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Thermochimica Acta 533 (2012) 5665

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

TG/DTA study on the oxidation of nickel concentrate


Dawei Yu , Torstein A. Utigard
University of Toronto, Department of Materials Science and Engineering, 184 College Street, Toronto, Ontario M5S3E4, Canada

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

Article history: The oxidation mechanism of nickel concentrate from ambient up to 1000 C was investigated by thermo-
Received 11 July 2011 gravimetric (TG) and differential thermal analysis (DTA) to improve the understanding of the oxidation
Received in revised form behavior of the nickel concentrate during industrial roasting. The reaction products at intermediate tem-
25 November 2011
peratures were analyzed by X-ray powder diffraction (XRD), SEM/EDS, electron probe micro-analysis
Accepted 22 January 2012
(EPMA), and chemical analysis. A reaction scheme was deduced, in which the preferential oxidation of
Available online 30 January 2012
iron sulde species took place in the temperature range of 350700 C, forming Ni1x S and Fe2 O3 . Subse-
quently, the resulting Ni1x S was transformed into Ni3x S2 . Ni3x S2 core melted at 813 C and accelerated
Keywords:
TG/DTA
its oxidation forming NiO and NiSO4 . At 942 C, NiSO4 decomposed and the complete oxidation of the
Nickel concentrate remaining nickel sulde took place due to the absence of the protective sulfate shell. The kinetic results
Oxidation indicate that the diffusion of O2 through the sample bed controls the reaction rate if the bed depth is
Roasting larger than approximately 125 m.
2012 Elsevier B.V. All rights reserved.

1. Introduction the thermal decomposition of metal sulfates that could be formed


during the roasting of the nickel concentrate, were briey reviewed.
Oxidizing roasting mechanisms of metal sulde minerals are The oxidation of a natural pentlandite (Fe,Ni)9 S8 was studied by
quite complex because they vary depending on the sulde species Dunn and Kelly [1] using TG and DTA. In their study, an exother-
in the minerals, the roasting conditions employed, and the interac- mal event was detected by the DTA at 520 C which was claimed
tions among all species present. Lab scale thermogravimetric (TG) to be the oxidation of iron sulde (FeS) forming iron oxide (Fe2 O3 ).
and differential thermal analysis (DTA) studies on the oxidation Another exothermal event at 575 C was suggested to be caused
of sulde minerals have much milder oxidation conditions than by the oxidation of the Fe8x Ni8y S16z phase which forms upon
the industrial scale uidized bed roasting in terms of the effective heating the natural pentlandite. Upon reaching 800 C, the temper-
gassolid contacting area and the heating rate. However, TG/DTA ature is in the vicinity of the melting point of the unquenchable
studies yield valuable information on the chemical reaction routes compound Ni3x S2 , which leads to its accelerated oxidation. This
and the kinetics of gassolid reactions during roasting due to its thermal event was also suggested in [2,3]. A reaction scheme was
ability to control precisely the experimental conditions and to mon- deduced and summarized in Table 1 [1]. The oxidation of synthetic
itor variable experimental parameters. In this study, attempts were millerite (Ni0.994 S) was also investigated by Dunn and Kelly [2] with
made on revealing the reaction sequences during the oxidation of a the same apparatuses in a dynamic oxygen atmosphere (0.2 L/min)
nickel concentrate by TG/DTA. Gas analysers were used to measure up to 1000 C. Under these conditions, a reaction scheme was pro-
the offgas SO2 and O2 contents continuously during the TGA runs. X- posed and is shown in Table 2.
ray powder diffraction (XRD), scanning electron microscopy (SEM), Kennedy and Sturman [4] investigated the oxidation of iron(II)
energy dispersive X-ray spectroscopy (EDS), electron probe micro- sulde Fe1x S in air and oxygen atmospheres using TG, DTA, XRD
analysis (EPMA) and inductively coupled plasma optical emission and chemical analysis. A reaction scheme reported in this study is
spectroscopy (ICP-OES) were employed to characterize the con- shown in Table 3. The rate of oxidation of ferrous sulde in a tiny
centrate and the oxidation products, namely calcines. The rate bucket was examined by means of a spring balance and X-ray pow-
controlling step in the TGA tests was also investigated. der diffraction analysis [5]. The bulk of sample in the bucket had a
Many researchers have studied the oxidation of various metal disk-type shape, with several millimeters thickness. By varying the
suldes in a laboratory scale. Studies on the oxidation of nickel, sample sizes to be roasted, the conclusion was drawn that the rate
iron, and copper containing sulde minerals, as well as studies on was controlled by the diffusion of oxygen and/or gaseous products
through the bed of the sample.
The oxidation of chalcopyrite was studied by means of TG, DTA,
Corresponding author. Tel.: +1 416 978 0912. XRD and colorimetry techniques [6]. The results indicate that in
E-mail address: dawei.yu@utoronto.ca (D. Yu). the range between 350 C and 440 C, the sample surface, which

0040-6031/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.tca.2012.01.017
D. Yu, T.A. Utigard / Thermochimica Acta 533 (2012) 5665 57

Table 1 Table 4
Various reactions occurring during the oxidation of pentlandite at 10 C/min in an Chemical composition of the Raglan concentrate.
air/oxygen ow of 0.2 L/min [1].
Constituents Weight%
<460 C (Ni,Fe)9x S8y Fe8x Ni8y S16z + NiS + FeS
Ni 17.9
460640 FeS + 2O2 FeSO4
Fe 30.8
460715 NiS + 2O2 NiSO4
Cu 4.54
520 2FeS + 3.5O2 Fe2 O3 + 2SO2
Co 0.36
575 Fe8x Ni8y S16z + O2 Ni2 FeO4 + SO2 + NiO + Fe2 O3
S 27.6
640760 2FeSO4 Fe2 O3 + (2SO2 + 0.5O2 )
MgO 5.43
(Ni,Fe)9x S8y Ni3x S2 + Fe8x Ni8y S16z Al2 O3 0.76
700740 Fe8x Ni8y S16z + O2 Ni2 FeO4 + SO2 SiO2 8.69
NiS + 1.5O2 NiO + SO2 Total 96.1
o2
775805 Ni3x S2 NiO + (SO2 + 0.5O2 )
>800 NiSO4 NiO + (SO2 + 0.5O2 )
2. Experimental

