Advanced Powder Technology 30 (2019) 451–460

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Advanced Powder Technology

journal homepage: www.elsevier.com/locate/apt

Original Research Paper

Utilization of limonitic nickel laterite to produce ferronickel concentrate

by the selective reduction-magnetic separation process
Deqing Zhu, Liaoting Pan, Zhengqi Guo ⇑, Jian Pan, Fang Zhang
School of Mineral Processing and Bioengineering, Central South University, Changsha, PR China

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

Article history: Attempts to economically upgrade low nickel content laterite ore face a number of challenges, including
Received 28 January 2018 limited ability to beneficiate the ore prior to processing due to its complex association and dissemination
Received in revised form 20 September structure. Limonitic nickel laterite, characterized by its relatively high iron grade and low nickel content,
2018
is very difficult to upgrade. The current work explores improving the beneficiation of nickel from limo-
Accepted 25 November 2018
nitic laterite ore through interaction of silica and calcium sulfate in a selective reduction-wet magnetic
Available online 29 November 2018
separation process. The results show that the ferronickel concentrate assaying 5.0% Ni can be obtained
at a nickel recovery of 95.9%, when limonitic laterite ore is reduced at 1250 °C for 60 min with the addi-
Keywords:
Limonitic laterite ore
tion of 3 wt% CaSO4, 8 wt% silica and 3 wt% graphite. The mechanism of additives in promoting the selec-
Silicate tive reduction of nickel laterite ore was also investigated by XRD, VSM, SEM-EDS and EPMA. The silicate
Calcium sulfate reacted with iron oxide to form the liquid, which decreased the iron metallization ratio. S2 from the ther-
Reduction roasting-magnetic separation mal decomposition of CaSO4 in a strong reducing atmosphere significantly promoted c Fe–Ni particle
Selective reduction growth by formation of an Fe-FeS eutectic with a low melting point.
Ó 2018 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Technology Japan. All rights reserved.

1. Introduction extremely difficult to beneficiate the nickel laterite ores by tradi-

Nickel is a commercially important base metal that is widely
used in modern industries and basic sciences, such as new materi-
als, chemical transformation, stainless steel and batteries [1–7]. It
is estimated that stainless steel production accounts for approxi-
mately 65 percent of total nickel consumption in the world [8].
The rapid development of these industries, particularly stainless
steel manufacture, has significantly increased the demand. Nickel
is extracted from two main types of ores, sulfide ore and oxide
ore; about 70% of the world’s nickel exists in the form of nickel
laterite [9,10]. With the increasing demand for nickel and the
depletion of high-grade sulfide ores, nickel laterite ore processing
has attracted attention.
Laterite ores can be divided into three categories: limonite
(oxide), nontronite (clay), and saprolite (silicate) [11,12]. Nickel
laterite is finely disseminated in these low-grade nickel laterite
ores and closely associated with iron oxide and silicate minerals
as isomorphous substitution for iron and magnesium in the lattice
[12,13]. Because of a very complex mineralogical structure, it is
⇑ Corresponding author at: Peace Building, No. 240, School of Minerals Processing
& Bioengineering, Changsha, Hunan, PR China.
E-mail address: guozqcsu@csu.edu.cn (Z. Guo).
tional physical separation processes. Efforts have focused on
improving the beneficiation of nickel from laterite ore by chemical
processes, such as high-pressure acid leaching (HPAL) [14,15],
reduction roasting ammonia leaching (Caron process) [16,17],
atmospheric leaching [18–20], the rotary kiln electric furnace
(RKEF) process [21,22] and the direct reduction-magnetic separa-
tion process [23–29].
The direct reduction process to upgrade this type of complex
and refractory nickel laterite ore has been a topic of metallurgical
interest. In the reduction roasting process, the nickel-bearing min-
erals are reduced to metallic nickel while controlling iron oxide
reduction. Crude Fe-Ni alloy, the finally product, is separated from
large quantities of iron-bearing gangue by the magnetic separation
process. To obtain high-nickel-grade ferronickel concentrate, vari-
ous additives, including CaCO3, CaO, Na2CO3, Na2SO4, and NaCl
[30–34], are employed to improve the selective reduction roasting.
The strengthening mechanism of additives in the selective
reduction of nickel laterite ore has been investigated. Research
suggests that the addition of sulfur compounds significantly pro-
motes ferronickel particle growth at low temperature and sup-
presses the reduction of iron oxide due to the formation of
troilite (FeS) [32,35]. Studies also indicate that sodium salt and
calcium oxide can destroy the laterite complex structure by

