A two-stage thermal upgrading process for

nickeliferous limonitic laterite ores

R. Elliott*, F. Rodrigues, C. A. Pickles and J. Peacey
Sulphide ore deposits are becoming increasingly less viable as a source of nickel, driving recent
interest in the development of nickel laterite deposits. The difficulties with the current methods of
nickel metal production from these oxide ores arise mainly from the inability to produce a con-
centrate analogous to that obtained in the flotation of sulphide ores, resulting in high production
costs. In this work, a two-stage reduction and thermal growth process is proposed for the treatment
of the nickeliferous limonitic laterite ores to produce a ferronickel product, recoverable by magnetic
separation. An initial reduction roast of the ore with 6% coal and 4% sulphur additions at 6008C for
1 h, followed by particle growth for 1 h at 10008C, produced a ferronickel concentrate with a nickel
grade of 4% and a nickel recovery of 93?2%. The impact of particle growth temperature and
retention time at temperature on the ferronickel particle size was also studied. For the control
conditions, typical ferronickel particles produced were 10–20 mm in size. The particle size did not
significantly change at temperatures higher than 12008C or for retention times beyond 60 min.

Les dépôts de minerai sulfuré sont de moins en moins viables comme source de nickel, poussant
l’intérêt récent du développement des dépôts de latérite de nickel. Les difficultés des méthodes
courantes de production du métal nickel à partir de ces minerais d’oxyde viennent principalement
de l’inhabileté à produire un concentré analogue au concentré obtenu par flottation des minerais
sulfurés, ayant pour résultat des coûts élevés de production. Dans ce travail, on propose un
processus à deux étapes de réduction et de croissance thermiques pour le traitement de minerais
de latérite limonitique nickélifère afin d’obtenir un produit de ferronickel, récupérable par sép-
aration magnétique. Un grillage réducteur initial du minerai, avec additions de 6% de charbon et
4% de soufre, à 6008C pendant une heure, suivi par la croissance de particule pendant une heure
à 10008C, a produit un concentré de ferronickel avec une qualité de nickel de 4% et une
récupération de 93?2% du nickel. On a également étudié l’impact de la température de la
croissance de particule et de la durée de rétention à la température sur la taille de particule du
ferronickel. Sous ces conditions de contrôle, les particules typiques de ferronickel produites
avaient une taille de 10 à 20 mm. La taille de particule n’a pas changé de façon significative à des
températures plus élevées que 12008C ou pour des durées de rétention au-delà de 60 min.
Keywords: Nickeliferous limonitic laterite, Reduction, Roasting, Carbothermic, Magnetic separation, Ferronickel

Introduction nickel from the nickeliferous laterite ores is increasing.

As the sulphide ore deposits become economically less
viable as a source of nickel, interest in the recovery of
Robert M. Buchan Department of Mining, Queen’s University, Kingston,
Ont., Canada K7L 3N6
*Corresponding author, email r.elliott@queensu.ca
Nickel oxide bearing laterites are typically found in
tropical or sub-tropical regions and generally consist of
three main layers. The uppermost layer, referred to as
limonite, contains a significant amount of goethite
(FeO?OH) and typically has 0?5–1?7% nickel, 40–60%
iron and a low silica content.1 The bottommost layer of
the laterite deposit is known as saprolite and typically
contains nickel-enriched serpentines and olivines, with

