Bioleaching of a low grade nickelcoppercobalt sulde ore

Congren Yang
a,b
, Wenqing Qin
a,b,
, Shaoshi Lai
a,b
, Jun Wang
a,b
, Yansheng Zhang
a,b
, Fen Jiao
a,b
,
Liuyi Ren
a,b
, Tian Zhuang
a,b
, Ziyong Chang
a
a
School of Minerals Processing and Bioengineering, Central South University, Changsha, Hunan 410083, PR China
b
Key Laboratory of Biometallurgy of Ministry of Education, Central South University, Changsha, Hunan 410083, PR China
a b s t r a c t a r t i c l e i n f o
Article history:
Received 21 July 2010
Received in revised form 20 November 2010
Accepted 21 November 2010
Available online 1 December 2010
Keywords:
Bioleaching
Nickel-bearing sulde ore
Jarosite
Magnesium silicate
The bioleaching behavior of copper and nickel froma low-grade nickel, copper, and cobalt-bearing sulde ore
was investigated. A recovery of 94% Ni, 62% Co and 70% Cu was achieved in 68 days of ask leaching including
18 days of acid pre-leaching and 50 days of bioleaching. However, a recovery of 46% Ni, 39% Co and 13% Cu was
achieved in 139 days of column leaching including 19 days of acid pre-leaching and 120 days of bioleaching
which indicates that nickel and cobalt have the same leaching behavior. Potassium, sodium and iron(III) ions
in the leach solution formed jarosite within the ore bed with some nickel and copper ions incorporated into
the jarosite precipitates thereby diminishing the overall metal recovery. Magnesium was preferentially
leached by acid from the gangue minerals leaving a magnesium depleted silicate skeleton, but discrepancies
in the residue analysis indicate that magnesium re-deposits into the silicate skeleton during bioleaching.
2010 Elsevier B.V. All rights reserved.
1. Introduction
In the last decade, extensive efforts have been made to expand
bioleaching technology to primary copper sulde ores, and to a lesser
extent nickel sulde ores (Brierley and Brierley, 2001; Ehrlich, 2001;
Watling, 2006, 2008). Recently, Cameron et al. (2009) investigated
the technical feasibility of using elevated-pH bioleaching on a
Canadian low-grade ultramac nickel sulde ore (containing ~35%
MgO) and found that nickel extraction frompentlandite was relatively
insensitive to acidity at low pH but sensitive at high pH. The opposite
trend was observed while examining the extraction of magnesium
(Cameron et al., 2009; Qin et al., 2009). Likewise, Zhen et al. (2009)
studied the bioleaching of a Chinese low grade nickel-bearing sulde
ore containing rather high levels of olivine, chlorite and antigorite
gangue minerals using mixed mesophiles and found that the tolerance
of the mixed bacteria to magnesium in solution could be improved
markedly from 10 g/L to 25 g/L Mg. On the other hand, Santos et al.
(2006) studied on the bioleaching of a low grade complex nickeliron
concentrate containing pentlandite together with signicant levels of
pyrrhotite and minor amounts of chalcopyrite. The external addition
of Fe(II) showed no effect on the extraction of nickel, emphasizing the
importance of pyrrhotite dissolution in the rst step of bioleaching.
Other recent investigations of bioleaching of a low-grade copper
nickel sulde ore from Radio Hill focused on the impact of aeration
and pH on copper and nickel extraction during column and heap
leaching (Maley et al., 2009a, b; Watling et al., 2009) where it was
found that soluble copper in the leachates re-precipitated as copper
sulde, mainly covellite.
In the present study, a low-grade nickelcoppercobalt sulde ore
obtained from Hami, Xinjiang Province, China, was subjected to ask
and column bioleaching. The purpose of this study was to investigate
the leaching behavior of the metals (Cu
2+
, Ni
2+
, Co
2+
, and Fe
3+
), as
well as magnesium, and especially the co-precipitation or adsorption
of copper and nickel ions with the jarosite formation.
2. Materials and methods
2.1. Mineral characteristics and preparation
The low grade nickel-bearing sulde ore used in the test was
obtainedfromHami, Xinjiang Province, China. The chemical analysis of
the ore sample showedNi 0.45%, Co 0.013%, Cu0.18%, Fe 9.07%, S 2.05%,
MgO 7.30%, CaO 7.95%, SiO
2
46.77% and Al
2
O
3
13.91%. Mineralogical
analysis of the ore sample showed that 84% Ni, 98% Cu and 62% Co was
present in a metal sulde mineral, whilst 37% Co was present in
silicates. The iron was present mainly as hematitelimonite (32%) and
silicate (32%) together with lesser amounts of carbonate (18%) and
metal sulde mineral (15%). The X-ray diffraction analysis of the
sample showed the main gangue minerals were feldspar, chlorite and
amphibole, together with lesser amounts of talc, mica, quartz.
