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Thermochimica Acta
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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.
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
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.
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. 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].
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.
(3 y)Ni1x S + (1 + 2x y)O2
Table 5
Summary of the reaction sequence for the oxidation of the Raglan concentrate at
15 C/min in air.
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
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
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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