ß 2015 Canadian Institute of Mining, Metallurgy and Petroleum

Published by Maney on behalf of the Institute
Received 09 December 2014; accepted 27 February 2015
DOI 10.1179/1879139515Y.0000000009 Canadian Metallurgical Quarterly 2015 VOL 00 NO 0 1
Elliott et al. Thermal upgrading process for nickeliferous laterite ores
nickel contents in the range of 1?5–3%, as well as lower
iron and higher silica contents, than the limonitic
deposit. These two layers are usually separated by a
transition layer dominated by smectite clays and quartz.
A major advantage of the sulphide ores is the ability
to produce a concentrate (61–5% Ni), before pyr-
ometallurgical processing. Nickel oxide ores are typi-
cally not amenable to beneficiation, because the nickel
oxide is incorporated into the crystal structure. This
results in the current disparity between the abundance of
nickeliferous laterite ores and the fraction of nickel
metal produced from these sources: nickeliferous later-
ites account for 70% of estimated resources, but only
40% of production.2 Conventional methods for proces-
sing nickel laterites typically require a high acid-con-
suming hydrometallurgical step, or an energy intensive
pyrometallurgical process. Limonitic ores are typically
treated by hydrometallurgical processes, in particular
high-pressure acid leaching (HPAL).3,4 The limonitic ore
is processed with sulphuric acid in an autoclave followed
by purification and either electrowinning or hydrogen
reduction of the nickel in solution to produce high purity
nickel. Although several of these processes have been
implemented on an industrial scale, production levels
have not been satisfactory and the operating costs have
been high.3,4 The Caron process is a hybrid pyro/hydro-
process for treating nickeliferous laterites and in par-
ticular the limonitic laterites. The ore is first heated in a
multi-hearth roaster under a reducing environment to
produce ferronickel, then leached with an ammoniacal
solution to produce high purity nickel; recoveries are
typically about 80%.5 Because of the limited nickel
recovery and the high operating costs, the process is not
generally considered economic.6 It is obviously desirable
to develop an alternative method for generating a nickel
concentrate from a limonitic ore.
The selective reduction of nickel oxides by roasting
with carbonaceous reagents to form a high-grade fer-
ronickel product is a particularly attractive option.
By controlling the reducing conditions it should be
possible to achieve reasonable enrichment and high
nickel recoveries while minimizing the reduction of the
iron oxides.7–9 The metallic product can then be recov-
ered by leaching or magnetic separation. Additionally, it
has been shown that sulphidation of the ore at moderate
temperatures allows for the recovery of the nickel by
conventional flotation techniques, although recoveries
are typically low, around 50%.10 Magnetic separation
should allow for selective recovery of the nickel from the
reduced ore, although the presence of magnetite, as well
as the disseminated nature of the nickel, presents a
particular challenge. The magnetite in the reduced ore
will also be recovered with the ferronickel product,
resulting in the production of a diluted concentrate with
a lower effective nickel grade.
An optimal reduction temperature of 600–650uC for
nickel recovery has previously been reported for limo-
nitic laterites by a number of researchers.11–13 At tem-
peratures lower than the optimum, the degree of
selective reduction was high, while at higher tempera-
tures, the grade was lower because of the increased iron.7
2 Canadian Metallurgical Quarterly 2015 VOL 00 NO
It has also been shown that the addition of sulphur to
the ore allows for the formation of a liquid nickel–iron–
sulphide phase, which should promote agglomeration of
the ferronickel particles and also improve the overall
recovery.11,13–16 Several studies have explored this
option primarily for the saprolitic ores. A variety of
reducing conditions and chemical additives have been
used to increase the nickel recovery and the nickel grade
in the ferronickel alloy. Zhu et al. treated a nickel laterite
(1?42% Ni, 23?16% Fe) at 1100uC with 6% calcium sul-
fate and 5% coal and reported a nickel grade of 6% and a
nickel recovery of 92%.17 Li et al. reduced a laterite
(1?91% Ni, 22?10% Fe) at 1100uC with 20% Na2SO4 and
achieved a nickel grade of 9?5% and a recovery of 83%.18
Jiang et al. treated a nickel laterite (1?49% Ni, 34?69%
Fe) at 1200uC with 10% Na2SO4 and 2% coal, and
reported a nickel grade of 9?9% and a recovery of 91%.19
In these studies, concentrates with nickel grades com-
parable to those in conventional flotation methods for
sulphide ores have been achieved with reasonable
recoveries. However, they typically require high ad-
ditions of the sulphur-containing compounds and elev-
ated reduction temperatures.
Some works have also been conducted on the limonitic
ores, demonstrating significant improvements in nickel
recovery with the addition of sulphur bearing species.
Valix and Cheung achieved 81% nickel recovery with a
5% sulphur addition at a reduction temperature of 600uC,
compared to 29% without sulphur.20 S and Good
reported a 92% nickel recovery with the addition of 1?2%
FeS2 at a reduction temperature of 700uC, compared to
63% without the addition of FeS2.15 In both studies, the
grade of the ferronickel was not reported.
In the present study, the objective was to develop a
method for producing a ferronickel concentrate using
milder temperatures (<1000uC) and moderate sulphur-
containing additions (<10%), while still achieving suit-
able nickel grades and recoveries. A two-stage reduction
and thermal particle growth process is proposed for the
treatment of the nickeliferous limonitic laterites. First, a
thermodynamic model is developed to determine the
optimum conditions for the reduction roast. Second,
experiments are conducted in which the ore is reacted
with coal and elemental sulphur at 600uC to produce a
high nickel-containing Fe–Ni–S phase. Finally, the
reduced product is thermally treated at 1000uC to form a
semi-liquid Fe–Ni–S phase, which facilitates the
agglomeration of the ferronickel particles. Provided that
the majority of the reductant was consumed during the
first reduction stage, only particle growth would be
expected at the higher temperature. In this way, both
high grade and relatively large ferronickel particles
could be obtained and then be effectively concentrated.
Experimental
Raw materials
The ore used in this study was provided by the Ivory
Coast operations of Xstrata. Table 1 gives the ore
composition, which was determined by inductively
coupled plasma mass spectrometry (ICP-MS) analysis.
0

