Minerals Engineering 24 (2011) 1188–1197

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Minerals Engineering
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High pressure acid leaching of a refractory lateritic nickel ore

Sß . Kaya, Y.A. Topkaya ⇑
Department of Metallurgical and Materials Engineering, Middle East Technical University (METU), 06531 Ankara, Turkey

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

Article history: This paper describes the experimental findings of the extraction of nickel and cobalt by high pressure acid
Available online 2 June 2011 leaching (HPAL) of a refractory limonitic nickel laterite ore from the Gördes region of Manisa in Turkey.
By optimizing the basic HPAL process parameters: leaching at 255 °C with 0.30 sulfuric acid to ore weight
Keywords: ratio with a particle size of 100% 850l for 1 h of leaching, it was found that 87.3% of nickel and 88.8% of
Hydrometallurgy cobalt present in the ore could be extracted into the pregnant leach solution (PLS). However, these extrac-
Laterite tion results were found to be relatively low compared with other similar studies. In order to understand
Leaching
the possible reasons for this relatively lower extraction, further investigations have shown that together
Nickel
Cobalt
with a problem related to the kinetics of the dissolution reactions, a persistent acid resistant refractory
mineral present in this sample also limited the leaching process. Attempts were made with different
additives to solve this problem. The effects of chemical additives such as HCl, Na2SO4, FeSO4, Cu+ and sul-
fur were tested and the effect of each addition on the degree of extraction of nickel and cobalt was
determined.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction sources in 1950. However, this ratio increased up to 42% in 2003,

Ferrous and non-ferrous alloying industries, petro-chemical
works, aerospace applications, nickel based catalysts and battery
production, military applications, coinage and coating practices
are some of the most common areas of nickel utilization in indus-
try which lead to a high demand for this metal throughout the
world. When the trends in this demand are investigated from
1950 to 2009, it is clearly seen that the need for nickel has risen
from below 200 ktpa to over 1300 ktpa, and this dramatic increase
is growing at an average rate of 4% per annum (INSG, 2010;
McDonald and Whittington, 2008).
Until recently this high demand for nickel has been supplied
mostly from the sulfide based nickel reserves; however, this trend
is changing towards the more abundant lateritic type nickel re-
sources, which account for about 70% of the world nickel reserves.
This is due to technical, economic and environmental reasons
(Moskalyk and Alfantazi, 2002). To illustrate, apart from the pre-
dominance of lateritic deposits over sulfides, their easier mining
by simple open-pit mining methods, unlike the extremely expen-
sive underground mining of sulfides, makes their utilization more
preferable. Finally, significant amounts of cobalt contained in late-
rites makes them more competitive in the nickel industry.
According to annual data of nickel production from sulfides and
laterites, less than 10% of nickel was produced from lateritic
⇑ Corresponding author. Tel.: +90 312 2102538; fax: +90 312 2102518.
E-mail address: topkaya@metu.edu.tr (Y.A. Topkaya).
and is expected to rise to 51% by 2012 (Dalvi et al., 2004; Sudol,
2005). In the light of this historical data and the changing trend to-
wards the lateritic type nickel deposits; technically, economically
and environmentally feasible processing techniques are steadily
gaining more and more importance.
Understanding the history of formation of a mineral deposit is
critical in establishing a possible processing route for that value.
Typically, the lateritic nickel ores vary widely in their chemical
composition and mineralogical structure when their history of for-
mation is considered. Depending on their lateritization history, dif-
ferent lateritic profiles may form on a single deposit having
different mineralogical formations and distribution. The zones in
a typical lateritic ore are classified and named as limonitic, transi-
tion (nontronitic) or saprolitic according to their mineral content
(Canterford, 1978). Naturally, the response of a specific ore to met-
allurgical treatment depends on the chemical composition and
mineralogical characteristics of that ore. Three metallurgical
extraction processes are currently being applied; pyrometallurgi-
cal, hydrometallurgical and the ‘Caron Process’. Roughly speaking,
the energy intensive pyrometallurgical method generally uses the
ferro-nickel production route or matte smelting process in order
to recover the nickel mostly contained in the saprolitic part of
the lateritic ore. However, the hydrometallurgical methods gener-
ally exploit the highly selective dissolution features of both nickel
and cobalt in the limonitic and nontronitic parts of the laterite ore
in sulfuric acid media. The Caron Process uses the pyrometallurgi-
cal and hydrometallurgical methods together in order to obtain the
metallic values (Moyes, 2010).

