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ISIJ International, Vol. 50 (2010), No. 3, pp.

380385

Mineral Change of Philippine and Indonesia Nickel Lateritic Ore


during Sintering and Mineralogy of Their Sinter

Xuewei LV, Chenguang BAI, Shengping HE and Qingyun HUANG

School of Materials Science and Engineering, Chongqing University, Chongqing, 400044 P.R. China.
E-mail: lvxuewei@163.com, bguang@cqu.edu
(Received on July 6, 2009; accepted on November 26, 2009 )

Mineral changes of Philippine and Indonesia nickel lateritic ores during the sintering and the mineralogy of
their sinter were studied in present work. A laboratory scale sintering pot was used to prepare the sinter
samples. Thermo-gravimetric (TG) tests, differential thermal analysis (DTA), and X-ray diffraction (XRD) ex-
periments were carried out to understand the mineral change of laterites. These measurements indicate
that chlorite (Fe,Mg,Al)3(Si,Al)2O5(OH)4 and serpentine Mg21Si2O28(OH)34H2O are the primary phases, while
FeO(OH) and (Fe,Mg,)3Si4O10(OH)2 are the minor phases in both Philippine and Indonesia nickel laterite. The
XRD, scanning electron microscope (SEM), and energy dispersive spectrometer (EDS) were used to analyze
the sinter samples; the results demonstrate that olivine (Mg,Fe)2SiO4 is the main bonding phase in both
Philippine and Indonesia laterite sinters, and spinel MgFe2O4 is also found as the solid bonding phase in the
Philippine laterite sinter.
KEY WORDS: sinter mineralogy; nickel laterite; thermal analysis; mineral change.

crease if the nickel laterite ores are hydrated and sintered by


1. Introduction
means of traditional sintering, and if the nickel lateritic sin-
Sulfide deposits and oxide ores are the two main resource ters are then reduced in the shaft furnace. To facilitate this
of nickel. Approximately 36% of the worlds nickel laterite process, a comparative study on sintering behaviors of
reserves occur as sulphide, and 64% occur as oxide ores.1) nickel laterite from the Philippines and Indonesia was car-
Demand for nickel had risen from under 200 000 tons/year ried out in this paper.
in 1950 to over 1 200 000 tons/year in 20032,3); it will reach
1 454 000 tons in 2008. The worldwide output of the stain-
2. Experimental
less steel was over 277 000 000 tons in 2007, and will reach
287 000 000 tons.4) The enormous gap between demand and The mineral composition of the nickel laterite samples
supply drives the price of the nickel higher in the world before sintering was determined with chemical analysis,
market. Therefore, the dominance of sulfide ores as the thermo-gravimetric (TG) tests, differential thermal analysis
major source of nickel was not challenged until several (DTA), and X-ray diffraction (XRD). After sintering, the
years ago. Because 70% of the worlds land-based nickel samples were examined by XRD, scanning electron micro-
resources are contained in laterites, they currently account scope (SEM), and energy dispersive spectrometer (EDS).
for only about 40% of world nickel production.2,3,5) Laterite The TG and DTA were carried out using NETZSCH STA
ores cannot be concentrated like sulphide; rather, they must 449C with heating speed of 25 K/10 min and a maximum
be processed as mined. Therefore, its vitally important to temperature of 900C. The XRD analysis was carried out
develop a practical and inexpensive process for using lat- using D/MAX 3C (Co Ka ). The SEM observation and EDS
erite. analysis were carried out with TESCAN VEGA II and OX-
Most plants produce nickel or ferronickel by pyrometal- FORD INCA Energy 350. The sinter samples were pre-
lurgical means using a rotary kiln and electric furnace. pared in a laboratory scale sintering pot shown in Fig. 1.
Extraction of nickel or ferronickel from the high-magnesia The sintering experiments were conducted separately with
lateritic nickel ores by this means requires a great deal of coal dosages of 8 mass% and 17 mass% respectively.
energy. For example, the original moisture content of ores
is 30 mass%; it is demanded to dry to a moisture content of
3. Results and Discussion
20 mass%, using 3.71 MJ per kilogram of water removed.1)
Sintering is an important procedure used by the iron-mak- 3.1. Raw Materials
ing industry to agglomerate fine ores. This process removes 3.1.1. Chemical Composition Analysis
water from the mixture of the iron ores, fluxing agent, and The chemical composition of the nickel laterites from
the coals at the same time. Energy requirements may de- Philippine and Indonesia are shown in Table 1. The laterite

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Fig. 2. XRD patterns for nickel literates from Philippine and In-
donesia.

Fig. 1. Schematic of laboratory scale sintering pot.

Table 1. Chemical composition of nickel laterite, mass%.

from Philippine has more FeO and MgO and less SiO2 than
that from Indonesia. Fig. 3. TG pattern for nickel literates from Philippine and In-
donesia.
3.1.2. XRD Analysis
The XRD patterns shown in Fig. 2 reveals that both the
two nickel laterites are typical saprolitic ore, containing
dominant amounts of Mg silicate and MgFe silicate miner-
als.6) In saprolitic ores, Ni occurs mainly in Mg silicates,
and Cr occurs mainly in Fe silicates or goethite.1) The min-
eral species contains much crystal water and hydroxyl
group. In addition, some aluminates are present.