Table 1 Chemical analysis of the as-received limonitic ore
(dry basis)
Component Ni Co Fe Si Mg Al
Wt-% 1?38 0?35 45?70 2?15 0?22 2?92
Based on the X-ray diffraction (XRD) analysis, which
shows goethite as the only identifiable mineral present,
the approximate mineralogical composition given in
Table 2 was estimated. Given the relatively low silica
and high iron contents, the ore is considered to be
limonitic.
Bituminous coal was used as the reductant, and the
composition of the coal sample used is given in Table 3.
Reagent grade elemental sulphur was used for all the
sulphur additions.
Thermogravimetric analysis
Thermogravimetric analysis (TGA) was performed on a
range of sample compositions using a Netzsch STA 449
F3 Jupiter. The ground ore was blended with the desired
coal and sulphur additions, placed in an alumina cruci-
ble and analyzed under a nitrogen atmosphere. The
sample masses were 25–35 mg and were heated from
30 to 1200uC at a rate of 10 K min21.
Reduction tests
The as-received ore was dried in an oven at 100uC for
24 h to remove free water, then ground to 2100 mesh
and stored at 65uC. The limonitic ore, bituminous coal
and reagent grade elemental sulphur were mechanically
mixed in varying proportions to give a total sample mass
of 3 g. The coal additions were varied in the range of 0–
6% and the sulphur additions in the range of 0–4%. The
control composition was 6% coal and 4% sulphur. The
ore mixtures were subsequently compacted at 8000 psi
into briquettes with a diameter of 1?3 cm and a height of
1 cm. The briquette was then placed in a quartz boat
lined with alumina powder and inserted into a tube
furnace. A schematic diagram of the experimental
apparatus is shown in Fig. 1.
For the control tests, the sample was held at a re-
duction temperature of 600uC for 1 h under an inert
nitrogen atmosphere, heated to a particle growth tem-
perature of 1000uC for a further hour, and then with-
drawn to a cooling zone at room temperature under
nitrogen. The particle growth temperature was varied in
Table 2 Estimated mineralogical composition of the limo-
nitic ore (dry basis)
Mineral NiO FeOOH Mg3Si2O5(OH)4 SiO2 Al2O3 Other
Wt-% 2?06 85?48 0?98 4?98 6?49 ,0?01
Table 3 Composition of bituminous coal sample used as a carbon source for reduction
Component Total Carbon Fixed Carbon
Wt-% 67?7 37?2
Elliott et al. Thermal upgrading process for nickeliferous laterite ores
the range of 1000–1300uC, and the retention time at
1000uC was varied in the range of 30–90 min. The
samples were then pulverized and screened to 2200
mesh. Magnetic separation tests were performed using a
CARPCO Wet High Intensity Magnetic Separator
(WHIMS) Model 3 | 4 L at an optimum field strength
of 2600 gauss.
Product analysis
The samples produced in the reduction tests were digested
in a solution of 5% bromine/95% methanol to selectively
dissolve metallics and sulphides, then analyzed for
nickel and iron using atomic absorption spectroscopy
(AAS).14,21 The mineralogical composition of the reduced
samples was determined by XRD using an Xpert Pro
Philips powder diffractometer and Cu ka radiation.
A secondary scan with a cobalt radiation tube was used
to counteract background noise caused by the high iron
content. Samples of interest were also examined using
environmental scanning electron microscopy (ESEM)
equipped with energy dispersive X-ray spectroscopy
(EDS). Environmental scanning electron microscopy
images were collected in the backscatter electron mode in
a low vacuum at 20 kV. Powdered samples were blended
with tungsten and iron chips in an alumina crucible and
fired at 1600uC under an oxygen atmosphere, in an Eltra
CS-2000 Carbon-Sulfur Determinator, to determine the
weight per cent of carbon and sulphur.
Thermodynamic modelling
Model description
A thermodynamic model of the carbothermic reduction
roasting of a nickeliferous limonite ore has previously
been reported.7 In this work, the model was modified to
account for the presence of sulphur in the system. The
equilibrium module of HSC Chemistry 6.1 was utilized
to calculate the multi-component equilibrium compo-
sition using the Gibbs free energy minimization
method.22 As in the previous work, the activity coeffi-
cients for the spinel phase ((Ni,Fe)O?Fe2O3) were those
proposed by Pelton et al., those for the monoxide
((Ni,Fe)O) were from the work of Hsieh and Chang, and
those for the ferronickel alloy (Ni–Fe) were adapted
from a review by Swartzendruber et al.23–25 Activity
coefficient equations for the sulphide species have been
adapted from previous research,26 as follows
 