The ore samples used for column leaching were crushed and
screened to 8 + 3 mm and further ground to 0.074 mm (90%)
for ask leaching.
Hydrometallurgy 106 (2011) 3237
Corresponding author. School of Minerals Processing and Bioengineering, Central
South University, Changsha, Hunan 410083, PR China. Tel.: +86 731 8830884; fax: +86
731 8710804.
E-mail address: qinwenqing369@126.com (W. Qin).
0304-386X/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2010.11.013
Contents lists available at ScienceDirect
Hydrometallurgy
j our nal homepage: www. el sevi er. com/ l ocat e/ hydr omet
2.2. Chemicals
All chemicals were of analytical reagent grade from the Beijing
Chemical Reagents Factory and were used as starting materials
without further purication. De-ionized water was used throughout
the Cu, Ni and Fe co-precipitation experiment.
2.3. Microbial culture
Acidithiobacillus ferrooxidans, Acidithiobacillu thiooxidans,
Leptospirillum ferrooxidans and At. caldus were obtained from the
Key Laboratory of Biometallurgy of Ministry of Education, Central
South University, Changsha, China. The microorganisms were cul-
tured in 250 mL shake asks using an orbital incubator with a stirring
speed of 160 rpm at a constant temperature (35 C). A sterilized 9 K
medium, composed of 3.0 g/L (NH
4
)
2
SO
4
, 0.1 g/L KCl, 0.5 g/L
MgSO
4
7H
2
O, 0.5 g/L K
2
HPO
4
and 0.01 g/L Ca(NO
3
)
2
, was used for
bacteria growth. Ferrous oxidising microbial culture was sub-cultured
into basal salts medium supplemented with ferrous ions (44.7 g/L
FeSO
4
7H
2
O) as the energy source. Sulfur oxidising microbial culture
was sub-cultured into basal salts medium supplemented with
elemental sulfur (1%, w/v) as energy source. All the bacterial cultures
were sub-cultured into basal salts medium supplemented with ore
powder (0.074 mm 90%) as the energy source. The resulting
mixed culture was used as inoculums for the shake asks experiments
and column experiments.
2.4. Bioleaching experiments
2.4.1. Leaching in shake asks
The low-grade ore powder (0.074 mm 90%), which was
prepared fromthe 8 +3 mmore samples, was initially added to 9 K
medium without ferrous ions at 10% w/v pulp density and the asks
were placed in an orbital shaker at 180 rpmand 35 C. The pHvalue of
acid leaching in the rst 18 days was controlled at pH 0.81.6 with
concentrated sulfuric acid since the ore contained high levels of acid-
consuming minerals (CaO 8.0% and MgO 7.3%), then 1% (v/v)
inoculums with the cell density of about 10
8
cell/mL was added into
the conical ask for bioleaching. Water lost by evaporation was
supplemented periodically by adding sterile water until the mass of
the ask equaled its initial mass.
2.4.2. Column leaching
Representative 8 + 3 mm ore sample was loaded into a column
(0.5 mtall, 7 cmdiameter) equipped with a 3 L solution reservoir, and
the column leaching experiment was carried out at room tempera-
ture. Before inoculation, the charge was ideally pre-leached by 2.5 L
diluted sulfuric acid solution to control the discharged solution pHat a
level for good bacterial activity (pH 1.72.2). Pre-leaching irrigation
was stopped when the pHof the solution was stabilized at pH1.52.2.
Then 5% (v/v) inoculums with a cell density of about 10
8
cell/mL and
nutrients of 3.0 g/L (NH
4
)
2
SO
4
and 0.5 g/L K
2
HPO
4
were added to the
pre-leached solution, and nally the solution pHvalue was adjusted to
1.71.9 for bioleaching.
2.5. Metal ion co-precipitation with jarosite formation
A solution of 10 g/L Fe(II), 0.5 g/L Cu or 1.5 g/L Ni in 90 mL fresh 9 K
media was mixed with 5 mL A. ferrooxidans solution and 5 mL
L. ferrooxidans inoculums (with a cell density of about 10
8
cell/mL
solution) and added to a clean, dry, sterile 250 mL conical ask. The
asks were weighed and placed in an orbital shaker (160 rpm) with
the temperature controlled at 30C. Samples (1.0 mL) were removed
for analysis using a sterile Pasteur pipette and the sample volume was
replaced with an equal volume of fresh 9 K media. Again, evaporation
losses were compensated periodically by the addition of sterile
deionised water. Samples were acidied and analyzed for Cu, Ni, Fe
and K using inductively-coupled plasma-atomic emission spectrom-
etry (ICP-AES).