0892-6875/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2011.05.004
 Sß. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 1188–1197
In this study, the response of limonitic nickel laterite ore from
the Manisa/Gördes region of Turkey to sulfuric acid was investi-
gated under high temperature and high pressure hydrometallurgi-
cal techniques, and the most cost effective process parameters
such as leaching temperature and duration, sulfuric acid/ore ratio
and particle size were examined in order to add value to this de-
posit. Moreover, attempts to solve the problems experienced due
to low nickel and cobalt extraction were made by using suitable
chemical additives.
2. Experimental
2.1. Material characterization
In order to determine the general characteristics of the lateritic
sample, physical, chemical and mineralogical characterization
steps were performed. For this purpose, the ore was sampled by
coning and quartering. Initially bulk and solid density measure-
ments were conducted on the representative limonitic nickel later-
ite ore sample. Bulk density measurements were done according to
the ratio of ore weight to ore volume, without joggle. On the other
hand, the solid density of the sample was determined by a bottle
pycnometer. After the density measurements, the moisture con-
tent determination of the as-received ore was determined by
weighing and drying a representative limonitic sample in a drying
oven at 105 °C until a constant dry mass was attained.
The limonitic sample was dried and ground to 100% 38l and
analyzed chemically by the Inductively Coupled Plasma (ICP)
method. Chemical analyses of the pregnant leach solutions after
the leaching experiments were conducted using AAS, while the
dried and ground solid leach residues were mainly analyzed by
using a Niton X-Met 820 X-ray Fluorescence (XRF) analyzer and
by Atomic Absorption Spectroscopy (AAS) together. In order to
determine the types of minerals present in the ore samples, a Rig-
aku D/MAX2200/PC model X-ray Diffractometer with a Cu-Ka X-
ray tube working under 40 kV and 40 mA was used during the min-
eralogical analysis of the limonitic nickel laterite sample. Also the
mineralogical analysis results were verified by the aid of a Nova
Nanosem 430 Scanning Electron Microscope (SEM). Investigation
of the thermal behavior of the minerals present in the limonitic
nickel laterite sample was the last step in the mineralogical char-
acterization study. For this purpose, the ore samples were dried
and ground to a size of 100% 38l and subjected to Differential
Thermal Analysis (DTA) and Thermo Gravimetric Analysis (TGA)
by a Simultaneous Setaram DTA and TGA device. These analyses
were conducted at a heating rate of 10 °C/min within the temper-
ature range of 35–1000 °C in air in an alumina crucible.
2.2. Experimental set-up and procedure
High pressure acid leaching experiments were conducted in a
Parr-4532 model, 2 l, titanium grade-4 autoclave which was
equipped with automatic heating and cooling units, and a magnet-
ically driven stirring system. To test the ore sample, a slurry of
150 g of limonitic nickel laterite ore was prepared with deionized
water according to a predetermined solid/liquid ratio of 30 wt.%
solids. After the slurry was prepared in the autoclave, technical
grade sulfuric acid (96–98 wt.%) was added and the lid of the auto-
clave was closed carefully in order to prevent any leakage during
the high pressure leaching operation. At this point, any analytical
reagent (AR) of high purity, to test its effect on leaching, was also
added before sealing the autoclave, and the system was allowed
to heat up to the desired set-point temperature. The start of the
reaction, defined as zero time, was defined as when the reactor
temperature reached the set-point and the reaction was left to pro-
1189
ceed until the target leaching duration was attained. After the re-
quired leaching duration was completed, the system was allowed
to cool to room temperature for approximately 1 h, by means of
water flowing through a titanium cooling coil. In order to perform
solid/liquid separation after leaching, the resultant slurry was fil-
tered by the aid of a vacuum pump and Whatman grade-40 filter
paper on a Buchner funnel. After loading the pregnant leach solu-
tion with leached metal cations, the solid that remained in the
Buchner funnel was washed well in order to completely remove
the pregnant leach solution. The resultant leach residue was then
dried overnight at 105 °C ready for chemical analysis. Leach resi-
dues and pregnant leach solutions obtained were analyzed chemi-
cally as explained previously. Meanwhile, the resultant pregnant
leach solutions were also analyzed for residual acid. Oxidation–
reduction potential (ORP) and density measurements were also
performed.
During the residual free acid determinations, 0.2 M sodium
hydroxide (NaOH) solution was used to neutralize the free acid
which remained in the pregnant leach solution. In order to sup-
press the interfering effect of some ions during titration, 280 g/L
di-potassium oxalate monohydrate (K2C2O4H2O) solution was
used as a chelating agent during the titration. At the same time
the pH meter was calibrated to pH 7.0 by a special buffer solution.
The titration procedure was as follows; 20 cc of 280 g/L di-potas-
sium oxalate monohydrate solution was diluted with 5 cc of deion-
ized water and the pH of this mixture was measured with the pre-
calibrated pH meter. Then, 5 cc of pregnant leach solution was
added into this mixture and the solution was homogenized by
the help of a magnetic stirrer. Finally, this solution was titrated
with 0.2 M sodium hydroxide solution to the initial pH level. Then,
from the amount of sodium hydroxide consumed, the residual acid
in the pregnant leach solution was determined. For the oxidation–
reduction potential measurements, a Pt-Ag/AgCl electrode (satu-
rated with KCl) was used and the measured values were reported
according to the Pt-Ag/AgCl reference electrode.
2.3. Experimental parameters studied
Throughout the experiments various process parameters were
studied. Initially, the experiments began with the investigation of
the effect of leaching temperature on nickel and cobalt extractions.
Then the effects of leaching duration, sulfuric acid/ore ratio (w/w),
and particle size were examined. In addition to these basic process
parameters, the effect of prior heat treatment and the effects of
various additives were studied and the list of process parameters
investigated is summarized in Table 1.
3. Results and discussion
3.1. Characterization results
The bulk and solid densities of the representative Gördes limo-
nitic nickel laterite ore were found to be 1.04 and 3.26 g/cm3,
respectively. According to the moisture content measurement, it
was calculated that the sample contained 23.47% of physically held
water. This suggested that it would be a very energy intensive pro-
cess just in terms of moisture content if a pyrometallurgical pro-
cessing route was selected for the treatment of this ore. Chemical
analysis of the limonitic nickel laterite sample is given in Table 2.
By combining the chemical analysis results together with XRD
and DTA/TGA findings, it was found that the limonitic sample con-
tained high amounts of quartz (SiO2), hematite (Fe2O3), and goe-
thite (FeOOH) minerals as well as the mineral smectite, having
the idealized mineral formula of (Na0.3Fe2(Si,Al)4O10(OH)2nH2O).
In order to verify the previous analyses, SEM studies on the laterite
1190 Sß. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 1188–1197