Table 2 2.1. Sample


Various reactions occurring in the oxidation of Ni0.994 S [2].
The nickel concentrate investigated in this study was Raglan
400785 C NiS + 2O2 NiSO4
concentrate from Xstrata Sudbury Smelter. XRD analysis and
500785 NiO + SO2 + 0.5O2 NiSO4
SEM/EDS indicate that it is mainly composed of pentlandite
540552 and 682692 NiS + 1.5O2 NiO + SO2
(Ni,Fe)9 S8 , pyrrhotite Fe1x S, chalcopyrite CuFeS2 , as well as small
682692 and possibly 3NiS + 2NiSO4 Ni3 S2 + 2NiO + 3SO2 quantities of silica ux which mainly comprises magnesium sil-
682692 10NiS + 2O2 Ni7 S6 + Ni3 S2 + 2SO2 icate. Its chemical composition is given in Table 4. EPMA was
682780 Ni7 S6 + 9.5O2 7NiO + 6SO2 applied to evaluate the stoichiometry of each mineral in the con-
and/or Ni7 S6 + 12.5O2 6NiSO4 + NiO centrate with their average stoichiometries shown as follows:
793 Ni3 S2(s) Ni3 S2(l) pentlandite (Fe4.27 Ni4.61 Co0.07 S8 ), pyrrhotite (Fe0.87 Ni0.01 S), chal-
793 Ni3 S2(l) + 3.5O2 3NiO + 2SO2 copyrite (Cu0.98 Ni0.06 Fe1.00 S2 ). The particles are ne with 93.3%
passing 200 mesh (74 m) and 76.7% passing 400 mesh (37 m).
>800 NiSO4 NiO + SO2 + 1/2O2

2.2. TG/DTA study


Table 3
Reaction scheme for the oxidation of iron sulde (Fe1x S) [4]. All the oxidation tests were conducted in a Setaram TGDTA 92
Fe1x S + (2 x)O2 (1 x)FeSO4 + xSO2 unit (SETARAM Inc., Newark, CA). For TGA runs, Raglan concentrate
3Fe1x S + (5 2x)O2 (1 x)Fe3 O4 + 3SO2 of typically 100 mg was put in an alumina crucible (I.D. 7.20 mm,
425520 C
4Fe1x S + (7 3x)O2 (2 2x)Fe2 O3 + 4SO2 depth 5.39 mm). The crucible was suspended from the microbal-
8Fe1x S + (2 4x)SO2 (1 2x)Fe3 O4 + (5 2x)FeS2
ance on top of the TGA unit by platinum wires. The temperature
520572 C 4Fe1x S + (7 3x)O2 (2 2x)Fe2 O3 + 4SO2 prole was set prior to each run. During each run, the atmosphere
FeS2 + 3O2 FeSO4 + SO2 was controlled by introducing either extra dried air, O2 , or argon
575625 C 12FeSO4 + 3O2 2[Fe2 (SO4 )3 ]2 Fe2 O3 gas into the TGA chamber from the top, with the gas owrate being
4Fe3 O4 + O2 6Fe2 O3 adjusted by a rotameter (OMEGA FL-3402C). The owrate of the
625725 C [Fe2 (SO4 )3 ]2 Fe2 O3 3Fe2 O3 + 6SO3 offgas was measured by a digital owmeter (OMEGA FMA-5610).
The offgas was analyzed continuously by two gas analyzers (ABB
EL3020) for its SO2 and O2 contents. A computer controlled data
acquisition system (FLUKE Hydra Series II) was used to record the
had free access to oxygen, was oxidized into iron sulfate, CuSO4 data from both the gas analyzers and the digital gas owmeter.
and Fe2 O3 . While below the surface where oxygen was relatively Most of the samples were air-quenched by lifting the crucible out
starved, bornite (Cu5 FeS4 ) could be formed as an inert atmosphere of the TGA chamber once the heating was nished. The TGDTA
product along with the formation of FeS and elemental sulfur. unit setting was switched to DTA mode for DTA runs, which was
Between 440 C and around 500 C these inert atmosphere prod- done by replacing the platinum wires with a DTA rod and plugging
ucts were oxidized signicantly. Iron sulfate was fully decomposed necessary connections for the DTA thermocouples. Raglan con-
at 700 C, after which CuSO4 would be decomposed to CuO with the centrate of 30 mg was put in an alumina crucible (I.D. 4.08 mm,
formation of an intermediate compound CuOCuSO4 . In the temper- depth 8.07 mm) which was then mounted on the DTA rod. Cal-
ature range between 800 C and 850 C, CuO, CuFe2 O4 and Fe3 O4 cined alumina powder of 30 mg was put in the other crucible as
were the only stable species. reference.
Thermal decomposition of nickel (II), copper (II), iron (II and III),
and cobalt (II) sulfates have been investigated by many researchers
2.3. Analytical methods
[713]. The decomposition temperatures of Fe2 (SO4 )3 , CuSO4 ,
NiSO4 and CoSO4 in air were reported to be 575 C, 625 C, 675 C
2.3.1. XRD
and 720 C, respectively, by TG/DTA [7]. The thermal decomposi-
Quenched samples were subject to XRD analysis for qualita-
tion process of copper(II) sulfate consisted of two steps, which are
tive mineral composition. X-ray diffractometer traces were taken
shown as Reactions (1) and (2) [7,10,13].
on a Philips PW2273/20 diffractometer from 15 to 65 in terms
of 2 angle using Cu K radiation. Due to the limited amount of
2CuSO4 CuOCuSO4 + SO3 (1) sample available, single crystalline silica slide was used as sample
holder. Sample powder was mixed with acetone to make slurry and
CuOCuSO4 2CuO + SO3 (2) agglomerate on the silica slide.
58 D. Yu, T.A. Utigard / Thermochimica Acta 533 (2012) 5665