1395
ln cFeS ¼ ð0·11X 2NiS 2 0·14X NiS Þ ð1Þ
T
 
1395
ln cNiS ¼ ð0·53X NiS 2 0·85X NiS þ 0·35Þ
2
ð2Þ
T
 
1395
ln cCoS ¼ ð0·53X 2NiS 2 0·85X NiS þ 0·35Þ ð3Þ
T
Volatiles Moisture Ash Sulphur
41?2 10?7 10?9 0?4
Canadian Metallurgical Quarterly 2015 VOL 00 NO 0 3
Elliott et al. Thermal upgrading process for nickeliferous laterite ores
1 Schematic diagram of the experimental apparatus
The species were grouped into five phases: gas, oxide,
sulphide, Fe–Ni–Co–S alloy, and carbon. A list of the 42
species considered and their respective phases are given
in Table 4. It was assumed that all of the monosulphides
will report to the Fe–Ni–Co–S phase. In the calcu-
lations, 100 kg of ore was utilized and this was equiv-
alent to 1?46 kmole. The carbon and sulphur additions
were represented in terms of kilogram of carbon or
sulphur per 100 kg of ore.
The input of the model was based on the estimated
mineralogy as given in Table 2. Coal was added to the
model as methane and carbon, as well as trace water and
sulphur, based on the analysis given in Table 3. Nickel
grades and recoveries for various coal and sulphur ad-
ditions were determined as a function of temperature.
Reported nickel grades refer to the nickel within the
ferronickel phase, representing a theoretical maximum
achievable grade. Likewise, reported recoveries refer to
the amount of nickel reporting to the ferronickel phase.
Model results
Figure 2 shows the effect of varying coal additions on
the nickel grade with no sulphur addition. The nickel
grade is initially high and rises to a maximum of ap-
proximately 95% at 400uC, then decreases significantly
as the temperature increases, especially for higher coal
levels. As has previously been reported in the litera-
ture,7,9,27 low amounts of coal allow for a greater degree
of selectivity during reduction, creating a higher grade
ferronickel alloy. Figure 3 shows the variation in nickel
recovery for the same conditions as in Fig. 2. It can be
seen that the nickel recovery is initially low and then
Table 4 Summary of phases (in bold) and species considered in the thermodynamic calculations
Gas
O2 S CoO
H2 S2 Co3O4
H2O SO MgFe2O4
CO SO2 Fe3O4
CO2 H2S FeO
CH4 H2SO4 Fe2O3
FeOOH
4 Canadian Metallurgical Quarterly 2015 VOL 00
quickly rises to a maximum at 500uC. Nickel recovery
remains relatively constant at 96% beyond 500uC for all
coal levels at or above 4%. For a 2% coal addition, the
nickel recovery drops significantly at temperatures
higher than 400uC. The high-grade ferronickel predicted
at low coal levels is therefore associated with a low
recovery, as lower coal additions are insufficient to
reduce and recover a significant fraction of the nickel.
A 2% coal addition yields a grade of 80% but a recovery
of only 47% at 1000uC, while a 4% coal addition yields a
grade of 50% and recovery of 95% at the same
temperature.
Figure 4 shows the effect of a 0?5% sulphur addition
on the nickel grade for the same range of coal additions
as in Fig. 2. A significant overall decrease in grade is
observed compared to the sulphurless system. The nickel
grade decreases from an initial maximum of 35–40% as
the temperature increases, with a significant decrease in
grade at about 600uC, especially for higher coal ad-
ditions. This is a result of the formation of iron mono-
sulphides, which are expected to report to the ferronickel
alloy phase, diluting the nickel content.
The addition of 0?5% sulphur suppresses the for-
mation of nickel oxide at higher temperatures, improv-
ing recovery significantly, especially at lower carbon
additions, as seen in Fig. 5. The nickel recovery remains
relatively constant at 96–98% for all coal additions
higher than 2% as the temperature increases, with a
maximum reached at 600uC. In a manner similar to the
sulphurless case, as shown in Fig. 3, the nickel recovery
is seen to decrease significantly beyond 500uC for a coal
addition of 2%.
Oxide Sulphide Alloy
2FeO? or ?SiO2 Mg2SiO4 NiS2 Fe
Fe2SiO3 SiO2 Ni3S2 Ni
Fe2SiO4 NiFe2O4 FeS2 Co
FeSiO3 CoFe2O4 Carbon FeS
MgO 2CoO? or ?SiO2 C NiS
MgSiO3 2NiO? or ?SiO2 CoS
NiO
NO 0