Fig. 1. Metal dissolution during ask bioleaching at 35 C.
Fig. 2. Solution pH and redox potential (ORP) during ask leaching.
Fig. 3. Total iron, potassium and sodium ion concentrations in the ask leach solution.
33 C. Yang et al. / Hydrometallurgy 106 (2011) 3237
2.6. Analytical techniques
The samples used in leaching were characterized on a Germany
Bruker-axs D8 Advance X-ray powder diffractometer (XRD) with Cu
K radiation ( = 1.5406 ). The operation voltage and current were
kept at 40 kV and 40 mA, respectively. Solutions were analyzed for Ni,
Cu, Co, Fe, K and Na using America Baird Co. PS-6 inductively coupled
plasma-atomic emission spectrometer (ICP-AES). The pH of the
supernatant at room temperature was measured with a pH meter
(PHSJ-4A) and the redox potential (ORP) in the leaching solution were
measured with a Pt electrode with reference to a saturated Hg/Hg
2
Cl
2
electrode.
3. Results and discussion
3.1. Leaching in shake asks
Extraction of 94% Ni and 65% Co was achieved in 53 days ask
leaching with 18 days acid pre-leaching, followed by 35 days
bioleaching (Fig. 1). Then the nickel and cobalt recovery decreased
and nally stabilized at about 80% and 60% respectively over the
following 15 days. At the same time about 70% copper was extracted
over 68 days. During the whole leaching process, iron bioleaching
exhibited three stages: a rapidly extracting stage, a stabilizing stage
with a maximum extraction of 31%, and a decreasing stage as jarosite
precipitates.
Nickel, copper, cobalt and iron were all extracted rapidly after
inoculating bacteria, but then the rates of extraction became very slow
10 days later. The variation of pH and ORP (redox potential) of the
pregnant leaching solution and the recovery of nickel, copper and
cobalt were consistent: after inoculating bacteria, the ORP increased
Fig. 4. (A) XRD spectra before and after leaching; (B) Mg, Al and Si dissolution during
ask leaching.
Fig. 5. Metal dissolution during column bioleaching.
Fig. 6. Solution pH and redox potential (ORP) during the column leaching at room
temperature.
Fig. 7. Total iron, potassium and sodium ion concentrations in the column leach
solution (3.0 g/L (NH
4
)
2
SO
4
and 0.5 g/L K
2
HPO
4
were added into the leaching solution).
34 C. Yang et al. / Hydrometallurgy 106 (2011) 3237
rapidly and stabilized at 660 mV, whilst the pH rst decreased and
thereafter increased (Fig. 2).
Fig. 3 shows the variations in the concentrations of iron, potassium
and sodium ions. The potassium concentration decreased rapidly in
the rst 29 days of leaching and then stabilized at a lower
concentration of about 20 mg/L whilst the sodium ion concentration
was stable at about 70 mg/L. Since iron(III) and potassium ions
generate jarosite (Eq. 1) these results indicate that potassium jarosite
is preferentially formed over sodium jarosite when both K
+
and Na
+
are present. At the same time, it appears that nickel ions are
incorporated into the jarosite scale, thereby diminishing the overall
nickel (and other metals) recovery. These ndings are consistent with
results reported by Watling et al. (2009).
M

+ 3Fe
3+
+ 2SO
2
4
+ 6H
2
OMFe
3
SO
4

2
OH
6
+ 6H

1
where M is a monovalent cation, e.g. H
3
O
+
, Na
+
, K
+
and NH
4
+
.
After the bioleaching, the residues were rinsed with dilute sulfuric
acid (pH1.8) and dried at roomtemperature and analyzed using X-ray
diffraction (Fig. 4A). However, there were discrepancies between the
Fig. 8. Solution proles during bio-oxidation of iron and jarosite precipitation in the presence of 0.5 g/L Cu or 1.5 g/L Ni. A. solution pH; B. solution ORP; C. total iron concentrations;
D. potassium concentration; E. copper concentration; F. nickel concentration.
35 C. Yang et al. / Hydrometallurgy 106 (2011) 3237
XRD results and the magnesium leaching results. The leaching of Mg,
Al and Si into solution (Fig. 4B) shows over 50% Mg extraction, but the
chemical analysis of the leaching residues showed only 26% Mg
extraction together with 18% Al and 28% Si extraction. It appears that
Mg
2+
is preferentially leached from gangue minerals and then re-
deposits in the remaining silicate skeleton, possibly as amorphous
magnesiumsilicate as the pHwithinthe skeletonrises. However, X-ray
diffraction analysis before and after leaching of magnesium did not
change the crystalline structure of mineral (Fig. 4A), as also found by
Cameron et al. (2009).