Fig. 1. Sample mass change, rate of mass change, SO2 concentration and O2 con-
sumption in the offgas for the TGA run in which 100 mg concentrate was heated to
950 C at 15 C/min in air. Fig. 2. DTA curve of Raglan concentrate heated at 15 C/min in air.

2.3.2. SEM/EDS each other. The powder nature of the sample tends to delay heat
Sample powders were mounted in the epoxy resin. After the transfer and leads to a drift of temperature range in which a specic
epoxy was cured, the surface was ground with silicon carbide thermal event occurs. As a result, the combined effect of the powder
papers with abrasive sizes of 180, 400, 600, 800, and 1200 sequen- sample size and the geometry of the sample which is dictated by the
tially. Final surface preparation was made on a polishing pad with geometry of the crucible should also contribute to the discrepancy
water based 0.3 m alumina suspension as polishing media. For between TGA and DTA results. Samples air-quenched from inter-
samples which contain water soluble sulfate species, oil based mediate temperatures in the TGA runs were analyzed by XRD for
1 m diamond suspension was used as polishing media instead. their mineral compositions. Their XRD patterns are listed in Fig. 4
The surface was then coated with carbon to render it electrically from the bottom to the top with the increase of temperature. Due
conductive. The SEM used is a JEOL, JSM-840, complemented by a to the complex nature of the system, assignments of some of the
PGT/AAT EDS detector (thin window) and an IXRF 500 digital pulse peaks were only tentatively suggested. Results of the wet chem-
processor, allowing for X-ray microanalysis and digital imaging, via ical analysis of the quenched samples by hot water leaching and
SE, BSE and X-ray signals. ICP is illustrated in Fig. 5 as the percentages of water soluble sul-
fates calculated on the basis of the content of each element in the
2.3.3. EPMA calcines. In order to better understand the oxidation mechanism of
Compositional analyses were acquired on a Cameca SX50 pentlandite in the concentrate, EPMA was applied to investigate the
electron probe X-ray microanalyzer equipped with 3 tunable wave- chemical composition change of the pentlandite sulde cores dur-
length dispersive spectrometers. Operating conditions were 40 ing the dynamic heating period. The results are plotted in a FeNiS
takeoff angle, and a beam energy of 20 keV. The beam current was ternary diagram as shown in Fig. 6.
20 nA, and the beam diameter was 1 m. Elements were acquired Mass changes are barely seen below 350 C from Fig. 1. After-
using analyzing crystals LiF for Fe K, Ni K, Cu K, Co K, PET wards, there is a gradual increase in mass till 498 C, where the
for S K, and PC1 for O K. The standards were hematite for O K, mass reaches a small peak and starts to decrease. Correspondingly,
cobaltite for Co K, pentlandite for S K, Fe K, Ni K, and chal- O2 in the feeding gas was consumed intensively and SO2 was
copyrite for Cu K. The counting time was 20 s for Fe K, Ni K, Cu emitted, which is denoted by the intensive SO2 and O2 peaks in
K, S K, 40 s for O K, and 60 s for Co K.

2.3.4. ICP-OES
Air-quenched samples of around 60 mg were water-leached
at 90 C for 30 min. Leachates were analyzed using ICP-OES
(PerkinElmer Optima 7200 DV) for Fe, Ni, Cu, Co, S, Mg, Al, and
Si contents.

3. Results and discussion

Fig. 1 displays the sample mass change, the rate of mass change,
SO2 concentration and O2 consumption in the offgas for the TGA
run in which 100 mg Raglan concentrate was heated in a 1 L/min
air stream from room temperature to 950 C at 15 C/min. The DTA
curve for the oxidation of 30 mg Raglan concentrate under the same
experimental conditions is shown in Fig. 2. In order to evaluate the
effects of oxygen partial pressure change on the possible thermal
events, a DTA run was also conducted in pure oxygen atmosphere
for comparison, its results being illustrated in Fig. 3. Due to the geo-
metrical difference of the crucibles used in the TGA and DTA runs,
the TGA and DTA curves may not necessarily correlate well with Fig. 3. DTA curve of Raglan concentrate heated at 15 C/min in O2 .
D. Yu, T.A. Utigard / Thermochimica Acta 533 (2012) 5665 59

Fig. 6. FeNiS diagram showing the change of chemical compositions during


dynamic heating in TGA runs analyzed by EPMA. The bottom part is the magnied
area of the trapezoid in the top ternary diagram.

in Fig. 1 is mainly due to two competing reactions, which are the


oxidation of chalcopyrite forming CuOCuSO4 and the oxidation
of pyrrhotite forming Fe2 O3 . These two reactions are expressed as
Reactions (3) and (4), the former leading to the mass gain while
the latter leading to the mass loss. Reaction (3) dominates below
498 C, causing an increase in the mass while the mass loss above
498 C is primarily due to Reaction (4).