2 Predicted nickel grades as a function of temperature for
coal additions in the range of 2–8%
3 Predicted nickel recoveries as a function of temperature
for coal additions in the range of 2–8%
4 Predicted nickel grade as a function of temperature for
coal additions in the range of 2–8% and a sulphur addition
of 0?5%
Elliott et al. Thermal upgrading process for nickeliferous laterite ores
5 Predicted nickel recovery as a function of temperature for
coal additions in the range of 2–8% and a sulphur addition
of 0?5%
The effect of further increasing the sulphur content of
the ore at a fixed 4% coal content was also investigated.
Figure 6 shows the effect of increasing the sulphur
content on the nickel grade. It can be seen that the nickel
grade increases rapidly to a maximum at 500uC, with
higher levels of sulphur addition producing a lower
nickel grade. A sulphur addition of 4% produces a
maximum nickel grade of only 5?3%, compared to 30%
for a 0?5% sulphur addition. Figure 7 shows the effect of
increasing sulphur additions on the nickel recovery for
the same conditions as in Fig. 6. A maximum recovery
can be observed for all cases at 500uC, with only mod-
erate improvements in recovery as the sulphur addition
increases beyond 0?5%.This is a result of the formation
of nickel oxide as part of a stable solid-state solution
with the wüstite phase at higher temperatures, limiting
the nickel available to report to the metallic alloy phase.
From these results, the optimal reduction conditions
have been identified as 4% coal, 0?5% sulphur and
600uC. As this modeling does not take into account the
mass transfer limitations of using a solid-state reductant
6 Predicted nickel grade as a function of temperature for a
4% coal addition and sulphur additions in the range of
0?5–4%
Canadian Metallurgical Quarterly 2015 VOL 00 NO 0 5
Elliott et al. Thermal upgrading process for nickeliferous laterite ores
7 Predicted nickel recovery as a function of temperature for
a 4% coal addition and sulphur additions in the range of
0?5–4%
in a real system, a slightly higher coal addition of 6%
was selected for the experimental work.
These predictions also do not account for the effect of
the sulphur addition on the size of the ferronickel par-
ticles. Although only moderate increases in the recovery
of nickel to the ferronickel were observed for increases in
sulphur content beyond 0?5%, it is expected that higher
sulphur contents will result in larger ferronickel particles.
The increased ferronickel particle size resulting from this
sulphur addition will aid in the magnetic separation
process, improving the recovery of the ferronickel alloy.
The model is also a closed system and does not account
for loss of gases from the briquette; it is expected that
higher sulphur additions may be required to achieve the
desired residual sulphur in the reduced ore.
It is also of interest to examine the iron containing
species, in particular magnetite. Figure 8 shows the
fraction of total iron present as magnetite in the absence
of sulphur and with coal additions in the range of 2–8%.
The fraction of iron present as magnetite decreases with
increasing temperature, with a greater decrease for
8 Predicted fraction of the total iron present as magnetite as
a function of temperature, for the sulphurless ore with
coal additions in the range of 2–8%
6 Canadian Metallurgical Quarterly 2015 VOL 00 NO
higher coal additions. A significant decrease in magne-
tite is also observed at 600uC for an 8% coal addition.
Despite this trend, a significant amount of magnetite is
expected to be present in the thermally treated ore. For a
6% coal addition at 1000uC, 73% of the iron would be
present in the form of magnetite.
Figure 9 shows the fraction of the total iron present as
magnetite for a fixed 4% coal addition and sulphur ad-
ditions in the range of 0–4%, as a function of tempera-
ture. In a manner similar to the sulphurless system
shown in Fig. 8, as the temperature increases the amount
of iron present as magnetite decreases in all cases.
Increased sulphur additions reduce the amount of iron
present as magnetite by forming iron sulphides.
At 1000uC, 57% of the iron is present as magnetite for
ore with a 6% coal and a 4% sulphur addition, compared
to 73% in the sulphurless case. Despite this further
decrease, it is expected that magnetite will comprise a
significant fraction of the processed ore. The solubility
of the nickel in the iron silicate phase may hinder nickel
recovery, but given the low silicate content of the ore,
this should have a limited impact. The dissolution of
nickel in the wüstite phase could also reduce recovery;
although based on the thermodynamic model presented
here, this is also expected to have a limited effect.
Results and discussion
TGA studies
The results of the TGA studies without and with sulphur
additions are shown in Figs. 10 and 11, respectively. The
initial mass loss up to 200uC was attributed to the
removal of free water. At about 250uC, a significant
mass loss was observed for all compositions, which is
consistent with the dehydroxylation of goethite to hae-
matite and magnetite.28,29 In the samples containing coal
and no sulphur, no further significant mass loss was
observed until about 700uC, at which point the reduction
of the metal oxides was observed. Although the nickel
oxide contained in the ore should be preferentially
reduced before the iron oxide, no observable mass loss
9 Predicted fraction of the total iron present as magnetite
as a function of temperature, for a 6% coal addition and
various sulphur additions in the range of 0–4%
0