3.1.3. TG-DTA Analysis


As shown in Fig. 3, due to the loss of water contained,
the mass of the laterite decreased with the heating. The
mass loss of Indonesia laterite was 18.65 mass%. It was
greater than that of Philippine which was 17.8 mass%. The Fig. 4. DTA pattern for nickel literates from Philippine and In-
DTA patterns of the two laterites are shown in Fig. 4. In the donesia.
DSC curves, there are three obvious endothermic reactions
and one exothermic reaction occurred in both Philippine measurement in the reference,8) chlorite (Mg,Al)3(Si,Al)2
and Indonesia laterites. Due to the evaporation of the free O5(OH)4 has an exothermal peak at 468C and begin to lose
water, the first reaction occurs at 86.3C with 8.93 mass% the hydroxyl group at 597C. Due to the decomposition of
mass loss for Philippine laterite and 99.3C with silicate, the exothermic reaction occurs at 821.0C for
11.87 mass% mass loss for Indonesia laterite. Due to the Philippine laterite and 823C for Indonesia laterite. It should
loss of crystal water, the second reaction occurs at 256.4C involve no mass loss; however, there is a 0.48 mass% mass
with 4.29 mass% mass loss for Philippine laterite and loss with the reaction at the TG curve for Philippine laterite
265.0C with 2.62 mass% mass loss for Indonesia laterite. and 0.90 mass% for Indonesia laterite. The likely reason for
Due to the loss of hydroxyl group, the third occurs at this phenomenon is the removal of hydroxyl group remain-
602.1C with 4.10 mass% mass loss for Philippine laterite ing in the minerals.
and 596.8C with 1.50 mass% mass loss for Indonesia lat- A comparison of the measurements with the atlas of TG-
erite. In addition, there is a small onset at 468.1C in the DTA for minerals8) prompted several conclusions: The re-
curve of Indonesia laterite. According to the TG-DTA moval of hydroxyl group of chlorite (Fe,Mg,Al)3(Si,Al)2

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ISIJ International, Vol. 50 (2010), No. 3

O5(OH)4 began from 602C for Philippine laterite, and


596.8C for Indonesia laterite; at 780C, most of the hy- 3.2.2. SEM-EDS Analysis
droxyl group were removed from both Philippine and In- The surface and the transversal section of the Philippine
donesia laterite. The chlorite group then decomposed into and Indonesia laterite sinter were observed by SEM, and
MgO and SiO2 at 821C for Philippine laterite or 823C for the micrographs and the EDS map scanning of the mineral
Indonesia laterite. All the crystal water of serpentine phases in sinter are shown in Figs. 710. The surface of the
Mg21Si2O28(OH)34H2O were lost above 480C for Philip- Philippine laterite sinter is shown in Fig. 7. The dark areas
pine laterite and 500C for Indonesia laterite, forming of the micrograph, which are marked by arrows, have more
Mg3Si2O5(OH)4, and the hydroxyl was removed between Si and less Fe. Both Mg and O are distributed homoge-
500C and 760C for Philippine laterite and between 520C neously over the image. Figure 8 demonstrates the micro-
and 800C for Indonesia laterite. With these reactions, graph and EDS map scanning for the transversal section of
Mg3Si2O7 formed, then decomposed to MgO and SiO2. The Philippine laterite sinter. Some micropores of various sizes,
gramenite (Fe,Al)Si2O5(OH)H2O lost crystal water at which are marked by arrows, are distributed throughout the
143C, and it lost the hydroxyl at 480510C. Goethite lost
crystal water at 309C. A combination of XRD patterns and
the TG-DTA indicated that chlorite (Fe,Mg,Al)3(Si,Al)2
O5(OH)4 and serpentine Mg21Si2O28(OH)34H2O are the
main mineral phases and that FeO(OH) and (Fe,Mg,)3Si4
O10(OH)2 are the minor phases in both Philippine and In-
donesia nickel laterite.
The mass of crystal water and hydroxyl is 4.29 mass%
4.10 mass%0.48 mass%8.87 mass% for Philippine laterite
and 2.62 mass%1.76 mass%1.50 mass%0.90 mass%
6.78 mass% for Indonesia laterite; they are very close to the
data measured by chemical analysis in Table 1. Over
95 mass% of the water was removed from both the Philip-
pine and Indonesia laterites when the temperature rises
above 750C.
Fig. 6. XRD patterns for Indonesia sinters.

