Int. J. Miner. Process. 60 2000.

914
www.elsevier.nlrlocaterijminpro

Kinetics of leaching laterite

E.O. Olanipekun)
Department of Chemistry, Ondo State Uniersity, P.M.B. 5363, Ado-Ekiti, Ekiti State, Nigeria
Received 19 August 1998; received in revised form 8 April 1999; accepted 1 October 1999

Abstract

The kinetics of leaching laterite with hydrochloric acid has been investigated at dilute solid
phase concentrations in a magnetically stirred reactor. The effects of hydrochloric acid concentra-
tion and temperature on the dissolution rate of iron are reported. Preroasting of the laterite alters
its mineralogical composition and increases its porosity and surface area, thus making it more
amenable to leaching. The leaching rates were analyzed with the shrinking core models for
reaction control. The leaching data for both raw and roasted laterites fit the diffusion kinetic
equation with associated apparent activation energies of 71.7 and 65.2 kJrmol, respectively.
q 2000 Elsevier Science B.V. All rights reserved.

Keywords: leaching laterite; hydrochloric acid; temperature

1. Introduction

Laterite is a highly weathered material rich in secondary oxides of iron, aluminium or

both, nearly devoid of bases and primary silicates but may contain abundant quartz and
kaolinite. In addition, laterite often contains minor amounts of nickel, cobalt, and
chromium. The high proportion of iron III. oxide in laterites represents a residual
accumulation brought about the removal of silica and alkalis.
Leaching of iron from laterites is important for the following reasons: 1. low iron
laterites less than about 2 wt.% Fe 2 O 3 . may find application in producing refractories;
2. deironing laterites before the Bayer process will reduce environmental contamination
due to red mud, thus making it possible to recover valuable elements such as nickel,
cobalt, and chromium; 3. the iron-free laterite may be used either for producing
alumina by the Bayer process or for producing anhydrous aluminium chloride.

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Tel.: q234-30-250-848.
E-mail address: lapek@ibadan.nipost.com.ng E.O. Olanipekun..

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10 E.O. Olanipekunr Int. J. Miner. Process. 60 (2000) 914

Recent work indicates that laterite exhibits a slow reaction kinetics toward hydrochlo-
ric acid Oderinde and Olanipekun, 1992.. Still, there is really no firm quantitative data
on the influence of a pyrometallurgical pretreatment, such as roasting on the leaching of
iron oxides from laterites.
The present work investigates the kinetics of leaching laterite in dilute hydrochloric
acid solutions with a view to elucidating the influence of roasting on the rate and
mechanism of iron dissolution. A particular advantage of this leaching process is that
hydrochloric acid as a leachant allows comparatively easier recovery of the useful free
acid from its waste solution than does sulphuric acid. Moreover, separation of metal
chlorides through solvent extraction is much easier than from sulphate medium. Hence,
the iron III. chloride solution generated during leaching can be separated by solvent
extraction, and Fe 2 O 3 of higher-than-pigment grade is recoverable with free HCl from
the back-extracted solution by the thermal decomposition method. The recovered acid is
suitable for the purpose of recycling.

2. Experimental
2.1. Materials
The laterite used in this study was collected from the deposit along Abeokuta Road,
about 10 km south of Ibadan Nigeria.. The ore was crushed and screened to produce the
y88 q 53 mm particle size fraction. The chemical analysis of the laterite is given in
Table 1. Mineralogically, the laterite consists of kaolinite, hematite, geothite, and quartz,
as the major components. The major aluminium mineral present in the laterite is
gibbsite, with small amounts of boehmite and diaspore.
For the leaching, hydrochloric acid Aldrich. was used.
2.2. Equipment
Roasting of the laterite was carried out in a muffle electric furnace.
Leaching was conducted in a Pyrex reaction flask. The flask, equipped with a
thermometer and a reflux condenser, was heated with a thermostatically controlled
heating mantle. Stirring was done magnetically.

Table 1
Chemical analysis of laterite
Constituent Weight percent
Fe 2 O 3 48.09
Al 2 O 3 25.60
SiO 2 9.12
TiO 2 4.57
MgO 1.84
Cr2 O 3 1.52
Ni 1.13
Mn 0.48
Co 0.04
LOI 8.86
 E.O. Olanipekunr Int. J. Miner. Process. 60 (2000) 914 11

The metal analyses were carried out with an atomic absorption spectrophotometer.
The mineralogical analyses were carried out with a conventional Phillips X-ray
powder diffractometer.

2.3. Laboratory procedures

2.3.1. Roasting
After the desired furnace temperature of 5008C had been attained, the laterite placed
in a platinum crucible was introduced into the furnace and left for 2 h. Under these
conditions, complete goethite-to-hematite conversion was achieved Sukla and Das,
1987..
Chemical analysis of the roasted laterite for total iron content showed an increase in
value relative to that of the raw. unroasted. X-ray diffraction spectrum of the roasted
ore indicated that the peaks associated with goethite originally present in the unroasted
ore had almost disappeared and there was also a marked increase in the intensity of
peaks based on hematite.