10 Thermogravimetric analysis results for the sulphurless
ore with coal additions in the range of 3–9%. Also
included is the as-received ore without a coal addition
11 Thermogravimetric analysis results for the ore with a 6%
coal addition and sulphur additions in the range of 0–6%.
Also included is the as-received ore without coal or
sulphur additions
was detected before 700uC, likely because of the low
nickel oxide concentration (1?38%Ni).
For samples with sulphur additions, increased mass loss
was observed between 200 and 400uC relative to the sul-
phurless samples with similar coal additions. This is a
result of both the formation of gaseous sulphur species and
the initial sulphidation of the metal oxides.10 Increasing
mass loss was observed as sulphidation continued until
about 800uC, where reduction by the coal addition began
to take place, following a similar trend to the sulphurless
samples. The higher temperatures required for the re-
duction of the metal oxides in the presence of sulphur
could be attributed to the sulphidation of metal oxides,
which reduces the oxide availability at higher tempera-
tures. The continuing minor mass loss observed at higher
temperatures is likely because of the loss of residual crys-
talline water.30
The results of this TGA study suggest that the
addition of sulphur results in the formation of metal
sulphides allowing for the retention of sulphur in the
Elliott et al. Thermal upgrading process for nickeliferous laterite ores
system at higher temperatures, while having limited
impact on the reduction of the remaining metal oxides,
by the coal addition. This is supported by the carbon
and sulphur assays of samples from the TGA, as given in
Tables 5 and 6, respectively.
The decreases in the carbon and sulphur contents of
each sample correspond to the onset of the sulphidation
and the reduction of the metal oxides as observed in the
TGA studies. The initial loss of carbon between 30 and
400uC can be attributed to the volatiles in the bituminous
coal. By 800uC, a significant drop in the weight per cent of
carbon is observed, corresponding to the reduction of the
metal oxides. As previously noted, the addition of sulphur
appears to delay the onset of reduction, supported here
by the higher levels of carbon present at 600–800uC in the
sulphur bearing sample. The decrease in sulphur content
in the range 30–600uC corresponds to the loss of sulphur
from the system as a gas before it can form a stable metal
sulphide. The dramatic change in the sulphur content
between 600 and 800uC can be attributed to the de-
composition of the metal sulphides, in particular pyrite,
and the subsequent loss of sulphur from the system.31–33
The apparent increase in sulphur content between
800 and 1200uC is the result of oxygen and carbon being
lost from the system, while some sulphur is retained as
metal sulphides. Based on these results, it is reasonable
to conclude that about 10% of the initial sulphur ad-
dition is retained at 1000uC. To achieve the desired 0?5%
retained sulphur, an initial addition of 5% is required.
Metallization studies
Reduced and thermally treated samples were digested in
a bromine-methanol solution and were analyzed by AAS
to determine the fraction of both nickel and iron
reporting to the ferronickel phase. The total metallics
represent the fraction of the nickel and iron in the ore
that have been reduced; these metals are expected to be
in the ferronickel phase and would be recovered during
magnetic separation. The per cent metallizations of
nickel and iron are the recoveries of each in the ferro-
nickel, as a percentage of the head grade.
Nickel metallizations were in the range of about 70–
80%, whereas iron metallizations were in the range of
40–50%. It was expected that greater than 98% of the
nickel would be recovered to the ferronickel. These data
suggest that complete reduction of the nickel had not
been achieved, although a greater fraction of the nickel
had been reduced than the iron.
The average nickel grade was estimated to be 4?76%
based on the nickel and iron metallizations in Table 7,
although this does not account for the small amount of
sulphur and other metals present in the alloy. This is
about half of the 10?2% predicted by the thermodynamic
model for a 6% coal and a 4% sulphur addition as shown
in Fig. 4, and significantly lower than the 21?5% predicted
for 4% coal and the same sulphur addition (Fig. 4).
XRD analysis
X-ray diffraction analysis of material reduced and
thermally grown under the control conditions was used
to identify the mineral species present. Figure 12 shows
Canadian Metallurgical Quarterly 2015 VOL 00 NO 0 7
Elliott et al. Thermal upgrading process for nickeliferous laterite ores

Table 5 Carbon content of various ore samples at temperatures from 30 to 12008C

Composition/wt-% 308C 4008C 6008C 8008C 10008C 12008C

Ore 0?0775 0?00 0?00 0?00 0?00 0?00

6% Coal 4?726 3?992 3?708 2?510 0?984 0?00
6% Coal, 4% S 4?502 3?929 4?166 3?595 0?998 0?00

Table 6 Sulphur content of various ore samples at temperatures from 30 to 12008C

Composition/wt-% 308C 4008C 6008C 8008C 10008C 12008C

Ore 0?00 0?00 0?00 0?00 0?00 0?00

6% Coal 0?0116 0?00 0?00 0?00 0?00 0?00
6% Coal, 4% Sulphur 3?160 2?730 2?245 0?279 0?447 0?757

Table 7 Metallization extents for samples reduced at 6008C

Coal/wt-% Sulphur/wt-% Growth zone temperature/8C Total metallics/wt-% Ni metallization/% Fe metallization/%

