Hydrometallurgy 51 Ž1999.

131–138

Short communication

Kinetics of leaching of a gibbsitic bauxite with

hydrochloric acid
B.R. Reddy ) , S.K. Mishra, G.N. Banerjee
Regional Research Laboratory (CSIR), Bhubaneswar, 751 013 Orissa, India
Received 21 November 1996; revised 10 September 1998; accepted 13 September 1998

Abstract

Leaching kinetics for the removal of iron from a low grade gibbsitic bauxite with hydrochloric
acid were studied. Temperature and acid concentration had strong influence on the removal of
iron. Calcium removal was quantitative within a short period with dilute acid. The mechanism for
the dissolution of iron followed first order equation, ylnŽ1 y a . s kt, with an apparent activation
energy of 81.0 kJrmol. Using 4 M acid removal of more than 98% iron was achieved from
hematite together with about 10% alumina from gibbsite phases of the ore. q 1999 Published by
Elsevier Science B.V. All rights reserved.

Keywords: Gibbsitic bauxite; Hydrochloric acid; Leaching kinetics

1. Introduction

The total reserve of bauxite in India has been estimated at 3037 million tonnes w1x.
Around 90% of the available reserve is used in metallurgical industry and the rest for
non-metallurgical applications. The non-metallurgical grade ore containing less than 2%
Fe 2 O 3 and 0.5% CaO is available in Gujarat. Sizeable quantity of low grade ore with
4–6% iron and 1–2% calcium is also generated during mining of good grade ore and
stockpiled at the mine site.
Removal of iron oxide from bauxite has recently become the objective of many
researchers w2,3x for two reasons: low-iron bauxite Žless than about 2 wt.% Fe 2 O 3 . finds
application in the production of refractories and removal of iron from bauxites before
the Bayer process reduces the environmental problems associated with the disposal of
red mud. Physical beneficiation methods attempted to remove iron and calcium from

)
Corresponding author. Fax: q91-674-581-750; E-mail: root@csrrlbhu.ren.nic.in

0304-386Xr99r$ - see front matter q 1999 Published by Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X Ž 9 8 . 0 0 0 7 5 - 9
132 B.R. Reddy et al.r Hydrometallurgy 51 (1999) 131–138

bauxite have met with marginal success w4–6x. Two samples of Alabama calcined
bauxite containing 2.7% and 8% Fe 2 O 3 subjected to hydraulic classification followed by
magnetic separation of the classified concentrate in a high-intensity magnetic separator
could reduce the iron to below 2.5% Fe 2 O 3 with a recovery of alumina less than 17%
w4x. In another study w5x the finely crushed Alabama bauxite ore containing 2.7% Fe 2 O 3
was treated by calcination and reduction roasting with hydrogen at 8008C. Magnetic
separation of the calcine at 4000 G in single stage produced a product with 1.5% Fe 2 O 3 .
Many investigators have reported the removal of iron from bauxite along with its
mechanism using hydrochloric acid leaching w7–10x. Kinetics of iron removal from
boehmitic w7,8x and diasporic w9x bauxite with acid followed first order and shrinking
core model reaction mechanism respectively. The activation energy varied from 80 to
106 kJrmol depending on the particle size and nature of the ore.
The present investigation deals with the kinetics of iron removal from low grade
gibbsitic bauxite of Saurashtra area, Gujarat, with hydrochloric acid. The process
parameters studied include agitation, acid concentration, temperature, time and particle
size of the ore.

2. Experimental

2.1. Materials

Low grade gibbsitic bauxite from Shaurastra area, Gujarat, was used for leaching
experiments. The XRD studies of the ore indicate gibbsite as the major mineral phase
and calcite, hematite, quartz and rutile as minor phases. The ore was crushed and
screened to different size fractions 250–500 mm, 125–250 mm, 90–125 mm and 50–90
mm in order to determine the possible effect of particle size on removal of iron and
calcium. All the leaching experiments were carried out using 125–250 mm size ore
except the study on the effect of particle size on iron dissolution. All the chemicals used
were of analytical grade. Iron, alumina and calcium were analysed by wet chemical
method w11x. The chemical analysis of various fractions ranging from 50–500 mm with
corresponding percentage of metal concentration is presented in Table 1.

2.2. Leaching procedure

Dissolution studies were carried out in a spherical reaction vessel containing suitable
concentrations of acid and ore. The vessel was immersed in a constant temperature bath

Table 1
Chemical analysis of bauxite
Component Ž%.
Fe 2 O 3 Al 2 O 3 CaO TiO 2 SiO 2 LOI
4.4–4.6 57.4–58.4 2.7–3.0 2.9–3.1 1.9–2.1 29.2–30.0
 B.R. Reddy et al.r Hydrometallurgy 51 (1999) 131–138 133

and mixing was effected with the a variable speed stirrer. From the liquor, 2 ml aliquots
were collected at appropriate time intervals and analysed for Fe, Ca and Al. The solid to
liquid content ratio was maintained at 25 grl.

3. Results and discussion

3.1. Chemical reactions

The possible chemical reactions that occur during leaching of bauxite with hydrochlo-
ric acid are as follows:
Fe 2 O 3 q 6HCl ™ 2FeCl 3 q 3H 2 O Ž 1.
CaCO 3 q 2HCl ™ CaCl 2 q CO 2 q H 2 O Ž 2.
Al 2 O 3 q 6HCl ™ 2AlCl 3 q 3H 2 O Ž 3.
TiO 2 q 2HCl™ TiOCl 2 q H 2 O Ž 4.
Reactions Ž1., Ž2. and Ž3. are of special interest for the process. However, reactions Ž3.
and Ž4. have been reported to proceed only to a small extent w12x and will not be
discussed here.