https://doi.org/10.1016/j.apt.2018.11.024
0921-8831/Ó 2018 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
452 D. Zhu et al. / Advanced Powder Technology 30 (2019) 451–460

reacting with gangues, enhancing the reduction of iron oxide and
promoting the growth of metallic iron grains, which is beneficial
in upgrading the nickel laterite [31,36–40]. Therefore, it is antici-
pated calcium sulfate enables to bring S and CaO simultaneously
to play a role of both sulfurizing agent and calcium flux in reduc-
tion roasting process.
Moreover, emphasis has been on the process of nontronite and
saprolite laterite ores, whereas relatively few studies have been
carried out on the reduction roasting process of limonitic laterite
ore with a high iron grade over 40%, probably since that non-
selective reduction of limonite laterite ore yields ferronickel pro-
duct powder with a low nickel grade. Fortunately, the addition of
silica might be effective in suppressing the reduction of iron oxide
due to the formation of fayatite. It may benefit to selective reduc-
tion of limonite laterite.
This paper describes an investigation conducted to improve the
beneficiation of limonite laterites by the reduction roasting-wet
magnetic separation process. Calcium sulfate and silica were
employed to improve upgrade of limonite nickel laterite. The
intensification mechanisms of the interaction of silica and calcium
sulfate on reduction and magnetic separation were revealed by
XRD, VSM, optical microscopy and environmental scanning elec-
tron microscopy (ESEM).
2. Experimental
2.1. Materials
2.1.1. Nickel laterite
The nickel laterite ore samples used in the study were collected
from Indonesia. The chemical composition of the sample shown in
Table 1 indicates that the ore sample is characterized by its rela-
tively high iron grade, i.e. 40.1% total iron, and low Ni content (only
0.97% Ni). The laterite ore sample is mainly composed of goethite,
hematite and lizardite.
Goethite, as the dominate phase within the laterite ore, is often
closely associated with silicate minerals, quartz and maghemite, as
shown in Fig. 1. In the earthy goethite matrix, Al and Si are
detected in Fig. 1(c) and (d), as well as Fe and Ni. Earthy goethite
mineral in the analysed areas contain high Ni in association with
high Fe and Si concentrations, which indicates nickel is rich in
goethite accompanied by intergrowth of silicate minerals. More-
over, the presence of Ni shows likelihood of being tracked with
Si and Al, whereas Fe exhibits the antithetical behaviour. Silicate
and goethite are the two Ni host phases, and they occur in associ-
ation and dissemination (as shown in Fig. 2). Therefore, nickel is
very difficult to upgrade effectively by traditional physical

Table 1
Chemical analysis of nickel laterite ores (wt%).
*
Element Fetotal FeO Ni Co Cr2O3 MnO SiO2 Al2O3 CaO MgO S P LOI
Content 40.09 1.14 0.97 0.09 2.86 0.82 12.55 6.52 1.51 4.65 0.035 0.0063 13.23
*
LOI: Loss on ignition.

Fig. 1. EPMA analysis of earthy goethite in laterite nickel ore.