6 2 1000 19?9 68?7 41?5

6 4 1000 21?1 72?7 43?9
6 2 1100 22?7 78?4 47?4
6 4 1100 23?7 81?8 49?4

that for the control conditions wüstite, fayalite, and
metallic iron were all present. Wustite is the target iron
oxide species, as it is non-magnetic and should be
rejected during magnetic separation. Fayalite is an iron
silicate and also non-magnetic. The metallic nickel is
associated with the metallic iron, forming a ferronickel
alloy. As no magnetite was detected, it is possible that
the reaction environment was more reducing than pre-
dicted in the thermodynamic model, over reducing the
iron oxides to metallic iron.
ESEM studies
Figure 13 shows typical micrographs of ore reduced
under the control conditions with a 6% coal addition
and various sulphur additions in the range of 0–4%.
Ferronickel particles up to 50 mm were observed,
although the majority was in the range of 10–20 mm.
Figure 13a shows that without added sulphur, the fer-
ronickel particles formed were only 1–3 mm, whereas
Fig. 13b shows that sulphur additions can increase the
12 X-ray diffraction pattern of upgraded ore showing peaks
associated with wüstite, metallic iron and fayalite
size of the ferronickel particles. Evidence of a liquid or
semi-liquid iron–nickel–sulphide phase was observed, as
seen in Fig. 13c. Figure 13d shows that the ferronickel
particles were surrounded by large iron silicate particles
in an iron oxide matrix.
Figure 14 shows the effect of particle growth tem-
perature and thermal growth retention time on the fer-
ronickel particle size. A maximum observed particle size
was reported for each set of conditions. This particle size
increased and then leveled off with both increasing
temperature and increasing processing time.
A maximum particle size of 110 mm was observed for a
treatment temperature of 1200uC and a retention time of
60 min.
Effect of sulphur additions on nickel grade and
recovery
A study was conducted on the influence of sulphur ad-
ditions on nickel grade and recovery at a fixed 6% coal
addition, as shown in Fig. 15. The recovery of nickel
improved from about 15% at 0% sulphur to 75% at 4%
sulphur. Correspondingly, the grade increased from
about 1?4% to 2%. As expected, sulphur additions sig-
nificantly increased the recovery of nickel. As shown
previously in Fig. 13, the sulphurless samples contained
only very small ferronickel particles, which became
entrained in the surrounding iron oxide matrix, pre-
senting a challenge for recovery by magnetic separation.
Increased sulphur addition correlated with an increase in
ferronickel particle size (Fig. 13), which resulted in
improved recovery during magnetic separation.
A minimal increase in nickel grade was observed, which
was likely the result of over reduction increasing the
amount of metallic iron formed, diluting the ferronickel
product. In the range of coal and sulphur additions
tested, 6% coal and 4% sulphur were found to yield the

8 Canadian Metallurgical Quarterly 2015 VOL 00 NO 0


13 Backscattered images showing a a briquette reduced and then grown at 10008C without sulphur; b a briquette reduced and
then grown at 10008C with 4% sulphur; c a single ferronickel particle from same; and d phases typically present in the
reduced ore
best results. A summary of the results from tests run at
these conditions is given in Table 8.
These results show that a ferronickel concentrate with
a nickel grade and recovery of 4?0% and 93?2%, re-
spectively, can be achieved by the two-stage process with
the addition of 6% coal and 4% sulphur. Nickel grades
were lower than the 10?2% predicted by the thermo-
dynamic model, as shown in Fig. 4, but are in close
agreement with the value of 4% predicted by the
metallization study (Table 8). This lower than expected
nickel grade is the result of iron recoveries being higher
than expected, with iron being recovered both as met-
allic iron and as various iron oxides. As there is no
evidence of magnetite in the reduced ore, it is likely that
the addition of coal was higher than necessary, resulting
in the reduction of the iron oxides to metallic iron.
As the magnetic concentrate was not entirely metallic,
Elliott et al. Thermal upgrading process for nickeliferous laterite ores
it is also likely that poor liberation of the ferronickel
particles from the surrounding material led to the
co-recovery of the iron oxides and silicates.
The nickel recoveries were high, up to 93%, and close
to the predicted maximum of 98% given in the thermo-
dynamic model (Fig. 5). It should be noted that the Fe/
Ni ratios presented here assume that the presence of
other components in the recovered ferronickel (for
example residual sulphur) is negligible and as such rep-
resent an upper limit. It is also of note that the recoveries
reported here are higher than what would be expected
based on the metallization extent of nickel observed
during the metallization studies; this suggests either that
the metallization study underreports nickel metallization
or that nickel contained in a non-metallic, non-sulphide
phase is also being recovered during the magnetic sep-
aration step.
Canadian Metallurgical Quarterly 2015 VOL 00 NO 0 9
Elliott et al. Thermal upgrading process for nickeliferous laterite ores