Fig. 4. XRD patterns for calcines quenched from intermediate temperatures after 2CuFeS2 + 7O2 CuOCuSO4 + Fe2 O3 + 3SO2 (3)
heating at 15 C/min in air in TGA runs.
2Fe1x S + (3.5 1.5x)O2 (1 x)Fe2 O3 + 2SO2 (4)

Fig. 1, indicating the occurrence of vigorous oxidation reactions. The evidence to Reaction (3) is the XRD patterns, showing the
This is further conrmed by two partly overlapped exotherms in dramatic consumption of chalcopyrite and the formation of Fe2 O3
the vicinity of 500 C in Fig. 2, indicating the presence of at least and CuOCuSO4 between 450 C and 509 C. Occurrence of Reaction
two exothermic reactions leading to the mass change and SO2 (4) is based on the fact that pyrrhotite disappeared between 450 C
emission. These two reactions were greatly promoted by increas- and 509 C and that a substantial amount of Fe2 O3 was formed
ing the oxygen partial pressure shown as a much stronger single at 509 C, as suggested by the XRD patterns in Fig. 4. Dunn and
peak at 437 C in Fig. 3, which conrms the oxygen involvement in Kelly [1] observed the same reaction at 520 C. This disagreement
these two exotherms. The mass change between 450 C and 509 C of temperature under which the oxidation of Fe1x S occurs is
partly caused by the difference between experimental conditions
employed in the two studies. Another factor that may contribute
to the disagreement is the difference of the samples being studied.
Since their sample is a natural pentlandite, there would be no
Fe1x S unless it is formed from the decomposition of pentlandite.
While the sample in this study is a concentrate containing not only
pentlandite, but also around 16 wt% pyrrhotite, 13 wt% chalcopyrite
and some silica ux. Figs. 79 illustrate the morphological features
of the oxidized pyrrhotite air-quenched from 605 C, 733 C and
880 C, respectively. Reaction (4) would result in the volume
reduction of 24% (calculated based on the densities of Fe2 O3 and
Fe3 O4 ). From this, one would expect a porous micro-structure of
the oxidized pyrrhotite particles. However, the pyrrhotite particle
seems to be rather dense in Fig. 7. It became porous after heating
to higher temperatures as shown in Figs. 8 and 9. We resort
to the FeSO predominance diagram to help understand the
change of micro-structure as a function of temperature. Fig. 10 is
the FeSO predominance diagram at 500 C, 700 C and 900 C
calculated using a thermodynamic software package [14]. The
pyrrhotite particles experienced an oxidative atmosphere with the
Fig. 5. Chemical analysis results for the contents of the water soluble sulfates in the
O2 partial pressure of approximately 0.21 atm at the beginning of
calcines quenched from intermediate temperatures after heating at 15 C/min in air oxidation. The propagation of the oxidation reaction as Reaction
in TGA runs. (4) in the bulk of the sample bed consumed O2 from the local gas
60 D. Yu, T.A. Utigard / Thermochimica Acta 533 (2012) 5665

Fig. 7. SE image of an oxidized pyrrhotite particle quenched from 605 C in the TGA
run.
Fig. 10. Superimposed FeSO predominance diagram for 500 C, 700 C and 900 C
calculated using HSC Chemistry [14].

the oxidized pyrrhotite particle in Fig. 7 by EDS. This is indicative


of the presence of Fe2 (SO4 )3 which is disseminated in Fe2 O3 . The
formation of Fe2 (SO4 )3 alone from pyrrhotite would result in the
volume increase by 223%. It is thus easy to imagine that even a
small fraction of Fe2 (SO4 )3 would offset the volume reduction
caused by the formation of Fe2 O3 . This formation of Fe2 (SO4 )3
along with Fe2 O3 resulted in a rather dense nature of the oxidized
pyrrhotite at relatively low temperature as seen in Fig. 7. The
formation of Fe2 (SO4 )3 became more difcult with the increase of
temperature indicated by the shrinkage of the predominant area
for Fe2 (SO4 )3 in Fig. 10 as temperature increases. The particles
became porous at higher temperature as can be seen in Figs. 8 and 9
since Fe2 (SO4 )3 is no longer stable. This characteristic columnar
reaction interface with distinct orientations in these two gures
Fig. 8. SE image of an oxidized pyrrhotite particle quenched from 733 C in the TGA
was reported to be due to the inward preferential oxidation along
run showing its characteristic columnar structure. certain crystallographic plains [15,16].
Below 495 C, very little amount of sulfates formed, illustrated
by the proles in Fig. 5. But an increase in the content of water-
environment and released SO2 , which in turn lead a drop in the
insoluble CuOCuSO4 is shown in the XRD patterns till 495 C.
partial pressure of O2 and an increase in the partial pressure of
Decomposition of chalcopyrite would result in the formation of bor-
SO2 . Once the partial pressure of SO2 exceeded 105 atm, the gas
nite (Fe5 CuS4 ), as indicated by previous studies [6,16]. This phase
environment in the bulk of sample bed would favor the formation
was not detected by XRD in any of the quenched samples in this
of Fe2 (SO4 )3 at 500 C. Indeed around 2.5 wt% S was detected in
study, probably because the content of this phase was too low to
be identied by XRD. However, bornite was identied by SEM/EDS.
As illustrated in the backscattered electron (BSE) image of Fig. 11,
bornite formed around the chalcopyrite core with a clear bound-
ary between them. The porous surface layer is Fe2 O3 formed by the
preferential oxidation of iron species from chalcopyrite. The inten-
sity of the peaks for CuOCuSO4 decreased after 495 C, meaning
its content was decreasing as the heating proceeds. While at the
same time, the content of CuSO4 started to increase. This coinci-
dence suggests that CuOCuSO4 is a precursor for the formation of
CuSO4 , which has also been reported by other researchers [17].
Another reaction possibly has occurred up to 605 C based on
the XRD patterns. The consumption of pentlandite and formation of
Mss, Ni1x S, and Fe2 O3 are obvious and illustrated by the XRD pat-
terns at 450 C, 495 C and 509 C in Fig. 4. As a result, this reaction
is suggested to be the oxidation of pentlandite forming (Ni,Fe)1x S,
Ni1x S, and Fe2 O3 with the assignment of Reaction (5). SO2 pro-
duced from Reaction (5) and the O2 in the feeding gas provide
suitable atmosphere for sulfates formation, which is revealed by
Fig. 9. SE image of an oxidized pyrrhotite particle quenched from 880 C in the TGA
the massive metal sulfates formation in between 509 C and 605 C
run. in Fig. 5. This, as a result, gives rise to an accelerating mass increase,
D. Yu, T.A. Utigard / Thermochimica Acta 533 (2012) 5665 61