3.2. Effect of agitation

The effect of agitation in the range between 300 and 1000 rpm with an increment of
100 rpm on the leaching of bauxite with 4 M hydrochloric acid was studied at 338 K for
120 min. The dissolution of iron increased with agitation speed from 300–500 rpm and
afterwards remained constant. These observations indicate that diffusion of acid across
the solid–fluid boundary layer could be avoided by keeping the speed at more than 500
rpm. The removal of calcium was 100% and aluminium was 7–9%.

3.3. Effect of acid concentration

The effect of acid concentration Ž1–5 M. was carried out at 348 K with an agitation
speed of 600 rpm. The percentage dissolution of iron increases sharply from 10% to
98% with increase in acid concentration from 1–4 M and reaches 100% at 5 M acid. On
the other hand, variation of acid concentration has negligible effect on calcium removal
and is quantitative even at 1 M acid. The dissolution of aluminium was in the range
5.2–6.9%.

3.4. Effect of particle size

The effect of particle size on dissolution of ore with 4 M HCl at 348 K was studied
using three size fractions, namely 50–90 mm, 125–250 mm and 250–500 mm. It was
observed that the percentage dissolution of iron increases with increase in time and
134 B.R. Reddy et al.r Hydrometallurgy 51 (1999) 131–138

decreases with particle size. The percentage dissolution of iron was varied in a close
range for all the size fractions. It was in the range of 23 to 28% at 10 min and 94 to 97%
at 90 min. In between time intervals, the amount of iron dissolved varied by about
10–12%. Based on the above results studies on the kinetics of iron dissolution from
bauxite were carried out using the following conditions: 600 rpm, 4 M acid and
125–250 mm particle size.

4. Dissolution kinetics

4.1. Effect of temperature

The effect of temperature Ž333–363 K. and time Ž10–90 min. on the percentage
dissolution of iron from bauxite with 4 M acid was studied ŽFig. 1.. The plots indicate
that the percentage extraction of iron increases steadily with both time and temperature.
Identification of the kinetic model for the dissolution of iron from the ore was carried
out by plotting the experimentally obtained values of a Žfraction reacted. against trt 0.5
Ž t 0.5 s time to reach a s 0.5. and comparing with the calculated standard reduced time
plots for different kinetic model equations w13,14x. The results shown in Fig. 2 indicate
that the mechanism of iron dissolution appears to follow closely first order chemical
reaction model wF1 i.e., ylnŽ1 y a . s kt x as well as contracting volume model wR3 i.e.,
1 y Ž1 y a .1r3 s kt x up to a s 0.7. As the reduced time method has its limitations both
F1 and R3 models were considered. Further the integral form of both the models w15,16x
as a function of time at different temperatures presented in Fig. 3 showed that the
reaction mechanism followed the F1 model wylnŽ1 y a . s kt x for longer span of time.

Fig. 1. Effect of leaching time and temperature on dissolution of iron. Conditions: wHClx, 4 M; stirring rate,
600 rpm.
 B.R. Reddy et al.r Hydrometallurgy 51 (1999) 131–138 135

Fig. 2. Reduced time plot: fraction reacted, a as function of reduced time, tr t 0.5 .

Fig. 3. Kinetic plots for F1 and R3 model equations.

136 B.R. Reddy et al.r Hydrometallurgy 51 (1999) 131–138

Fig. 4. Arrhenius plots.

The relationship between the rate constant k and temperature is given by the Arrhenius
equation
k s A exp Ž yErRT . Ž 5.
where A is the frequency factor and E is the apparent activation energy. Apparent
activation energy ŽFig. 4. for R3 and F1 models are 78 and 81 kJrmol, respectively.

Fig. 5. Integral approach, ln ta vs. 1r T.

 B.R. Reddy et al.r Hydrometallurgy 51 (1999) 131–138 137

Further, the activation energy was obtained by the integrated form of the rate
equation w17x
g Ž a . s kt s AeyE r RT t Ž 6.
ln g Ž a . s ln A y ErRTq ln ta Ž 7.
or
ln ta s ln g Ž a . y ln A q ErRT Ž 8.
Assuming that the mechanism of dissolution does not change over the range of
temperature considered, a plot of ln t a as a function of 1rT yields a series of parallel
straight lines ŽFig. 5. with a slope of ErR. The average E value of about 81.0 kJrmol
matches the value obtained from the F1 model, which further supports the model
obtained through kinetic analysis. Many investigators on the leaching of iron oxide from
bauxite by hydrochloric acid have also reported activation energy in the range 86.6–91.7
kJrmol w18–21x.

5. Conclusions

The following conclusions can be drawn.

Ži. Both temperature and acid concentration have a significant effect on the dissolu-
tion of iron from bauxite.
Žii. Dissolution of calcium was faster than that of iron and was quantitative.
Žiii. Dissolution of aluminium was about 5–7%.
Živ. The rate of iron dissolution followed first order reaction mechanism wylnŽ1 y a .
s kt x with an apparent activation energy of about 81.0 kJrmol.

Acknowledgements

The authors are thankful to Prof. H.S. Ray, Director, Regional Research Laboratory,
Bhubaneswar for permission to publish this work.

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