Table 1
List of process parameters studied during HPAL experiments.

Experiments Fixed parameters Studied parameters Additive

Leaching temp. (°C) 60 min, 850l, 0.3 acid/ore ratio 245, 250, 255, 260, 265, 270 No addition
Leaching duration (min) 255 °C, 850l, 0.3 acid/ore ratio 0, 60, 90, 180, 360 No addition
Sulfuric acid/ore ratio (w/w) 255 °C, 60 min, 850l 0.275, 0.300, 0.325, 0.350 No addition
Particle size (l) 255 °C, 60 min, 0.3 acid/ore ratio 38, 425, 850, 1400, 2000 No addition
Prior heat treatment 255 °C, 60 min, 850l, 0.3 acid/ore ratio Limonite heat treated at 350 °C No addition
HCl addition (kg/ton dry ore) 255 °C, 60 min, 850l, 0.3 acid/ore ratio 33.33, 66.67 HCl (37 wt.%)(AR)
Na2SO4 addition (gpl) 255 °C, 60 min, 850l, 0.3 acid/ore ratio 12.5, 25.0 Na2SO4 (AR)
FeSO4 addition (gpl) 255 °C, 60 min, 850l, 0.3 acid/ore ratio 14.3, 28.6 FeSO4 (AR)
Cu+ addition (gpl) 255 °C, 60 min, 850l, 0.3 acid/ore ratio 1, 2, 3 Cu2O (AR)
Sulfur addition (kg/ton dry ore) 255 °C, 60 min, 850l, 0.3 acid/ore ratio 1, 2, 3 S (AR)

Table 2
Chemical analysis of limonitic nickel laterite sample.

Constituent Fe Ni Co Cr2O3 MnO As Al2O3

Content (wt.%) 28.70 1.28 0.083 1.99 0.59 0.68 5.83
Constituent SiO2 MgO CaO K2O TiO2 CuO S
Content (wt.%) 28.8 2.26 1.27 0.12 0.13 0.04 0.43