3.2. Column leaching
A recovery of 46% Ni, 39% Co, 13% Cu and 14% Fe was achieved in
139 days column leaching including 19 days acid pre-leaching and
120 days bioleaching. Fig. 5 shows that nickel and cobalt had similar
leaching behavior and were more easily leached than copper and iron
whilst Fig. 6 shows the value of solution pHand redox potential (ORP)
during the column leaching.
Like the ask leach solutions, the concentrations of potassium and
sodium were very low in column leach solution with the potassium
concentration much lower than that of sodium ions (Fig. 7). These
ions, together with iron(III), led to the formation of jarosite within the
ore bed, particularly after 89 days when additional K
2
HPO
4
and
(NH
4
)
2
SO
4
was added to the leach solution. Watling et al. (2009) and
Klauber (2008) reported a layer of jarosite scale on particle surfaces
which encapsulated sulde grains and was of sufcient depth and
integrity to have hindered the transfer of reactants and reaction
products between the bulk solution and mineral surfaces. Clearly,
excessive jarosite formation could deplete the solution of ferric ions
and inhibit nickel leaching since Yang et al. (2008) reported that the
extraction of nickel was favored by the high ferric concentrations.
Fig. 5 also shows that the copper extraction was very low which is
similar to the results of heap leaching Radio Hill ore that indicated
copper extraction lagged behind nickel extraction by 56 months
(Watling et al. 2009). It was hypothesised that the copper had been
leached from the chalcopyrite, but subsequently re-deposited in the
ore bed. Both Hiroyoshi et al. (2001) and Watling et al.(2009)
reported that moderately low solution potential was expected to
enhance the oxidation of chalcopyrite, but in our study, the solution
potential was rather high at 550650 mV and the copper concentra-
tion in the ore was too low to determine whether chalcopyrite
remained or was transformed into other copper suldes.
3.3. Cu, Ni and Fe co-precipitation with jarosite formation
Fig. 8 shows the progress over 12 days of total soluble iron,
potassium, nickel and copper concentration, pH and ORP for cultures
with 9 K media. In the rst 3 days, the pH value and ORP increased
rapidly due to iron(II) oxidation by bacteria (Fig. 8A and B), but in the
following 9 days, the pH and total iron values decreased due to the
jarosite-family precipitation (Eq. (1)). Fig. 8C and D together with the
XRDanalysis (Fig. 9), further conrmthat the precipitates are jarosite.
Over time, the total soluble copper and nickel concentrations
slowly decrease (Fig. 8E and F) together with decreasing total iron and
potassiumconcentrations. However, it is not clear whether the copper
and nickel ions are incorporated into sites of the jarosite structure or
encapsulated within jarosite aggregate or absorbed onto the jarosite
surface (Acero et al., 2006; Grfe et al., 2008; van Hille et al., 2010;
Welch et al., 2007, 2008).
Daoud and Karamanev (2006) reported that the optimal pH and
temperature combination giving the least amount of jarosite was pH
1.61.7 at a temperature of 35 C. These conditions yielded very
appealing results, giving good oxidation rates by A. ferrooxidans with
little jarosite precipitation, which therefore minimises copper and
nickel precipitation.
4. Conclusions
The bioleaching of a low-grade nickel, copper, cobalt bearing
sulde ore was technically feasible through 68 days ask leaching and
139 days column leaching after acid pre-leaching to react with basic
magnesium and calcium minerals. The results indicated that nickel
and cobalt had similar leaching behavior and were more easily
leached than copper. The presence of potassium, sodium and iron(III)
ions in the leaching system led to the formation of jarosite within the
ore bed which incorporated nickel and copper ions into the jarosite
precipitate, thereby diminishing the overall recovery of metal value.
Discrepancies between the magnesium leaching results, residue
analysis and XRD analysis suggest that Mg
2+
is preferentially leached
from gangue minerals and then re-deposited into the remaining
silicate skeleton.
Acknowledgements
This work was supported by the High-tech Research and
Development Program of China (No. 2007AA060902) and the
National Basic Research Program of China (No. 2010CB630905).
References
Acero, P., Ayora, C., Torrent, C., Nieto, J.M., 2006. The behavior of trace elements during
schwertmannite precipitation and subsequent transformation into goethite and
jarosite. Geochim. Cosmochim. Acta 70, 41304139.
