerite concentrate. Miner. Eng. 910, 10531056.
Pankratova, A.B., Nevskaya, E. Yu, Kutepov, A.M., Gorichev, I.G., Izotov, A.D., Zaitsev, B.E.,
2001. Dissolution kinetics of manganese(III, IV) oxides in sulfuric acid in the presence
of ethylenediaminetetraacetic acid. Theor. Found. Chem. Eng. 35 (2), 168174.
Sahoo, R.N., Nayak, P.K., Das, S.C., 2001. Leaching of manganese from low grade manga-
nese ore using oxalic acid as reductant in sulfuric acid solution. Hydrometallurgy
62, 57163.
Shen, Q., Yang, X.W., Liu, C.X., Xie, K.Q., 2006. Study on leaching silver from silver
manganese ore reduced by FeSO4. J. Kunming Univ. Sci. Technol. (Sci. Technol.)
31 (6), 1216 (in Chinese).
Tian, Q.H., Jiao, C.Y., Guo, X.Y., 2012. Extraction of valuable metals from manganesesilver
ore. Hydrometallurgy 119120, 815.
Zhang, X.Y., Tian, X.D., Zhang, D.F., 2006. Separation of silver from silver-manganese ore
with cellulose as reductant. Trans. Nonferrous Metals Soc. China 16, 705708.