Fig. 11. BSE image of a chalcopyrite particle after heating the Raglan concentrate in Fig. 12. BSE image of a partly oxidized pentlandite particle air-quenched from
air at 450 C for 1 h (Cpy: chalcopyrite, CuFeS2 ; Bor: bornite, Cu5 FeS4 ). 733 C in the TGA run.

indicated by the peak in the rate of mass change curve in Fig. 1, also formed in the present study and signicant SO2 release was
corresponding to the right uplifting shoulders of the offgas curves. occurring above 509 C, Reaction (7) was tentatively suggested.
(Ni,Fe)1x S in Reaction (5) represents a non-stoichiometric iron
nickel sulde called monosulde solid solution (Mss) with hexag- (Ni, Fe)9 S8 + O2 (Ni, Fe)3 S4 + Fe2 O3 (6)
onal pyrrhotite structure [18]. Apart from the XRD observation,
some other evidence also supports the occurrence of Reaction (5). (Ni, Fe)3 S4 + O2 (Ni, Fe)1x S + SO2 (7)
Firstly, Raglan concentrate was heated in argon at 450 C for 1 h
The following thermal event is indicated by the uplifting shoul-
and quickly cooled down to room temperature with (Ni,Fe)1x S,
der of the DTA curve from 550 C to 690 C in Fig. 2, corresponding to
Ni1x S and Fe1x S found in the product. Dunn and Kelly [1] also
the wide peaks in the rate of mass change curve and offgas curves
found (Fe,Ni)1x S, NiS and FeS as the decomposition product of
at 660 C. In Fig. 3, this exotherm is shown as a wide peak from
pentlandite in a dynamic oxygen atmosphere below 460 C. Sec-
468 C to 700 C peaking at 562 C. This reaction can be deduced
ondly, Raglan concentrate was oxidized isothermally at 450 C for
based on the XRD patterns in Fig. 4 along with the composition
1 h and its product was examined under microscope, a thin layer
change of the pentlandite sulde cores in Fig. 6. Although no Mss
of iron oxide was found to have formed on the surface of the pent-
at 605 C was detected by XRD illustrated in Fig. 4, its presence
landite particle, with its core being converted to Mss. This suggests
was positively proved by EPMA in Fig. 6. The data points at 605 C
iron cations in pentlandite are oxidized preferentially via outward
are sulfur excessive with various Fe:Ni ratios. There was a relation-
diffusion mechanism. Preferential oxidation of iron species from
ship between the Fe:Ni ratios and the size of the particles analyzed,
pentlandite was studied by many researchers and well recognized
which was that a smaller particle tended to have a lower Fe/Ni
[15,16,19,20]. Iron cations tend to migrate out from the pentlandite
ratio. This makes sense because in a smaller particle which has a
particles toward the oxygen/oxide interface close to the surface of
larger surface to volume ratio, the average path for the Fe2+ ion
the particles where they were combined with O2 forming Fe2 O3 .
to diffuse out of the sulde core and be preferentially oxidized was
(Ni, Fe)9 S8 + O2 (Ni, Fe)1x S + Ni1x S + Fe2 O3 + SO2 (5) shorter, which means a shorter time was needed for the depletion of
Fe2+ ion from the sulde core. This phenomenon also suggests that
Violarite solid solution (Ni,Fe)3 S4 was also formed in the TGA smaller particles usually have larger oxidation rate, provided other
samples quenched from 450 C, 495 C and 509 C, which is denoted conditions unchanged. At 733 C, all the pentlandite sulde cores
by two stoichiometric forms FeNi2 S4 and Ni3 S4 . Although (Ni,Fe)3 S4 were transformed into Ni1x S containing around 2.5 atm% Fe whose
was reported to be stable only below 461 3 C in the presence of percentages reached a minimum and did not go any lower with
an equilibrium sulfur vapor [21], the dynamic heating conditions the increase of temperature. XRD patterns also show the increas-
applied in the present study sustained its presence up to 509 C. ing contents of Ni1x S and Fe2 O3 , as well as the full consumption
In nature, violarite is often intimately associated with pentlandite. of the intermediate product Mss from 495 C to 733 C. All of the
And violarite forms readily from pentlandite because pentlandite evidence suggests that this thermal event is the oxidation of Mss
structure can be easily converted to that of violarite, with a min- forming Ni1x S and Fe2 O3 , represented by Reaction (8). The mech-
imum of reorganization, by removal of excess metal atoms and anism behind this reaction is also the preferential oxidation of iron
redistribution of the remainder [22]. Based on this, violarite in the species from Mss via diffusion, forming iron oxide shell and nickel
present study is considered to be produced by the transformation sulde core in each pentlandite grain. Fig. 12 is a BSE image of a
of pentlandite. The removal of the excess Fe atoms was acceler- pentlandite particle quenched from 733 C showing its particular
ated by the oxidizing condition forming Fe2 O3 as a by-product. The structure of a nickel sulde core surrounded by a porous layer of
transformation reaction is represented as Reaction (6). This reac- iron oxide. EDS analysis indicated the iron sulfates were dissemi-
tion coincides with the mild mass increase and no signicant SO2 nated in the iron oxide. There is a discrepancy in the temperature
release up to 500 C. Thermal decomposition of violarite occurred range in which Reaction (8) occurs in the TGA and DTA modes,
above 509 C as indicated by the XRD results showing the disap- which is probably caused by the geometrical difference of the cru-
pearance of it at 605 C. Dunn and Howes [23] studied the oxidation cibles used in these two modes, as well as a larger sample size used
of violarite and reported that its decomposition in the oxidizing in the TGA mode.
atmosphere leads to the formation of Mss and SO2 as its oxida-
tion product in the temperature range 405475 C. As Mss was (Ni, Fe)1x S + O2 Ni1x S + Fe2 O3 + SO2 (8)
62 D. Yu, T.A. Utigard / Thermochimica Acta 533 (2012) 5665