Brierley, J.A., Brierley, C.L., 2001. Present and future commercial applications of
biohydrometallurgy. Hydrometallurgy 59, 233239.
Cameron, R.A., Lastra, R., Mortazavi, S., Bedard, P.L., Morin, L., Gould, W.D., Kennedy, K.J.,
2009. Bioleaching of a low-grade ultramac nickel sulphide ore in stirred-tank
reactors at elevated pH. Hydrometallurgy 97, 213220.
Daoud, J., Karamanev, D., 2006. Formation of jarosite during Fe
2+
oxidation by
Acidithiobacillus ferrooxidans. Miner. Eng. 19, 960967.
Ehrlich, H.L., 2001. Past, present and future of biohydrometallurgy. Hydrometallurgy
59, 127134.
Grfe, M., Beattie, D.A., Smith, E., Skinner, W.M., Singh, B., 2008. Copper and arsenate co-
sorption at the mineralwater interfaces of goethite and jarosite. J. Colloid Interface
Sci. 322, 399413.
Hiroyoshi, N., Miki, H., Hirajima, T., Tsunekawa, M., 2001. Enhancement of chalcopyrite
leaching by ferrous ions in acidic ferric sulfate solutions. Hydrometallurgy 60,
185197.
Klauber, C., 2008. A critical review of the surface chemistry of acidic ferric sulphate
dissolution of chalcopyrite with regards to hindered dissolution. Int. J. Miner.
Process. 86, 117.
Maley, M., van Bronswijk, W., Watling, H.R., 2009a. Leaching of a low-grade, copper
nickel sulde ore 2. Impact of aeration and pH on Cu recovery during abiotic
leaching. Hydrometallurgy 98, 6672.
Maley, M., van Bronswijk, W., Watling, H.R., 2009b. Leaching of a low-grade, copper
nickel sulde ore. 3. Interactions of Cu with selected sulde minerals. Hydromet-
allurgy 98, 7380.
Qin, W.Q., Zhen, S.J., Yan, Z.Q., Campbell, M., Wang, J., Liu, K., Zhang, Y.S., 2009. Heap
bioleaching of a low-grade nickel-bearing sulde ore containing high levels of
magnesium as olivine, chlorite and antigorite. Hydrometallurgy 98, 5865.
Fig. 9. XRD patterns of the precipitate.
36 C. Yang et al. / Hydrometallurgy 106 (2011) 3237
Santos, L.R.G., Barbosa, A.F., Souza, A.D., Leo, V.A., 2006. Bioleaching of a complex
nickeliron concentrate by mesophile bacteria. Miner. Eng. 19, 12511258.
van Hille, R.P., van Zyl, A.W., Spurr, N.R.L., Harrison, S.T.L., 2010. Investigating heap
bioleaching: effect of feed iron concentration on bioleaching performance. Miner.
Eng. 23, 518525.
Watling, H.R., 2006. The bioleaching of sulphide minerals with emphasis on copper
sulphides a review. Hydrometallurgy 84, 81108.
Watling, H.R., 2008. The bioleaching of nickelcopper suldes. Hydrometallurgy 91,
7088.
Watling, H.R., Elliot, A.D., Maley, M., van Bronswijk, W., Hunter, C., 2009. Leaching of a
low-grade, coppernickel sulde ore. 1. Key parameters impacting on Cu recovery
during column bioleaching. Hydrometallurgy 97, 204212.
Welch, S.A., Christy, A.G., Kirste, D., Beavis, S.G., Beavis, F., 2007. Jarosite dissolution I
trace cation ux in acid sulfate soils. Chem. Geol. 245, 183197.
Welch, S.A., Kirste, D., Christy, A.G., Beavis, F.R., Beavis, S.G., 2008. Jarosite dissolution II
reaction kinetics, stoichiometry and acid ux. Chem. Geol. 254, 7386.
Yang, X.J., Zhang, X.X., Fan, Y.L., Li, H.Y., 2008. The leaching of pentlandite by
Acidithiobacillus ferrooxidans with a biologicalchemical process. Biochem. Eng. J.
42, 166171.
Zhen, S.J., Yan, Z.Q., Zhang, Y.S., Wang, J., Campbell, M., Qin, W.Q., 2009. Column
bioleaching of a lowgrade nickel-bearing sulde ore containing high magnesiumas
olivine, chlorite and antigorite. Hydrometallurgy 96, 337341.
37 C. Yang et al. / Hydrometallurgy 106 (2011) 3237