 D. Zhu et al. / Advanced Powder Technology 30 (2019) 451–460 453

Fig. 2. Microstructure of nickel laterite (h-hematite, M-maghemite, G-goethite, L-Lizardite).

beneficiation processes due to the low Ni grade and complicated
micro structure of limonitic laterite ore.
2.1.2. Reductant
Graphite was used as the reductant. The proximate analysis of
the reducing graphite is presented in Table 2. It was crushed and
screened to a size of
0.074 mm, served as the reductant.
2.1.3. Additives
The silica and calcium sulfate used in the study were of chem-
ical grade with particle sizes less than 0.074 mm.
2.2. Experimental methods
2.2.1. Reduction roasting and magnetic separation
The experimental flowsheet is shown in Fig. 3. First, the laterite
ore was crushed and ground to 80 wt% passing 0.074 mm. The
ground sample was mixed manually for approximately 10 min
with the required amounts of additives and graphite. Then, the
uniformly mixed raw materials were loaded into cylinders with a
diameter of 10 mm and depth of 10 mm to form briquettes, which
were subsequently dried at 105 °C for at least 3 h in a drying oven.
Approximately 60 g of dry briquettes loaded in a graphite crucible
was roasted between 900 °C and 1300 °C for a predetermined
time in a muffle furnace with inbuilt temperature control software
(furnace configuration dimension: 200  250  120 mm; MoSi2
heating element). After reducing, the crucible was removed from
the furnace, and the reduced briquettes were cooled to ambient
temperature under the protection of nitrogen with 0.5 L/min flow-
rate in preparation for the subsequent beneficiation process.
Prior to grinding, the reduced briquettes were crushed to a par-
ticle size less than 1 mm. A 20 g sub-sample of the cooled bri-
quettes was ground to approximately 90 wt% passing 0.043 mm
in an XMQ240  90 ball mill. The mix slurry was dressed by one-
stage wet magnetic separation for 10 min in an XCGS-73 Davies
Magnetic Tube at a magnetic field strength of 1800 G. The wet con-
centrates and tailings were filtered and dried at 75 °C in a vacuum
oven for 2 h. After that, both dry magnetic and non-magnetic prod-
ucts were weighed and chemically analysed; the yield and grade of
Fe and Ni were calculated, respectively. In particular, Fe and Ni
Additives Nickel laterite Reductant
Mixing
Roasting

Crushing & Grinding

Table 2
Proximate analysis of reductant graphite and chemical composition of its ash (Air
dried base, wt%).

Industrial analysis/%
Magnetic separation
Fixed carbon Ash Moisture Volatile matter
98.7 0.2 0.6 0.5
Chemical composition of the ash/% Magnetic
Tailings concentrates
SiO2 Al2O3 CaO MgO Fe2O3 K2O Na2O P S
40.56 28.89 8.34 9.98 9.32 1.56 1.29 0.02 0.04
Fig. 3. Experimental procedure.
454 D. Zhu et al. / Advanced Powder Technology 30 (2019) 451–460