Fig. 13. XRD patterns for calcines quenched from intermediate temperatures after heating at 15 C/min in air in DTA runs.

Previously formed Ni1x S was further oxidized giving rise to


another exotherm peaking at 731 C in Fig. 2. Quenched sam-
ples from 695 C to 785 C in the DTA runs were analyzed by
XRD to evaluate this exotherm, with their XRD patterns shown
in Fig. 13. The disappearance of Ni1x S and formation of heazle-
woodite (Ni3 S2 ) can be clearly seen on the basis of these two XRD
patterns. The formation of Ni3 S2 is indicative of the unquenchable
compound Ni3x S2 , which was suggested by Dunn and Kelly [1],
and was further conrmed in this study using SEM/EDS. As a result,
this exotherm is suggested to be the oxidation of Ni1x S forming
Ni3x S2 , represented by Reaction (9). The temperature discrep-
ancy between TGA and DTA runs can be observed by comparison
between the XRD patterns for TGA runs in Fig. 4 and those for DTA
runs in Fig. 13. The XRD patterns for 695 C in the DTA mode t
well with that for 733 C in the TGA mode. The formation of Ni3 S2
is only observed in the TGA sample quenched from 880 C, which
resemble the DTA sample quenched from 785 C. Due to this tem-
perature discrepancy, Reaction (9) did not occur by 785 C in the Fig. 14. BSE images of an oxidized pentlandite particles air-quenched from 880 C
TGA mode, which can be seen from the TGA curves and XRD results in the TGA run. Textures of the sulde cores are exhibited with enhanced contrast.
in Figs. 1 and 4, respectively.

(3 y)Ni1x S + (1 + 2x y)O2

(1 x)Ni3y S2 + (1 + 2x y)SO2 (9)

The following thermal event shows as a sharp peak at 813 C in


the DTA curve in Fig. 2, corresponding to an intensive O2 consump-
tion peak at 822 C in Fig. 1. This exotherm is believed to be the
oxidation of Ni3x S2 which has an incongruent melting point in the
vicinity of 800 C. Ion diffusion in the sulde was greatly increased
after Ni3x S2 melted, resulting in the accelerated oxidation reaction
rate. This exotherm was also reported by others [1,2]. Along with
NiO, substantial amount of NiSO4 was also formed in this exotherm,
which can be clearly seen in the XRD pattern at 880 C in Fig. 4 and
its chemical analysis results in Fig. 5. The very weak emission of
SO2 at 822 C in Fig. 1 compared with its corresponding intensive
O2 consumption peak also indirectly suggests the occurrence of
sulfation rather than mostly forming gaseous SO2 . As a result, this
exotherm is tentatively suggested as Reaction (10). Figs. 14 and 15
are BSE images of two partly oxidized pentlandite particles air- Fig. 15. BSE images of an oxidized pentlandite particles air-quenched from 880 C
quenched from 880 C, showing their morphological features. It in the TGA run.
comprises complex layers of iron oxides and a nickel sulde core.
D. Yu, T.A. Utigard / Thermochimica Acta 533 (2012) 5665 63