sample indicated that the nickel was mainly present in the crystal
lattices of the minerals goethite (FeOOH), hematite (Fe2O3), ser-
pentine ((Mg, Fe)3Si2O5(OH)4) and smectite (Na0.3Fe2(Si,
Al)4O10(OH)2nH2O). Cobalt, however, was mainly present in the
crystal structure of the mineral asbolane having the idealized for-
mula of (Co, Ni)1y(Mn4+O2)2x(OH)22y+2xnH2O. Similar results
were reported by Büyükakinci for Gördes limonites in a previous
study (Büyükakinci and Topkaya, 2009).
3.2. Extraction results
The effect of temperature on the degree of nickel and cobalt
extractions was initially investigated and then the effects of leach-
ing duration, sulfuric acid/ore ratio and particle size were tested
separately in order to obtain the optimum nickel and cobalt extrac-
tions with the most cost effective process parameters. The overall
results of these experiments are discussed in the following
sections.
3.2.1. Effect of temperature
According to the extraction behavior of nickel with increasing
temperature, it was noticed that there was an increasing trend in
the extraction of nickel with the process parameters given in Ta-
ble 1. However, beyond 265 °C this increasing trend seemed to dis-
appear with further increase in temperature. Georgiou and
Papangelakis in 1988 reported similar behavior between the tem-
peratures of 230 and 270 °C. A study conducted by Chou et al. in
1977 showed that leaching up to 275 °C increases nickel yield,
but leaching conducted at 300 °C leads to a decrease in the degree
of nickel extraction. The cause of this behavior was reported in the
literature by indicating that in excess of 270 °C, the possibility of
nickel–magnesium sulfate (Mg, Ni)SO4H2O co-precipitation in-
creases severely due to the lower solubility of magnesium at higher
temperatures (Whittington and Muir, 2000). This precipitation is
generally accompanied with nickel and cobalt losses to the precip-
itate. It is also reported that as the temperature of pressure leach-
ing goes beyond 280 °C, the possibility of Fe(OH)SO4 (basic iron
sulfate) and Al(OH)SO4 (basic aluminum sulfate) formations in-
crease, with accompanied acid losses which are not desirable dur-
ing the pressure acid leaching process.
When the extraction behavior of cobalt is considered, it is seen
from Fig. 1 that cobalt is not as sensitive to increasing process tem-
peratures as nickel and its intensity decreases beyond 265 °C.
When this result is compared with the reported data in the litera-
ture, it is evident that almost 80% of the cobalt is rapidly taken into
the leach solution, possibly due to the presence of cobalt in the
readily-leached manganese mineral ((Co, Ni)1y(MnO2)2x(OH)
22y+2xn(H2O)), asbolane (Georgiou and Papangelakis, 1998).
Georgiou and Papangelakis (2009) showed that treating lateritic
ore between the temperatures of 230 and 270 °C had essentially
no effect upon the rate of cobalt extraction. Cobalt was leached
readily in the first 10 to 20 min of leaching, and its dissolution rate
slowed down thereafter. Chou et al. also emphasized the high ini-
tial rate of cobalt extraction. Therefore, the extraction behavior of
cobalt is generally reported to be less affected by increasing tem-
perature (Chou et al., 1977). Other than nickel and cobalt extrac-
tions, it is interesting to note that as a result of increasing leach
temperatures, remarkable changes in the extractions of iron, alu-
minum and, to a limited extent, chromium were observed. This is
as a result of temperature rise in the pressure leach process, the
precipitation rates of iron and aluminum increasing in parallel
with temperature with inverse solubility of hematite and alunite
precipitates. This has also been supported by Georgiou and Papan-
gelakis (1998) who report that the increasing leaching tempera-
tures favor increasing nickel and cobalt concentration ratios ‘[(Ni
or Co)/(Fe + Al)]’ as a result of the inverse solubility of hematite
and alunite in the pregnant leach solution.
The pressure acid leach experiments conducted at different
leaching temperatures showed that more nickel and cobalt could
be extracted into the pregnant leach liquor in just 1 h of leaching
at higher leaching temperatures in the autoclave. However, since
higher leaching temperatures mean higher initial investment and
operational costs, the optimal process temperature should be se-
lected whether or not the extra nickel and cobalt credit compen-
sates for the former production expenses. Therefore, for the rest
of the tests a leaching temperature of 255 °C was selected, and
higher nickel and cobalt extractions were obtained by optimizing
the other process parameters effectively.
3.2.2. Effect of leaching duration
The data obtained from leaching duration experiments showed
that the nickel and cobalt behaved similarly when the leaching dura-
tion was prolonged. It is shown in Fig. 2 that from the starting point,
up to 180 min of leaching duration, the nickel and cobalt extractions
increased as intended. However, although increasing nickel extrac-
tion continued from 180 min up to 360 min of leaching duration, this
 Sß. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 1188–1197 1191

Fig. 1. Effect of temperature upon degree of nickel and cobalt extractions.

Fig. 2. Effect of leaching duration upon degree of nickel and cobalt extractions.