Table 9 Comparison of selectivity factors obtained in the

present work with those of other researchers

Initial Final
grade grade

Ni Selectivity
Ni Fe Ni Fe recovery factor (b) Ore type Reference

1?38 56 4 96 93?2 1?69 Limonite Present

work
1?49 34?69 9?87 90?13 90?9 2?55 Saprolite Jiang
et al.19
1?91 22?1 9?48 90?52 83?01 1?21 Saprolite Li et al.18
1?42 23?16 9?48 90?52 92?1 1?71 Saprolite Zhu
et al.17

respectively. In this way, the selective reduction of nickel

14 Effect of particle growth temperatures in the range of 1000–
13008C and retention times in the range of 30–90 min
at 10008C on the maximum size of ferronickel particles
for ore samples containing 6% coal and 4% sulphur
15 Effect of sulphur additions on the recovery and the
grade of nickel in the magnetic concentrate, 10 g
samples with 6% coal
in ores of varying nickel and iron grades can be com-
pared on the basis of the fraction of nickel reporting to
the ferronickel product relative to the fraction of iron
reduced to the metallic state. Selectivity factors calcu-
lated for the current work, as well as similar works by
other researchers, are summarized in Table 9.
It can be seen that the Fe/Ni ratio of the ore used in
this work was much higher than in the other studies.
However, the selectivity factor was similar to those
reported for ores with significantly lower iron contents.
In this work, high nickel recoveries were also achieved
with moderate coal and sulphur additions at a reduction
temperature lower than those previously reported in the
literature.17–19 With additional improvements in selec-
tivity during the reduction process, it should be possible
to further increase the ferronickel grade and enhance the
rejection of iron oxides, thereby increasing the nickel
grade in the recovered magnetic concentrate. The rela-
tively high temperature utilized in this work was similar
to the reduction temperatures reported in the literature,
and thus the energy requirements should be similar.17–19
However, the enhanced particle growth in the two-stage
process should lead to improved nickel grade and
recovery in the concentrate.

Table 8 Nickel grades and recoveries achieved with 6% Conclusion

coal, 4% sulphur at a particle growth temperature of
10008C and separated using WHIMS
(1) A thermodynamic model has been developed and
Magnetic applied to the analysis of the carbothermic re-
fraction/wt-% Ni grade/wt-% Recovery/% Fe/Ni ratio duction roasting of a nickeliferous limonitic laterite
ore in the presence of sulphur. The effects of tem-
27?7 3?8 83?7 25?3
28?8 4?0 93?2 24?0 perature and coal and sulphur additions on the
31?0 3?8 93?1 25?3 recovery of nickel and the nickel grade of the
resulting ferronickel alloy have been determined.
It was found that the grade decreased and the
In order to compare the present results with other
recovery increased with increasing carbon and sul-
experimental findings reported in the literature for ores
phur additions. It was possible to achieve significant
with different nickel and iron grades, a selectivity factor
enrichment of nickel in the ferronickel by control-
(b) is used as follows.
ling the reducing conditions. The thermodynamic
X Ni Y Fe results obtained were in general agreement with the
bNi ¼ ð4Þ experimental results of the present work, as well as
Fe X Fe Y Ni
those available in the literature, in terms of the
where X and Y are the concentrations of the nickel and effect of temperature on the nickel recovery and
the iron in the as-received and the reduced ore, also the optimum reduction temperature.

10 Canadian Metallurgical Quarterly 2015 VOL 00 NO 0


(2) The results of the TGA show that no reduction
occurs below 600uC, and that significant reduction
of the iron oxide takes place between 800 and
1000uC. In addition, the majority of the sulphur in
the ore is lost below 400uC, with 10% of the initial
sulphur remaining as residual sulphur at 1000uC.
From this, it can be determined that a minimum
sulphur addition of 4% is required to achieve suf-
ficient residual sulphur for particle growth.
(3) A ferronickel concentrate was produced in a two-
stage process consisting of a reduction step at 600uC
and a particle growth stage at 1000uC, followed by
WHIMS at 2600 gauss. For a carbon addition of
6% and a sulphur addition of 4%, a concentrate was
produced with a nickel grade of 4% and nickel
recovery of 93?2%. The achieved nickel grade is
lower than the predicted grade of 10?2%, indicating
that more iron was recovered. This iron was
recovered both as metallic iron in the ferronickel
and non-magnetic iron oxides, such as wüstite,
entrained in the magnetic concentrate.
(4) The effect of particle growth temperature and
retention time on the size of the ferronickel particles
was investigated. It was found that the particle size
increased with increasing temperature and retention
time, with minimal improvement beyond 1200uC
and 60 min. For the control conditions, the typical
particle size was 10–20 mm. The maximum particle
size of 120 mm was observed for reduction con-
ditions of 1200uC and 60 min.
Acknowledgements
The authors thank the Natural Sciences and Engineering
Research Council of Canada and Xstrata for support of
this research.
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