content in roasted products, magnetic and non-magnetic products
were chemically analysed by chemical titration, and the detail
method as seen in reference [35].
2.2.2. Material characterisation
The EPMA analyses of the sample were carried out in the Centre
for Microscopy and Microanalysis (CMM) using a JEOL Super Probe
8800L equipped with wavelength-dispersive spectrometer. The
mineral phases of the samples were investigated using an X-ray
diffractometer (XRD, RIGAKU, D/Max-2500). Microstructures of
reduced briquettes were determined using a Leica DMLP optical
microscope, an FEI Quata-200 scanning electron microscope and
an EDAX32 genesis spectrometer. SEM images were recorded in
backscatter electron modes operating in low vacuum mode at
0.5 Torr and 20 keV. The metallic particle size and size distribution
of reduced briquettes were measured by Image J software. Equilib-
rium compositions and phase diagram were obtained by FactSage
7.0 software. The changes of the sample magnetism were investi-
gated by VSM (Vibration sample magnetometer, BHV-50HTI, Riken
Keiki, in Japan).
3. Results and discussion
3.1. Thermodynamic analysis
Previous studies have reported that in the selective reduction
process of nickel laterite ore, nickel oxide is reduced prior to iron
oxide, and the step of further reducing wustite to metallic iron
can be inhibited in a weak reduction atmosphere by adjusting
the dosage of reductant to attain superior Fe-Ni alloy with high
grade nickel [41,42]. In this paper, we just emphatically conducted
thermodynamic analysis of iron oxide reaction with silicate and
calcium sulfate.
3.1.1. Thermodynamic analysis of iron oxide reactions with silicate
oxide
The generation of metallic nickel should be maximized and the
further reduction of the wustite appropriately suppressed to avoid
excessive metallic iron formation in the reduction process. Silica
was employed to achieve the desired results.
Previous studies have reported that the reaction between silica
and wustite forms fayalite (2FeOSiO2). The fayalite, as one type of
complex iron compound, is more difficult to reduce to metallic iron
than wustite [37,38]. As seen from Fig. 4(A), many low-melting-
point minerals may be generated in the FeO-SiO2 system, such as
2FeOSiO2 (melting point 1205 °C), 2FeOSiO2-FeO (melting point
1177 °C), and 2FeOSiO2-SiO2 (melting point 1178 °C). Fig. 4(B)
shows the simulated results obtained using FactSage 7.0 software
based on the equilibrium compositions in an inert environment
at different values of SiO2 mass%, which further shows that the
addition of silica improves liquid formation and suppresses the
generation of metallic iron.
Furthermore, in view of dynamic, the diffusion rate of the
reduction gas is decreased significantly once excessive liquid phase
generates in reduction process, resulting in a weaker reduction
atmosphere and lower rate of reduction reactions [43,44].
3.1.2. Thermodynamic analysis of iron oxide reactions with calcium
sulfate
The main reactions during selective reduction of calcium sulfate
can be represented by the following equations:
2CaSO4 (s) = 2CaO(s) + 2SO2 (g) + O2 (g) ð1Þ
2CaSO4 (s) + 2CO(g) = 2CaO(s) + 2SO2 (g) + 2CO2 (g) ð2Þ
2CaSO4 (s) + C(s) = 2CaO(s) + 2SO2 (g) + CO2 (g) ð3Þ
2CaSO4 (s) + 6CO(g) = 2CaO(s) + S2 (g) + 6CO2 (g) ð4Þ
2CaSO4 (s) + 3C(s) = 2CaO(s) + S2 (g) + 3CO2 (g) ð5Þ
The standard Gibbs free energy of the above reactions was cal-
culated and the results are shown in Fig. 5. As shown in Fig. 5, the
above reactions except for Eq. (3) can proceed spontaneously
above 1000 °C. The reduction of CaSO4 by CO to form CaO, S2 and
CO2 (Eq. (4)) is predominant since the standard Gibbs free energy
of Eq. (4) is more negative than that of others. Although a propor-
tion of the sulfur might escape from the system as gaseous S2 dur-
ing the laterite ore reduction, there is a strong possibility that S2

100
1800
A B
90
CO2 SiO2
1700 80 CO

70
1600 Cristobalite+Liquid Liquid
Mass fraction/%
T(°C)

60
1500 Liquid
1470°C 50

1400 40

Tridymite+Liquid 30
1300
Fe
Iosiderite 20
1205°C
1200 1178°C +Liquid
10
Tridymite+Fayalite Iosiderite+Fayalite
1100 0
SiO2 0.2 0.4 0.6 Fe2SiO4 0.8 FeO 0 2 4 6 8 10 12 14
FeO/(FeO+SiO2) Mass SiO2/wt.%

Fig. 4. Thermodynamic analysis of iron oxides with silica.