trend resulted in an extraction value of around 95%, which sug-
gested that further increase in leaching duration would be of limited
use in increasing the degree of nickel and cobalt extractions. Thus, it
was thought that, together with a problem related with the kinetics
of the chemical reactions, a persistent leaching behavior limited the
process. In other words, these results suggested that there may be
very acid resistant refractory minerals present in this limonitic nick-
el laterite sample which prevented the leaching of nickel and cobalt
from the lattice of these minerals. When the mineralogical charac-
terization step is referred to again, the presence of hematite within
the limonitic sample appeared to be the possible reason for this
extraction behavior. This difficulty in the leaching behavior of hema-
tite was also reported by Kui Lui et al. who stated that leaching be-
comes more difficult among the nickel containing minerals in the
following order; Lizardite > goethite > maghemite > magnetite >
hematite > chromite  ringwoodite (Liu et al., 2009, 2010). There-
fore, this incomplete extraction of nickel stemming from the primary
hematite was examined throughout this study to see whether it is
possible to overcome this problem.
Apart from nickel and cobalt, marked decreases in the extrac-
tion of iron, aluminum and chromium were observed after pro-
longed leaching, due to increased precipitation reactions favored
by extended leaching.
The pressure acid leach experiments conducted at different
leaching durations showed that more nickel and cobalt could be
extracted into the pregnant leach liquor at 255 °C by increasing
the duration of leaching in the autoclave. However, as in the case
of temperature, there was a limit to this increase, possibly due to
the difficulty in leaching refractory minerals suspected to be
mainly hematite. Therefore, prolonged leaching may be helpful in
increasing the desired level of nickel and cobalt extractions. How-
ever, since prolonged leaching decreases the overall capacity of the
plant and thus increases the costs, the optimal leaching duration
should be selected whether the extra nickel and cobalt credits
compensate for the former production expenses. Therefore, for
the remaining tests just 60 min of leaching was selected, and high-
er nickel and cobalt extractions were obtained by suitable addi-
tives and optimizing other process parameters more effectively.
3.2.3. Effect of sulfuric acid/ore ratio
While examining the results of the effect of sulfuric acid con-
centration on nickel and cobalt extractions, the amount of residual
acid in the pregnant leach liquor after leaching is also of impor-
tance. It has been reported from other research that for high nickel
and cobalt extractions sufficient free acid should remain in the
pregnant liquor in order to maintain the stability of dissolved spe-
cies and prevent undesired nickel and cobalt losses (Whittington
1192 Sß. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 1188–1197
Table 3
Free acidity with respect to sulfuric acid concentration.
Acid amount (kg/ton dry ore) 275 300 325
Free acidity (gpl) 39.2 41.2 44.5
and Muir, 2000). However, while various researchers have reported
the positive effect of residual acidity in the pregnant leach liquor,
there is also a limiting value to the amount of this residual acid
present in the solution. During the solution purification and metal
recovery steps this residual acid should be neutralized somehow,
CaCO3 often being the most suitable reactant. Therefore, the
amount of residual acid becomes directly related with the con-
sumption of basic reagent and, in turn, it determines the viability
of the process economics in terms of the rising cost of
consumables.
Practical data from various processing plants help to clarify the
above. Testwork on Ramu ore at 250 °C suggests that 30 g/L of
residual acid was optimal for sufficient nickel and cobalt extrac-
tion. Similarly, 30–40 g/L and 40 g/L of free acid were necessary
for Bulong and Murrin Murrin ores respectively (Whittington and
Muir, 2000). Therefore, for Gördes limonitic nickel laterite ore
40 g/L residual sulfuric acid was targeted for satisfactory results.
The actually measured residual acid values are given in Table 3.
Therefore, when the nickel and cobalt extraction results in Fig. 3
and the residual acid measurement values in Table 3 are evaluated
together, 300 kg of sulfuric acid per ton of dry limonitic nickel lat-
erite ore seemed to be the most appropriate selection among the
other alternatives, since the extra acid addition did not satisfy
the required increase in extraction values, in fact increasing the
acid and base consumptions pointlessly. In addition to the above,
the leach residue samples were analyzed by XRF and the sulfur
contents of the leach residue samples were also determined.
According to the obtained results, the sample leached with
300 kg of sulfuric acid was found to contain 1.89% sulfur, whereas
the sample leached with 350 kg of sulfuric acid contained 2.25%
sulfur, which showed that the increased sulfuric acid addition also
increased the sulfur losses in the leach residue needlessly. There-
fore, this finding also showed that the addition of 300 kg of sulfuric
acid would give the best result when the overall considerations
were taken into account.
3.2.4. Effect of particle size
The results of particle size experiments given in Fig. 4 show that
the responses of nickel and cobalt extractions were positive when
finer particles were fed into the autoclave. As seen from Fig. 4, the
Fig. 3. Effect of sulfuric acid concentration upon degree of nickel and cobalt extractions.
particle size became more important in terms of nickel extraction
when the feed size was decreased below 425 lm, and further
350 reduction in the particle size seemed to give more effective results.
44.9 Similarly, the extraction of cobalt was increased in such a way that
as the particle size was reduced from 2000 lm to 425 lm, there
was an almost linear increase in the cobalt extraction. However,
this trend became steeper and led to an exponential increase in
the extraction of cobalt into the pregnant leach solution when
the size was reduced from 425 lm to 38 lm. This was due to
the effect of increased specific surface area of refractory minerals,
such as hematite and quartz, containing small fractions of nickel
and cobalt, which was verified by scanning electron microscopy
of the limonitic nickel laterite sample.
In addition to changes in nickel and cobalt extractions, Chou
et al. also showed that excessive grinding of the ore created extra
surface area, which in turn provided additional nucleation sites
for iron and aluminum precipitation. Therefore, the impurity con-
centration of pregnant leach solution decreased as a result of over
grinding. Similar trends in the extractions of iron and aluminum
were observed during the leaching experiments. Extractions of iron
and aluminum tended to decrease as a result of reduction in the
feed size which was in agreement with the statement made by
Chou et al. in 1977.
When the overall results of the particle size experiments are
considered, it can be said that grinding was beneficial in terms of
higher nickel and cobalt extractions and cleaner PLS characteristics
for further downstream processing. However, this is limited by
technical and economical reasons, as grinding becomes more diffi-
cult and energy consuming when the particle size is reduced exces-
sively. The rheology of the pulp fed into the autoclave is also a very
important consideration which should be kept in mind during the
final decision making process. Since the rheological properties and
ease of stirring in the autoclave are a function of the feed size it be-
comes very difficult to provide effective stirring when very coarse
particle sized feed is fed into the system. Therefore, in the light of
these considerations, the limonitic samples ground to 100%
850 lm were used in the remaining experiments. By using the
above mentioned process parameters, 87.3% of nickel and 88.8%
of cobalt present in the ore were extracted into the pregnant leach
solution and the solution contained 4677 ppm Ni, 266 ppm Co,
2620 ppm Al, 1364 ppm Mn, 4754 ppm Mg, 98 ppm As, 123 ppm
Cr, and 2296 ppm Fe.
3.2.5. Effect of prior heat treatment
Previously the effects of temperature, leaching duration, acid/
ore ratio, and particle size on nickel and cobalt extraction results
 Sß. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 1188–1197 1193