It is difcult to determine the stoichiometry of the iron oxides lay-


ers by EDS or EPMA when the oxide layers are either porous or
too thin. Their stoichiometries were tentatively suggested based
on other observations as follows. The outer dark porous layer of
iron oxide shown in Figs. 14 and 15 was not seen in any partly
oxidized pentlandite particles quenched from below 880 C. Same
phenomenon occurred to pyrrhotite. As illustrated in Figs. 8 and 9,
a similar dark porous layer of iron oxide was formed on the surface
when the sample was heated to 880 C. By checking XRD patterns,
it is obvious that magnetite re-occurred at 880 C. Thus this porous
layer is believed to be magnetite formed from the decomposition
of hematite represented by Reaction (11). There were conditions
causing the decomposition of hematite between 785 C and 880 C.
As is depicted in Fig. 10, the formation of Fe3 O4 is easier at higher
temperature since the predominant area for Fe3 O4 expands to the
right with the increase of temperature. It suggests that the already
formed Fe2 O3 would thermally decompose to Fe3 O4 if the O2 partial
pressure drops to a level at which Fe3 O4 is the thermodynamically Fig. 16. BSE image of an oxidized pentlandite particle air-quenched from 950 C in
stable phase. The melting of nickel sulde core above 800 C accel- TGA run.
erated its oxidation and would have brought down the oxygen par-
tial pressure within the bulk of the sample bed low enough to cause oxidized thereafter, leaving a hole in the oxidized pentlandite par-
the decomposition of Fe2 O3 forming Fe3 O4 . The porous nature of ticle.
the Fe3 O4 is possibly due to the volume reduction of around 2% for
Reaction (11). NiSO4 NiO + SO2 + 1/2O2 (12)
The sulde core in Fig. 14 was isolated and exhibited with
Ni3x S2(l) + (3.5 0.5x)O2 (3 x)NiO + 2SO2 (13)
enhanced contrast in its top right corner. This sulde core is com-
posed of alternating layers of two nickel sulde phases, one of There is another endotherm at 850 C
right after Reaction (10).
which is Ni3 S2 , the other is possibly Ni7 S6 . These two phases were Samples were collected at 825 C and 885 C from DTA runs for
probably formed by the exsolution of the molten sulde core dur- XRD analysis in order to evaluate this endotherm. XRD patterns
ing quenching, which provides evidence for the presence of the indicate the increase of NiO and decrease of NiSO4 with regard
unquenchable compound Ni3x S2 in Reactions (9) and (10). On the to their contents after this endotherm. It becomes clear that this
surface of the sulde core where O2 is accessible, a layer of NiSO4 endotherm is also the thermal decomposition of NiSO4 . This means
was formed via Reaction (10). The extent of Reaction (10) was even- a single reaction, which is represented by Reaction (12), gave rise to
tually retarded by the NiSO4 layer formed on the surface of the two endotherms in this test. The explanation for this is tentatively
molten sulde core due to the limited O2 diffusion rate through interpreted as follows. The melting of Ni3x S2 and the following
this dense sulfate layer to reach the surface of the sulde where intensive thermal oxidation represented by Reaction (10) raised
the reaction proceeded. the temperature of the sulde core dramatically well above the
furnace temperature, even higher than 942 C. Meanwhile, the for-
Ni3x S2(s) Ni3x S2(l) , and Ni3x S2(l) + O2 mation of NiSO4 layer on the molten sulde core from Reaction (10)
would eventually terminate the oxidation reaction by inhibiting the
NiO + NiSO4 + SO2 (10) O2 diffusion. The local temperature of the sulde core was already
raised high enough for the quick decomposition of the NiSO4 layer
around the core, leading to the endotherm at 850 C. With the
6Fe2 O3 4Fe3 O4 + O2 (11) proceeding of the DTA run, while the furnace temperature was
increasing, the local temperature of the sulde core dropped due
An endotherm occurred at 942 C, represented by a valley in to the termination of the exothermic Reaction (10) as well as the
the DTA curve in Fig. 2. It correlates to a quick mass loss and occurrence of the endothermic Reaction (12). Reaction (12) stopped
offgas peaks at 917 C. This endotherm is easily deduced on the as a consequence due to this temperature drop, which is indicated
basis of the chemical analysis results in Fig. 5, where water sol- by the termination of the endotherm at 850 C. The decomposition
uble Ni species, which should be NiSO4 , dropped dramatically in of NiSO4 resumed when the temperature was raised by the heating
the temperature range from 880 C to 950 C. It is thus appar- element to 942 C, giving rise to the second endotherm.
ent that this endotherm is the thermal decomposition of NiSO4 , Sulfates formation and decomposition is the second focus of this
leading to the quick mass loss and emission of SO2 . This would study. As can be seen in Fig. 5, sulfation and sulfates decomposition,
be simply represented by Reaction (12). Evidence also suggests which played a key role in the sample mass change, spanned wide
the occurrence of another reaction along with the decomposition temperature ranges. Massive sulfation started from around 500 C,
of NiSO4 , which is expressed as Reaction (13). The NiSO4 layer, leading to the increase of mass till 733 C. Sulfates decomposition
which covered the remaining molten sulde core and protected prevailed at relatively higher temperatures, resulting in the mass
the core from being oxidized, was decomposed and exposed the loss after 733 C. It is surprising to see that the sulfation for Cu is
molten sulde core to the oxidative atmosphere, leading to the over 85% at 785 C. It is also worth mentioning that Mg contain-
complete oxidation of the remaining sulde through Reaction (13). ing species, which is silica ux materials in the concentrate, is also
The assignment of this reaction is supported by the occurrence of prone to sulfation. This is illustrated by the increasing sulfation
the corresponding O2 consumption peak in Fig. 1, as well as the for Mg to over 50% at 950 C. NiSO4 is relatively hard to produce,
disappearance of Ni3 S2 at 950 C in the XRD patterns. Fig. 16 is a which is due to its dense nature tending to inhibit further sulfa-
BSE image of an oxidized pentlandite particle air-quenched from tion. The quick increase in NiSO4 from 785 C to 880 C is because
950 C, showing the outcome of Reactions (12) and (13). With- the melting of nickel sulde leads to the acceleration of the kinet-
out the shield of the NiSO4 layer, the molten sulde core was ics for sulfation, as has been discussed earlier. The percentage of
64 D. Yu, T.A. Utigard / Thermochimica Acta 533 (2012) 5665

Table 5
Summary of the reaction sequence for the oxidation of the Raglan concentrate at
15 C/min in air.

450498 Ca 2CuFeS2 + 7O2 CuOCuSO4 + Fe2 O3 + 3SO2


450509 Ca 2Fe1x S + (3.5 1.5x)O2 (1 x)Fe2 O3 + 2SO2
350605 Ca (Ni,Fe)9 S8 + O2 (Ni,Fe)1x S + Ni1x S + Fe2 O3 + SO2
350509 Ca (Ni,Fe)9 S8 + O2 (Ni,Fe)3 S4 + Fe2 O3
509605 Ca (Ni,Fe)3 S4 + O2 (Ni,Fe)1x S + SO2
468700 Cb (Ni,Fe)1x S + O2 Ni1x S + Fe2 O3 + SO2