 D. Zhu et al. / Advanced Powder Technology 30 (2019) 451–460 455

100 100
Ni Recovery
800 90

Eq.(8)
Eq.(3) 80 90
400 70

Recovery rate (%)

60 80

Grade (%)
0 50
Eq.(5) Eq.(2) TFe
70

-400 Eq.(3) 5
60
Eq.(4) 4
-800 3
50
Fe Recovery
2 TNi

0 400 800 1200 1600 2000

Temperature (°C)
Fig. 5. Gibbs energy of reactions of CaSO4 during selective reduction.
may react with those minerals due to the encapsulation of the bri-
quette within the crucible and the porous structure of goethite and
silicates after the dehydration reaction.
The equilibrium compositions of the Fe2O3-SiO2-CaSO4-C reac-
tion system, which are calculated with different mass fractions of
CaSO4 at 1250 °C, are shown in Fig. 6. The generation of metallic iron
is suppressed and the liquid phase content is increased with an
increase in the ratio of CaSO4. Simultaneously, the amount of FeS
is increased in the liquid phase with an increase of CaSO4, which is
possibly because S2 from the decomposition of CaSO4 in the reduc-
tion atmosphere, reacts readily with metallic iron to form FeS.
3.2. Selective reduction and magnetic separation of laterite ore
1 40
1100 1150 1200 1250 1300 1350
Reduction temperature (°C)
Fig. 7. Effect of reducing temperature on nickel and iron concentration of laterite
(Roasting for 60min with 3% reductant, 3% additive and 8% silica).
reduction temperature from 1100 °C to 1250 °C, the nickel grade
and recovery were elevated from 1.6% and 77.1% to 5.0% and
95.1%, respectively. When the reduction temperature was further
increased, the nickel grade and recovery were steady. Conversely,
once the reduction temperature was beyond 1200 °C, iron recovery
dropped dramatically. This is because the too high temperature
may lead to excessive liquid phase, which impedes the internal dif-
fusion of reducing gas in the direct reduction process [44]. There-
fore, a reduction temperature of 1250 °C was recommended for
further reduction tests.

3.2.1. Effect of reduction temperature 3.2.2. Effect of reduction duration

Fig. 7 shows the nickel and iron enrichment in the concentrate The laterite briquettes were reduced for various durations to
as a function of the reduction temperature. With an increase in the determine the effect of reduction duration on magnetic separation

100 100
A CO2 B
90 90 CaO

80
CO 80
Mass fraction of liquid/%

70 70
SiO2
Mass fraction/%

60 60

50
Liquid 50

40 40

30 30

20 20
Fe FeO
10 10
FeS
0 0
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10
CaSO4/wt.% CaSO4/wt.%

Fig. 6. Calculated mole fractions of main products at different Ca2SO4 Wt.% (8 wt% C, 1250 °C).
456 D. Zhu et al. / Advanced Powder Technology 30 (2019) 451–460

and the results were shown in Fig. 8. By increasing the reduction
duration from 20 min to 60 min, the nickel grade and recovery
were improved from 4.1% to 5.0% and 78.7% to 95.6%, respectively.
When the reduction duration was over 80 min, the nickel concen-
tration indexes were apt to deteriorate. This is because if the
reduction duration is excessive long, the reduction agent would
be rapidly exhausted at this high temperature, resulting in re-
oxidation of generated metallic nickel. Therefore, the nickel recov-
ery and nickel grade were decreased.
A short reduction duration is unfavourable for the aggregation
and growth of fine Fe-Ni particles, whereas an excessive reduction
duration results in more metallic iron generation, which dilutes the
nickel concentration. A reduction duration of 60 min is recom-
mended to obtain an optimum nickel grade of 5.1% and a nickel
recovery of 95.6% in the final product.
3.2.3. Effect of reductant dosage
The influences of inner reductant dosage on the beneficiation of
nickel and iron are shown in Fig. 9, indicating that with an increase
in reductant dosage from 1% to 6%, the nickel grade decreased from
7.9% to 2.6% and the iron grade increased from 68.2% to 82.8%. Both
100
95
90 Ni Recovery
85
80
TFe
75
iron and nickel recoveries were increased in the tested range. The
data also shows that nickel grade and recovery were very sensitive
to reductant dosage. With the addition of graphite, the reducing
atmosphere is improved and reduction reactions are accelerated
to promote iron and nickel oxide reduction. However, the reduc-
tion of excessive iron oxides is harmful for the concentration of
nickel in the selective reduction process. The optimum reductant
dosage is recommended to be 3%.
3.2.4. Effect of addition of silica and CaSO4
The magnetic separation results of laterite briquettes reduced
with variable dosages of calcium sulfate (ranging between 0%
and 5%) are shown in Fig. 10. Nickel grade and recovery increased
with a gradual addition of CaSO4. Nickel grade increased from 2.9%
to 5.1%, while nickel recovery increased from 88.3% to 98.7%. How-
ever, with CaSO4 dosage varying from 0% to 5%, iron recovery had a
sharp downward trend, although iron grade of the concentrate
increased gradually.
The descending iron recovery indicates that CaSO4 can suppress
the complete metallization of iron oxide and achieve a greater
selective enrichment of Ni. According to thermodynamics calcula-
tions, CaSO4 decomposed to S2, O2 and CaO instead of SO2 and CaO
under the reducing atmosphere. The sulfur is enriched on the sur-
100
face of metallic particles and enables to decrease the surface ten-
sion of metallic particles to promote their growth [22,40–42].
90 Newly formed sulfur, exhibiting high activity, reacted readily with
iron oxides to form iron sulfide (FeS), And the reaction was
80 expressed as follows:
3S2 (g) + 4FeO = 4FeS + 2SO2 (g) ð6Þ
Recovery (%)