Fig. 4. Effect of particle size upon degree of nickel and cobalt extractions.

have been described and further tests were then performed at
255 °C with 0.30 acid to ore weight ratio, with a particle size of
100% 850 lm for 1 h duration. When these optimum parameters
were used and the leach residue sample was analyzed by XRD, it
was found (Fig. 5) that there were no considerable changes in
the quartz peaks after leaching, showing that quartz had remained
almost intact during the leaching operation. However, the charac-
teristic peaks of smectite and goethite within the limonitic nickel
laterite ore had disappeared, indicating that these minerals were
leached out from the original ore sample. After leaching, the inten-
sity of the characteristic hematite peaks increased in the XRD pat-
tern of the leach residue, verifying that iron had tended to
precipitate in the form of secondary hematite. Therefore, it is likely
that nickel present within the primary hematite mineral may be
the main reason for the low extraction results experienced with
these limonitic nickel laterite samples. In order to verify this, the
limonitic sample was heated to 350 °C in order to transform all
the goethite to hematite. The selection of heat treatment tempera-
ture was based on the thermal analysis result for the limonitic
sample given in Fig. 6. As clearly seen in Fig. 6, at about 270 °C goe-
thite present in the limonitic sample has transformed into hema-
tite according to the dehydroxylation reaction of goethite.
However, in order to be on the safe side, the heat treatment tem-
perature was chosen as 350 °C. The nickel and cobalt extraction re-
sults obtained after pressure leaching for the heat treated limonitic
ore are given in Fig. 7 together with those of the original ore ob-
tained under the same experimental conditions, for comparison
purposes. It is obvious from Fig. 7 that on transforming the goe-
thite to hematite, there was a tremendous decrease in the extrac-
tion of nickel and cobalt which means that it is more difficult to
leach and obtain nickel from hematite compared with goethite.
Moreover, a scanning electron microscopy study on the leach res-