509733 Cc
MeS + 2O2 MeSO4
for Fe
or
509785 Cc
MeO + SO2 + 1/2O2 MeSO4
for Cu
509785 Cc
for Co
509880 Cc
for Ni

>495 Cc MgO + SO2 + 1/2O2 MgSO4


731 Cb (3 y)Ni1x S + (1 + 2x y)O2 (1 x)Ni3y S2 + (1 + 2x y)SO2

Fig. 17. BSE image of a particle composed of mixture of NiSO4 and MgSO4 quenched 733785 Cc
from 880 C. for Fe
MeSO4 MeO + SO2 + 1/2O2
>785 Cc for
Co
iron sulfates formation is low, which is probably caused by the low 785950 Cc
stability of iron sulfates. Sulfate formation can take place by two for Cu
possible reaction routes, which can be shown by Reactions (14) 942 Cb for Ni
and (15) in general [20]. The former is the direct oxidation of sul- 813 Cb Ni3x S2(s) Ni3x S2(l) , and Ni3x S2(l) + O2 NiO + NiSO4 + SO2
de, whereas the latter is the formation of sulfur trioxide from SO2 >813 Cb 6Fe2 O3 4Fe3 O4 + O2
and O2 , followed by the sulfation of the oxide with sulfur trioxide. 942 Cb Ni3x S2(l) + (3.5 0.5x)O2 (3 x)NiO + 2SO2

No attempts have been made to determine by which route these a


Temperature determined from TGA results.
b
various sulfates were formed in this study. Sulfates decomposition Temperature determined from DTA results.
c
Temperature determined from ICP results.
can be generally represented by Reaction (16). Temperature ranges
for the sulfates formation and decomposition for various species
can be seen in Fig. 5 and will be summarized later. taking place at a certain depth level in the bed, the O2 partial pres-
It is also found from this study that at relatively high sure must had dropped to near zero in the area below the reaction
temperatures, various metal sulfates tended to form sulfates mix- level. As a result, the reaction front where most oxidation reactions
ture. Fig. 17 illustrates a particle of NiSO4 MgSO4 mixture in were taking place propagated downwards, leaving the oxide prod-
the calcine quenched from 880 C. Mixtures of CuSO4 MgSO4 , ucts above and the materials below unaffected. The thickness of
NiSO4 CuSO4 MgSO4 , and even Fe2 (SO4 )3 NiSO4 CuSO4 MgSO4 the reaction front must be thin compared with that of the whole
were also found to have formed. This is possibly because sulfates sample bed.
of individual particles which have physical contact tend to diffuse The progress of reactions can be envisioned on the basis of the
into each other and form mixture. The formation of sulfates mix- mass change curves in Fig. 18. At the beginning of oxidation, the
ture increased the thermal stability of each individual sulfate by reactions occurring were mostly oxidation reactions releasing con-
lowering its activity, resulting in an increase in its decomposition siderable amount of SO2 , leading to the initial quick mass loss. O2
temperature. from above the sample bed diffused through the oxidized bed and
reached the reaction front, where most of it was consumed, releas-
MeS + 2O2 MeSO4 (14)
ing SO2 as a gaseous product. The resulting SO2 needed to diffuse
MeO + SO2 + 1/2O2 MeSO4 (15)

MeSO4 MeO + SO2 + 1/2O2 (16)

For the oxidation of the Raglan concentrate at 15 C/min in air,


the reaction scheme is summarized in Table 5 based on this study.
A set of TGA runs was also performed to evaluate the effect of
sample size on its oxidation kinetics. Samples were heated up in
argon to 760 C and oxidized by switching the feeding gas to 1 L/min
air and maintaining this temperature. Mass changes in weight per-
cent were plotted against oxidation time, as shown in Fig. 18. At
the onset of the oxidation, mass changes were normalized to 0. The
initial rates of mass change at the onset of oxidation in both mg/s
and weight%/s were plotted as a function of both the sample size
and the sample bed thickness in the crucible in Fig. 19. For the runs
with sample sizes larger than 5 mg, the initial rate of mass change
(mg/s) is roughly the same and independent of the sample size.
This indicates that reactions did not take place uniformly within
the bulk of the sample, but instead occurred gradually downward
from the top surface of the sample. This happened based on the fact
that the diffusion of O2 through the bed played an essential part
in the progress of reactions. Due to the O2 consumption reactions Fig. 18. Mass change in wt% vs. time with the variation of sample size.
D. Yu, T.A. Utigard / Thermochimica Acta 533 (2012) 5665 65

well as the formation of nickel sulfate, which lowered the O2 partial


pressure in the bulk of the sample bed, leading to the decompo-
sition of Fe2 O3 forming Fe3 O4 . Decomposition of NiSO4 at 942 C
exposed the remaining nickel sulde core to the oxidative atmo-
sphere, leading to the complete oxidation of the sulde. Sulfates
of various metals started to form at around 500 C probably due to
the emission of SO2 which favors the sulfation by providing a suit-
able atmosphere. These sulfates tended to decompose at higher
and varying temperatures, depending on their individual thermal
stability. Mixtures of sulfates were formed at relatively high tem-
perature, which increased their individual thermal stability.
The reaction rate controlling step was the O2 diffusion through
the bed of sample for TGA runs with sample sizes larger than 5 mg.
The reaction front of around 125 m in depth held most of the oxi-
dation reactions and propagated downwards in the sample bed due
to the limited access of O2 .

Acknowledgments
Fig. 19. Initial rate of mass change vs. sample size and bed thickness.
Funding by the Centre for Chemical Process Metallurgy and Nat-
upwards through the oxidized bed before it was swept away by the ural Sciences and Engineering Research Council (NSERC) of Canada
feeding gas. The resulting counter diffusion action of SO2 and O2 , is gratefully acknowledged. We also wish to thank G. Kretschmann
as well as the presence of the oxides as catalyzes for the oxidation and Y. Liu of the Geology Department of the University of Toronto
of SO2 forming SO3 , provided an ideal atmospheric environment for their assistance in the characterization of the samples.
for the sulfation of oxides. With the downward propagation of the
reaction front, the thickness of the oxidized bed increased, giving References
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