70
70
Grade (%)

FeS is non-magnetic, so the formation of FeS decreased the iron

60 metallic rate and was beneficial for nickel enrichment through
5 TNi
magnetic separation. The results also is consistent with the signif-
4 50 icant decrease of iron recovery and increase of nickel grade as the
3 addition of dosage seen in Fig. 10.
40
2 Fe Recovery
Reduction tests were further carried out with different addi-
tions of silica to determine its effect on magnetic separation.
1 30
Fig. 11 shows that nickel grade, nickel recovery and iron grade
0
increased significantly with the progressive addition of silica from
20 40 60 80 100 120
Reduction duration (min) 0 to 8%. In contrast, iron recovery decreased in the test. Based on
the above results of thermodynamic analysis, the addition of silica
Fig. 8. Effect of reduction duration on nickel and iron concentration of laterite is beneficial to generate fayalite and impede the reduction of iron
(Roasting at 1250 °C with 3% reductant and 3% additive and 8% silica).
oxides. When further increasing the dosage of silica, all indexes

85 100
100 100

90 Ni Recovery 90 Ni Recovery
95
80
80 TFe
80
Recovery rate (%)

TFe
70 90
Recovery rate (%)

70
Grade(%)

60
Gate (%)

50
60
8 5
TNi Fe Recovery 40
55
6
30 4
TNi 50
4
20 3 Fe Recovery 45
2
10
0 2 40
1 2 3 4 5 6 0 1 2 3 4 5
Reductant dosage （%） CaSO4 (%)

Fig. 9. Effect of reductant dosage on nickel and iron concentration of laterite Fig. 10. Effect of the dosage of calcium sulfate on nickel and iron concentration of
(Roasting at 1250 °C for 60min with 3% additive and 8% silica). laterite (Roasting at 1250 °C for 60min with 8% silica and 3% reductant dosage).
 D. Zhu et al. / Advanced Powder Technology 30 (2019) 451–460 457

85 100

80

75 TFe
95
70 Ni Recovery

Recovery rate (%)

65
Grade(%)

90

7
6 70
Fe Recovery
5
60
4
3 TNi 50
2
40
1
0 2 4 6 8 10
Silica dosage (%)

Fig. 11. Effect of the dosage of silica on nickel and iron concentration of laterite
(Roasting at 1250 °C for 60min with 3% CaSO4 and 3% reductant dosage). Fig. 12. X-ray diffraction pattern of laterite reduction samples (Roasting at 1250 °C
for 60min with 3% reductant dosage).