3.2. Nickel Laterite Sinter


3.2.1. XRD Analysis
As shown in Fig. 5 and Fig. 6, XRD patterns clearly
shows that hydroxyl remained as (Fe,Mg)3Si4O10(OH)2 in
both Philippine and Indonesia sinters, although it should
have lost over 1 000C. The hydroxyl may have been re-
tained because the minerals were bonded quickly by the liq-
uid phases created, worsening the kinetic condition of the
dehydration. The main phases in the sinter are (Fe,Mg)2
SiO4 and MgFe2O4.
In the process of heating, the minerals in laterite decom-
pose to Fe2O3, SiO2 and MgO, which can form MgSiO4,
MgFe2O4, and (Fe,Mg)2Si2O6. In addition, Ni replaces the
Mg in MgSiO4 lattice, forming MgNiSi2O6. Cr replaces Fe
in Fe3O4 lattice, forming Cr1.3Fe0.7O4.

Fig. 7. SEM observation and EDS for the surface of Philippine


Fig. 5. XRD patterns for Philippine sinters. sinter.

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Fig. 8. SEM observation and EDS for transversal section of


Philippine sinter.
Fig. 10. SEM observation and EDS for the surface of Indonesia
sinter.

section. The EDS analysis indicates that the micropores are


rich in Fe and lack Si and Mg. As shown in Fig. 9 and Fig.
10, there are two quite different SEM patterns observed on
the surface of the Indonesia laterite sinter. The bright areas
in Fig. 9, which are marked by arrows, have more Si and
Mg and less Fe according to their EDS analysis. The bright
dot lines in Fig. 10, which are marked by lines, have more
Fe and less Si and Mg, whereas, the dark areas near the
bright lines are rich in Si and Mg. The mineral particles and
the adhesive phase are easy to identify in Fig. 9, whereas,
its hard to distinguish in Fig. 10. It seems that there are
more liquid phases formed in Fig. 10 than Fig. 9. These
observation and analysis indicate that magnesium silicate
(Mg,Fe)2SiO4 is the main adhesive phases bonding both the
Philippine and Indonesia laterites.
A comparison of SEM patterns of the surface and the
transversal section of Philippine sinter with Indonesia sin-
ters are shown at high resolution in Fig. 11 and Fig. 12. As
shown in Fig. 11, the mineral particles with various shapes
are bonded together by the adhesive phase on the surface of
the sinters. As shown in Fig. 12, there are many micropores
in the transversal section of the sinters.
The pattern inside the micropores of Philippine sinter is
shown in Fig. 13, demonstrating some liquid phase was
generated around the micropores, bonding the particles to-
gether. Additionally, some circular particles of various sizes
Fig. 9. SEM observation and EDS for the surface of Indonesia are visible inside the microporosity. The EDS indicates that
sinter. the phases inside the micropores are rich in Fe and Cr, with

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Fig. 13. A comparison of pattern of transversal section in Philip-


pine and Indonesia sinters.

Fig. 11. A comparison of pattern of adhesive phase in Philippine


and Indonesia sinters.

Fig. 14. SEM observation and EDS for (Mg,Fe)2SiO4 phase in


Indonesia sinter.

atom fractions as high as 45.7% (63.9 mass%) and 10.1%


(13.4 mass%) respectively. On the other hand, the phases
around the microporosity are rich in Fe, Si, and Mg, with
the atom fractions of 21.9% (43.8 mass%), 13.3% (13.4
mass%), and 11.9% (10.4 mass%) respectively. The XRD
pattern agrees well with the EDS analysis, and both of them
validates the formation of (Fe,Mg)2SiO4. The enrichment of
Fe and Cr in the micropores is likely the result of the partial
reduction of the mineral Cr1.3Fe0.7O4 by the carbon or car-
bon monoxide and the blocking of oxygen outside by a
layer of bonding phases. The similar EDS result was found
in the Indonesia laterite sinter, as shown in Fig. 14, the area
marked by A is the (Fe,Mg)2SiO4 phase, and area B with
strip shape is the mineral from the raw materials. Fig. 15
shows the micrograph and EDS analysis for MgFe2O4 phase
found in Philippine laterite sinter. The EDS analysis reveals
that there is little difference between zones A and B. The
average ratio of Mg : Fe in atom is 1 : 3.4; therefore, the
molar ratio of MgO and Fe2O3 is 1 : 1.7. According to the
phase diagram of MgO and Fe2O3.10) The minimum temper-
ature for the appearance of liquid phase at this chemical
composition is 1 700C, which is impossible under the
experimental conditions described here. The MgFe2O4
phase found with the XRD pattern is apparently the product
Fig. 12. SEM observation and EDS for microporosity in Philip- of recrystallization of MgO and Fe2O3 in solid states.
pine sinter.

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ISIJ International, Vol. 50 (2010), No. 3

900C.
(3) Olivine (Mg,Fe)2SiO4 is the main bonding phases in
both Philippine and Indonesia laterite sinter, and spinel
MgFe2O4 is also found as the solid bonding phase in the
Philippine laterite sinter.

Acknowledgments
The authors are especially grateful to Jingguang Corp.
Ltd., Sichuan, China for the financial support, and the
Chongqing University Postgraduates Science and Innova-
tion Fund (200911B1A0120328).

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