Fig. 5. XRD result comparison of limonite ore and its leach residue.
1194 Sß. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 1188–1197
Fig. 6. DTA/TGA analysis results of limonitic sample.
Fig. 7. Effect of prior heat treatment upon degree of nickel and cobalt extractions.
idue has also shown that the losses of nickel were mainly related to
the iron minerals. Therefore, in the following stages, it was at-
tempted to overcome this difficulty by making various changes
to the leaching environment.
3.2.6. Effect of HCl addition
On evaluation of the results of hydrochloric acid addition shown
in Fig. 8, the findings were satisfactory only in terms of increasing
the nickel and cobalt extractions, as the extremely corrosive
behavior of the acidic mixture resulted in damage to the leaching
equipment. As a result of severe acidic attack, some rupture plates
on the autoclave have exploded during acid mixture testing which
led to the termination of further tests. Thus, the overall conclusion
was that HCl together with H2SO4 might be an alternative in order
to enhance the extraction behavior of nickel and cobalt from the
refractory minerals of the limonitic nickel laterite ore. However,
the autoclave should be designed to endure the severe corrosive
leaching conditions.
3.2.7. Effect of Na2SO4 addition
Although some studies report the beneficial effects of Na2SO4
addition, the experimental results of Gördes limonitic nickel later-
ite ore given in Fig. 9 were unsatisfactory due to the observed de-
crease in the degree of nickel and cobalt extractions. However, the
contribution of Na2SO4 in changing the solution impurity concen-
trations and residue mineralogy could not be ignored, as when
the extractions of Fe, Al, Mn, Mg, and Cr in the pregnant leach solu-
tion were considered, a remarkable decrease in their amounts was
observed. The reason for the decrease of these ions is explained by
the increased stability of natroalunite and/or natrojarosite and
their precipitation as a result of sodium ions present in the solution
(Johnson et al., 2005). In addition to the observed decrease in the
concentration of impurity elements, nickel and cobalt may also
substitute into the alunite/jarosite structure during precipitation,
which may be the reason for the observed low nickel and cobalt
extraction values (Whittington and Muir, 2000). Parallel to the for-
mation of natroalunite and/or natrojarosite, the amount of residual
acid was measured and it was seen that the free acid in the solu-
tion continuously decreased from 41.2 gpl to 37.8 and 33.9, respec-
tively as a result of increases in the Na2SO4 concentration. The
decrease in residual acid and the formation of natroalunite and/
or natrojarosite were explained and formulated according to the
chemical reactions given below (Johnson et al., 2005):
3Fe2 ðSO4 Þ3 þ Na2 SO4 þ 12H2 O ! 2NaðFeÞ3 ðSO4 Þ2 ðOHÞ6 þ 6H2 SO4
ð1Þ
3Al2 ðSO4 Þ3 þ Na2 SO4 þ 12H2 O ! 2NaðAlÞ3 ðSO4 Þ2 ðOHÞ6 þ 6H2 SO4
ð2Þ
 Sß. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 1188–1197 1195

Fig. 8. Effect of HCl addition upon degree of nickel and cobalt extractions.

Fig. 9. Effect of Na2SO4 addition upon degree of nickel and cobalt extractions.

According to these reactions and from the residual acid mea-
surements, the presence of sodium ions in the solution affects
the iron and aluminum chemistry and inhibits the regeneration
of sulfuric acid to the solution.
The changes observed in the reaction chemistry and residue
mineralogy also affected the filtration behavior of the leach residue
after pressure leaching. As a result of changes in the precipitation
reactions, the leach residue showed colloidal behavior during fil-
tration which could be explained by the reduction in free acidity
having hydrolyzed the silicic acid to colloidal silica, which in turn
complicated the solid–liquid separation process (Whittington and
Muir, 2000). Therefore, although the addition of Na2SO4 was very
effective for solution purification purposes, it seemed that this
additive would not solve the problem of low nickel and cobalt
extraction results.
3.2.8. Effect of FeSO4 addition
Various researchers have reported the positive effect of the
presence of reducing species in the pregnant leach solution during
pressure acid leaching of lateritic nickel resources. Therefore, in
this part of the study, the effect of divalent iron addition to the
leach solution was investigated in order to enhance the nickel
and cobalt extraction values. As stated in the literature, the addi-
tion of divalent iron led to a drastic fall in the reduction potential
of the leach solution. To be more specific, the reduction potential of
the pregnant leach solution decreased from 489 mV to 366 and
344 mV, respectively after the FeSO4 additions, and this reducing
solution led to the desired increase in the nickel and cobalt extrac-
tion values, as shown in Fig. 10. This behavior was explained by
Tindall and Muir (1997) as the presence of divalent iron species
facilitates bond breakage and aids iron oxide dissolution via elec-
tron transfer in the leach solution, thus increasing the extraction
of valuable metals from the goethite and hematite matrix. Also re-
lated to the FeSO4 addition is that the amount of iron present in the
leach solution increased due to iron sulfate addition as expected.
Before ferrous ion addition, most of the iron in the PLS was in
the form of ferric ion. However after this addition the amount of
ferrous ion was naturally increased, which is a disadvantage for
downstream processes, as iron present in the ferrous state should
be oxidized to the ferric state during downstream processes, mak-
ing the process more complicated. So apart from the negative effect
of ferrous ions during the downstream solution purification pro-
cesses, this addition was effective in enhancing the extraction
behaviors of nickel and cobalt on changing the solution character-
istics to a more reducing character.
3.2.9. Effect of Cu+ addition
After obtaining somewhat encouraging results from the FeSO4
addition experiments, further tests to evaluate the positive effects
of reducing solution characteristics were attempted with the
1196 Sß. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 1188–1197