were kept steady. Therefore, 8% silica was selected as the optimum

dosage of silica addition for selective reduction of nickel laterite.
3.3. Analysis of magnetic separation final product
Through the above experiments, a satisfactory product was
obtained under the optimum conditions of briquetting the nickel
laterite ore mixture with 8% silica, 3% calcium sulfate, and 3%
reductant by reducing the briquettes at 1250 °C for 60 min, grind-
ing the reduced briquettes up to 100% passing 0.074 mm, and con-
ducting magnetic separation at 1800 G. The chemical composition
of the final concentrate is shown in Table 3.
Nickel was successfully enriched in the concentrate with mass
yield of only 25%, which means that slag in the subsequent melting
process could be reduced by over 75%, leading to higher output and
lower electricity consumption.
peak of iron sulfide was not observed in the XRD pattern because of
its low content within the reduced briquettes [45–47].
Moreover, when further adding 8% silica, the peak of the metal-
lic iron phase became much weaker, and that of fayalite and wus-
tite appeared to increase and be stronger, which further confirmed
the function of silica in the selective reduction process. The results
also agreed well with thermodynamic analysis.
The magnetic hysteresis loops of the products roasted under
different conditions were analyzed by VSM, and the results are
shown in Fig. 13. As presented in Fig. 13, the saturation magnetiza-
tion (Ms) of roasted samples without CaSO4 and silica was about
29.97 emu/g, while the value decreased to 19.62 emu/g and
12.18 emu/g when adding CaSO4 and both CaSO4 and silica, respec-
tively, which is to be expected from the decrease of metallic iron
content in the roasted samples with the addition of CaSO4 and

3.4. Mechanisms on selective reduction of laterite ore 40

With 8% silica and 3% CaSO4
29.97 emu/g
3.4.1. Phase transformation of limonitic laterite during the reduction With 3% CaSO4
process Without CaSO4 and silica
19.62 emu/g
To reveal the mechanism of silica and CaSO4 to improve selec- 20
tive reduction of limonitic nickel laterite, XRD analysis was carried 12.18 emu/g
M/(emu/g)

out to demonstrate the difference in mineral compositions

between three types of reduced briquettes and the results are
0
shown in Fig. 12. The XRD pattern of the roasted ore without silica
and CaSO4 exhibited a high content of kamacite, as shown in Fig. 12
(a), which was caused by the reduction of more iron oxides. Fer-
ronickel concentrate was manufactured from the reduced ore at -20
a high iron recovery and low Ni grade (as shown in Fig. 10). With
the addition of 3% CaSO4 in the nickel laterite ore, the peak inten-
sity of kamacite in the reduced ore decreased because S2 from the
decomposition of CaSO4 reacted with iron oxides to form non- -40
-15000 -10000 -5000 0 5000 10000 15000
magnetic FeS, leading to decrease of iron recovery and significant
Applied magnetic field/(Oe)
increase of nickel grade. Through thermodynamic analysis, the
addition of CaSO4 improved the formation of liquid; hence, the fay- Fig. 13. The magnetic hysteresis loops of roasted products (Roasting at 1250 °C for
alite may precipitate from the liquid during cooling. However, the 60min with 3% reductant dosage).

Table 3
Chemical analysis of nickel concentrate (wt%).

Element Fetotal Ni Cr MnO SiO2 CaO MgO Al2O3 P S

Concentrate 81.66 5.02 0.38 0.28 3.53 0.96 0.57 2.86 0.016 0.29
458 D. Zhu et al. / Advanced Powder Technology 30 (2019) 451–460

Fig. 14. Microstructure of reduced sample (1-Chromite, 2-Spinel, 3-Quartz, 4-Fayalite, 5-Wustite, 6-cFe-Ni) (Roasting at 1250 °C for 60min with 8% silica, 3% reductant
dosage and with 3% calcium sulfate).