2.3.2. Leaching
For each run, 200 ml of hydrochloric acid of pre-determined molarity was charged
into the reactor and heated to the desired temperature "18C.. About 2 g sample was
added and the contents were well-agitated. Solution samples of 2 ml were withdrawn at
appropriate times during a run and analyzed for iron by atomic absorption spectropho-
tometry.

3. Results and discussion

Initially, leaching experiments were carried out in 2, 3 and 4 M hydrochloric acid

concentrations at 708C. The results indicated that the leaching rates of both raw and
roasted laterites are influenced by concentration of hydrochloric acid. At all concentra-
tions, the roasted laterite was always leached at a relatively faster rate than the raw one.
Fig. 1 is typical of the results obtained with roasted laterite at various concentrations of
hydrochloric acid at 708C.
Evidence of the nature of heterogeneous reactions of this type can be obtained by
measuring the temperature dependence of the reaction rate. Consequently, the tempera-
ture dependence of the leaching rates was determined by additional experiments in 3 M
hydrochloric acid at 808C and 908C. The results presented in Fig. 2 show that the
leaching rates are influenced by temperature. At all of the studied leaching temperatures,
the reaction rates of both raw and roasted laterites initially rise very sharply up to around
60 min whereafter it tapers off. Best results were recorded at 908C for both raw and
roasted laterites.
The leaching of iron oxides hematite and goethite. from laterite by hydrochloric acid
occurs according to the reaction:
Fe 2 O 3 q 6HCl 2FeCl q 3H O.
3 2 1.
12 E.O. Olanipekunr Int. J. Miner. Process. 60 (2000) 914

Fig. 1. Fraction of iron dissolved vs. time plots for different HCl concentrations at 708C.

For the iron dissolution kinetics, two previously established shrinking core models
Habashi, 1979; Sohn and Wadsworth, 1979. were used, expressed by the following
equations:
1r3
1 y 1 y a. s k1 t , 2.
2r3
1 y 2r3a y 1 y a . s k2 t , 3.
where a is the fraction of iron dissolved at time t, k 1 and k 2 are the overall rate
constants. Eq. 2 assumes that the step controlling the leaching rate is the chemical
reaction taking place on the surface of the mineral, and Eq. 3 assumes that the
controlling step is the diffusion through the product layer.
Examination of plots of the above kinetic equations as functions of time showed that
only Eq. 3 gives perfectly straight lines for both raw and roasted laterites Fig. 3.. The
 E.O. Olanipekunr Int. J. Miner. Process. 60 (2000) 914 13

Fig. 2. Fraction of iron dissolved vs. time plots for different temperatures in 3.0 M HCl solution.

other kinetic model failed to give straight lines in function vs. time plots. These results
indicate that preroasting of laterite does not alter the reaction mechanism for the
leaching of iron oxides by hydrochloric acid. The X-ray diffraction patterns of the
reaction residues obtained after 3 h of leaching at 908C confirmed the formation of a
product layer consisting mainly of Al 2 O 3 , TiO 2 , SiO 2 , and the unleached Fe 2 O 3 around
the shrinking core of the unreacted material. The reaction rate is controlled by diffusion
through this porous product layer.
The rate constants, k 2 , for the leaching reaction were calculated from the slopes of
the plots in Fig. 3. The apparent activation energies calculated from the Arrhenius plots
of k 2 are 71.7 kJrmol for raw laterite and 65.2 kJrmol for the roasted. When viewed
under a low-powered microscope, there were more pores in the roasted laterite than in
the raw. Moreover, the measured specific surface area of the raw laterite is 20.8 m2rg
while that of the roasted is 59.4 m2rg. These results confirmed that the observed
relatively faster leaching rate of the roasted laterite is attributed to the increased
14 E.O. Olanipekunr Int. J. Miner. Process. 60 (2000) 914

Fig. 3. Plots of 1y2r3ay1y a. 2r 3 vs. time for different temperatures in 3.0 M HCl solution.

porosity, increased surface area, and change in reactivity of the ore due to extensive
dehydration and dehydroxylation of various hydrated oxide minerals.

References

Habashi, F., 1979. In: Principles of Extractive Metallurgy Vol. 1 Gordon & Breach, New York, pp. 1164.
Oderinde, R.A., Olanipekun, E.O., 1992. Kinetics of hydrochloric acid leaching of laterite. Pak. J. Sci. Ind.
Res. 35, 7780.
Sohn, H., Wadsworth, M.E., 1979. In: Rate Process of Extractive Metallurgy. Plenum, New York, pp.
141143.
Sukla, L.B., Das, R.P., 1987. Kinetics of nickel dissolution from roasted laterites. Trans. Indian Inst. Met. 40,
351353.