Fig. 10. Effect of FeSO4 addition upon degree of nickel and cobalt extractions.

addition of cuprous ions (Cu+) into the leach solution. The catalytic
mechanism of cuprous ions is correlated with the ease of electron
transfer between Cu+ and iron species. According to the proposed
mechanism in the literature, the dissolution of iron species in the
presence of cuprous ions is catalyzed by the following electro-
chemical reaction, while nickel present within the crystal lattice
of iron minerals is predicted to be liberated into the solution (Byer-
ley et al., 1979; Parker and Espenson, 1969);
Fe3þ þ Cuþ ! Fe2þ þ Cu2þ
According to the results shown in Fig. 11, the positive effect
of cuprous ions in extracting the nickel present in the hematite
crystal lattice was similar to that of previous studies performed
by other researchers. In the case of cobalt, previous work has
shown that the extraction of cobalt can be enhanced when the
potential of the solution is adjusted to a more reducing character
(Tindall and Muir, 1997). This was verified by the addition of
reducing ferrous ions into the leach solution. On addition of cu-
prous ions in increasing amounts, the reduction potential of the
solution was lowered from 489 mV to 449, 440, and 410 mV,
respectively. However, the expected enhancement in extraction
behavior of cobalt was not as good as that obtained by ferrous
ion addition. According to Fig. 11, only a slight increase in the
extraction of cobalt was observed when compared to nickel. This
was due to higher ORP values obtained in the case of Cu(I) addi-
tions as a result of the significant variation of FeSO4 to Cu(I) con-
centrations in the liquor.
3.2.10. Effect of S addition
Experimental evidence up to this stage has shown that there is a
close relationship between the electrochemical nature of the leach-
ing solution and the observed nickel and cobalt extractions. To
ð3Þ
confirm this, the same constant test parameters were used as in
the case of ferrous and cuprous ions additions, and the addition
of sulfur to change the reduction potential of the leach solution
was planned in order to facilitate electron transfer in the solution.
For the no-sulfur added experiment the reduction potential was
489 mV. However, on addition of sulfur the reduction potentials
were measured as 373, 349, and 334 mV, respectively with
increasing sulfur content. Thus sulfur seemed to be very effective
in controlling the reduction potential of the leach solution. Accord-
ing to the results given in Fig. 12, almost the same extractions of
nickel and cobalt were observed as in the case of cuprous ion addi-
tion. Slight increases in the extractions of nickel and cobalt were
believed to be the result of more reducing solution characteristics.

Fig. 11. Effect of Cu+ addition upon degree of nickel and cobalt extractions.
 Sß. Kaya, Y.A. Topkaya / Minerals Engineering 24 (2011) 1188–1197
Fig. 12. Effect of S addition upon degree of nickel and cobalt extractions.
4. Conclusions
In this experimental study the basic HPAL process parameters,
such as leaching temperature, leaching duration, sulfuric acid to
ore weight ratio and particle size of a limonitic nickel laterite ore
were studied. The observed enhancement in the degree of nickel
and cobalt extractions with increase in leaching temperature and
duration, together with decreased particle size, have shown that,
together with a problem related to the kinetics of the chemical
reactions, a persistent leaching behavior also limited the process.
On optimizing the basic HPAL process parameters – leaching at
255 °C with 0.30 sulfuric acid to ore weight ratio with a particle
size of 100% 850l for 1 h, it was found that 87.3% of nickel and
88.8% of cobalt present in the ore could be extracted into the preg-
nant leach solution. However, these results were found to be below
the desired values. Therefore, the possible reasons for this behavior
were investigated and the presence of difficult to leach hematite
mineral was found to be the most probable one. Heat treatment
of the limonitic nickel laterite ore prior to leaching has shown that
goethite present in the ore had fully transformed to hematite and
after this transformation a tremendous decrease in the nickel and
cobalt extractions was observed. Therefore, in order to dissolve the
nickel and cobalt present in the difficult to leach hematite mineral
present in the limonitic nickel laterite ore, additions of HCl, ferrous
ions, cuprous ions and sulfur were tried, respectively. The data ob-
tained for the overall extraction with the various additives showed
that the improvement of nickel and cobalt extractions was 3%.
Acknowledgements
The authors would like to express special thanks to META Nikel-
Kobalt A.Sß. both for supplying the limonitic nickel laterite ore sam-
ple of Gördes and for doing the chemical analyses by XRF and AAS.
Also, METU Center Laboratory for DTA-TGA analyses and METU
Metallurgical and Materials as well as Chemical Engineering
Departments for performing XRD and AAS analyses are gratefully
acknowledged.
1197
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