Fig. 15. Effect of calcium sulfate additives on metallic particle size (Roasting at 1250 °C for 60min with 8% silica and 3% reductant dosage).
 D. Zhu et al. / Advanced Powder Technology 30 (2019) 451–460
silica. The VSM results are in accordance with the X-ray diffractom-
etry analyse, further verifying interactions between CaSO4 and sil-
ica can control the reduction of iron oxide and realize the selective
reduction of nickel over iron.
3.4.2. Microstructure of the reduced sample
The microstructure of the reduced sample is shown in Fig. 14.
The phases observed in Fig. 14 include kamacite, quartz, fayalite,
spinel, wustite and chromite. The reduced sample margin was
saponaceous, which shows that the roasted ore was molten in
the reduction roasting process. The cFe-Ni particles mainly dis-
tributed around the edge of fayalite and spinel. Many ferrous min-
erals, such as fayalite, spine and wustite, were formed, indicating
the formation of metallic iron was inhibited and selective reduc-
tion of nickel laterite was realized. These results are also consistent
with the previous thermodynamic analysis of iron oxide reactions
with CaSO4 and silica which shows that the addition of calcium
sulfate during laterite ore reduction can suppress the reduction
of iron oxide to its metallic phase.
3.4.3. Growth of metallic particle in the reduction process
Fig. 15 presents the micrographs of reduced briquettes in the
absence and presence of CaSO4, respectively. The metallic particles
aggregated together and became larger than those without CaSO4.
The growth of ferronickel particles is extremely important for
the subsequent magnetic separation process because if they are
too small, there is insufficient mineral liberation from the non-
magnetic gangue in the grinding operation. Generally, when the
metallic particles have a particle size less than 10 lm, they are very
difficult to liberate during the milling process and very difficult to
recover even if liberated [48–50]. Through image J software analy-
sis, the reduced ore with calcium sulfate additive achieved coarser
metallic particle size; the mean size increased from 6.9 lm to
17.8 lm attributing to addition of CaSO4.
In the experiments, the CaSO4 can be reduced to S2(as seen in
thermodynamic analysis). However, the S2 easily reacted with
metallic Fe to form FeS. Particular care should be taken with FeS,
which was present as a greyish white phase, existed around the
taenite particles or bridges different big metallic particles, and
reacted with Fe to form an Fe–FeS solution. According to the previ-
ous research, the molten phase favours metallic grain coarsening
where the smaller particles go into solution preferentially and pre-
cipitate on larger particles, accelerating the mass transfer rate as
liquids diffuse much faster than solids [27,32–35]. Therefore, the
Fe-FeS solution as the low-melting-point mineral could accelerated
the transfer rate of metallic particles in the molten ore and facili-
tated their growth. The results is also in line with previous
researches.
4. Conclusions
The technical feasibility of integrated technology to extract
nickel from low grade nickel limonitic laterite by the selective
reduction process in the presence of calcium sulfate and silica
was investigated, and the following conclusions can be drawn:
(1) A ferronickel concentrate with 5.1% Ni and 81.7% Fe was
obtained through reducing at 1250 °C for 60 min in the pres-
ence of 3% calcium sulfate and 8% silica, followed by wet
magnetic separation from low grade limonitic laterite. The
corresponding recoveries of Ni and Fe were 95.6% and
42.8%, respectively.
(2) During the reduction of low grade limonitic laterite, an
appropriate addition of silica and CaSO4 is favourable to
nickel enrichment by generating fayalite and suppressing
iron oxide reduction.
459
(3) Calcium sulfate plays an important role not only in the selec-
tive reduction of nickel laterite but also in the aggregation of
metallic particles. The addition of calcium sulfate inhibits
the reduction of iron oxides to form troilite (FeS) and pro-
motes the growth of metallic grains through generation of
a low-melting-point solution (Fe-FeS). Consequently, the
magnetic separation of ferronickel is enhanced.
Acknowledgements
The authors wish to express their thanks to the National Key
Technology R&D Program of China (NO. 2013BAB03B04) and
Innovation-driven Project of Guangxi Zhuang Autonomous Region
(No. AA18242003, No. AA148242003) for the financial support of
this research, and also would like to thank Co-Innovation Center
for Clean and Efficient Utilization of Strategic Metal Mineral
Resources of Hunan Province, which supplied us the facilities and
funds to fulfill the experiments.
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