Int. J. Miner. Process.

93 (2009) 79–83

Contents lists available at ScienceDirect

Int. J. Miner. Process.

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i j m i n p r o

A shrinking particle—shrinking core model for leaching of a zinc ore containing silica
Vida Safari a, Gilnaz Arzpeyma a, Fereshteh Rashchi b, Navid Mostoufi a,⁎
a
Department of Chemical Engineering, University of Tehran, PO Box 11155/4563, Tehran, Iran
b
Department of Metallurgy and Materials Engineering, University of Tehran, PO Box 11155/4563, Tehran, Iran

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

Article history: A new mathematical model was developed for leaching of zinc ores containing silicates such as
Received 10 January 2009 hemimorphite which produce a gel during leaching with sulfuric acid. This model is based on the shrinking
Received in revised form 24 May 2009 core model in which the particle size and the reacting core shrink simultaneously. It was shown that the
Accepted 11 June 2009
actual dissolution time of the ore particles is longer than the time corresponding to the dissolution of
Available online 23 June 2009
chemical zinc oxide itself. It was suggested that because of the existence of silicates in the ore, a gelatinous
Keywords:
layer was formed around the reacting core. Since the gel product is soft, it breaks apart when the particles
Leaching collide and as a result, the particles shrink. However, a thin gelatinous layer always covers the reacting core
Kinetics which increases the mass transfer resistance and increases the leaching time. This model was applied to
Zinc silicate leaching of a zinc-rich tailing containing hemimorphite and the thickness of the gelatinous layer as well as
Shrinking core model the diffusion coefficient in this layer was determined.
Gelatinous silica layer © 2009 Elsevier B.V. All rights reserved.

1. Introduction
The main source of zinc metal production is zinc sulfide ore.
Currently, depletion of these sulfide ores has brought more emphasis
on zinc extraction from oxides, silicates or even secondary sources.
Zinc extraction is performed mainly by hydrometallurgical methods.
In the hydrometallurgical process, the ore is first leached by a solvent
and then before electrowinning a purification process is used to
prepare the solution for eletrolysis.
During the leaching process of zinc oxidized ore, soluble zinc
sulfate forms which stays in solution. In this process, the lead
compounds form lead sulfate precipitates which transfer to the
leaching filter cake during the solid/liquid separation. Leaching of the
ore at pH ca. 2, transforms the silicate compounds of the ore to
colloidal silica, i.e., a gel (Matthew and Elsner, 1977).
Process kinetics and optimum operating conditions have been
studied for the leaching of zinc silicate ore tailings. Monhemius and
Terry (1983) investigated the influence of different parameters on the
kinetic of acid dissolution of both natural and synthetic willemite
(Zn2SiO4) and hemimorphite (Zn4Si2O7(OH)2.H2O). Specific rate
constants were estimated for leaching of both willemite and
hemimorphite in different acidic media. They found that the
dissolution was mixed chemical/diffusion controlled in hemimor-
phite and chemically controlled in the case of willemite. Abdel-Aal
(2000) investigated the kinetics of sulfuric acid leaching of low-grade
zinc silicate ore. In their study, diffusion through the product layer was
⁎ Corresponding author. Tel.: +98 21 6696 7797; fax: +98 21 6640 1024.
E-mail address: mostoufi@ut.ac.ir (N. Mostoufi).
determined as the rate controlling step. Espiari et al. (2006) verified
extraction of zinc from tailings of lead flotation plant. They studied the
effect of different parameters on kinetics of zinc dissolution and found
that the rate determining step is the physicochemical desorption
process. Souza et al. (2007) studied the effect of particle size,
temperature and initial acid concentration on leaching of zinc silicate
ores. They concluded that the grain model with porous diffusion
control is the rate controlling step.
Some researchers have reported the possible existence of internal
diffusion resistance. For instance, Pecina et al. (2007) have reported
formation of a sulfur layer in zinc sulfide leaching with high
concentration of sulfuric acid solution containing hydrogen peroxide
and indicated that this layer reduces leaching efficiency. Mulak et al.
(2005) found that in leaching of spent nickel oxide catalyst with
sulfuric acid, an aluminium-rich layer surrounds the unreacted core of
the particle and grows inward as the particle reacts. In leaching
process of sphalerite containing a lower concentration of iron, the
decrease in zinc dissolution rate (as compared to a greater iron-
containing sphalerite mineral) was attributed to formation and
growth of a polysulfide surface layer during the initial rapid leach
period (Weisener et al., 2004).
Based on the above evidences, it can be concluded that when a core
shrinks, an internal resistance layer, either a reaction product layer or
a gel film forms around the core and results in a decrease in the
extraction yield in the leaching process. However, in many cases, the
size of the particle (including unreacted core and the layer) decreases
with time. In other words, although the product layer forms around
the core, it shrinks as the core shrinks. In all the previous studies,
existence of this gelatinous layer around the particle was neglected
during the kinetics calculations and its effect on the kinetics of

0301-7516/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2009.06.003
80 V. Safari et al. / Int. J. Miner. Process. 93 (2009) 79–83

leaching was not taken into account. In the present study, a mathe- • In the absence of adequate information, the thickness of the silica
matical model has been developed based on the shrinking core model layer around the core was assumed to be constant during the
in which the resistance of the gelatinous product film is also con- leaching process.
sidered. This kinetic model consists of three steps: external diffusion • Although there exist many reactions in the leaching of zinc by
in the liquid, internal diffusion in the gelatinous product film and sulfuric acid from the ore, for the sake of simplicity, the main reac-
chemical reaction on the surface of the core. tion considered in this work is dissolution of zinc oxide in acid. In
other words, the main source of zinc in the leaching was assumed to
2. Model development be zinc oxide.
• Hemimorphite particles were considered as the source of silica
Zinc silicate ore, as hemimorphite, reacts with sulfuric acid according responsible for the gel formation.
to the following reaction: • Other substances present in the ore do not have any significant effect
on the kinetics.
Zn4 Si2 O7 ðOHÞ2 ·H2 O þ 4H2 SO4 →4ZnSO4 þ Si2 OðOHÞ6 þ 3H2 O ð1Þ • The temperature remains constant during the process.
• The particle and the gelatinous layer are both non-porous. Thus,
Zinc sulfate is soluble in water. However, disilicic acid, Si2O(OH)6, mass transfer occurs through molecular/ion diffusion in these
which apparently polymerizes to produce polysilicic acid, forms a phases.
gelatinous phase at specific acidic pH which remains around the
particles surface and leads to a decrease in the extraction yield. 2.2. Kinetic modeling
The most common models considered in leaching are illustrated in
Fig. 1. Fig. 1a corresponds to the case when the reaction takes place on Considering all the above assumptions, the first step for developing
the exposed surface of the particle and the product completely dissolves the model is to define a criterion indicative of the advancement of
in the liquid. This shrinking particle model (SPM) has been used by reaction versus time. The rate of reaction per unit surface of the core
researchers such as Espiari et al. (2006), Aydoğan et al. (2006) and can be related to the dissolution rate of zinc oxide as follows:
Velardo et al. (2002). If the product does not dissolve in the liquid, the
M dn
particle size would not change but the reacting core shrinks inside the Rr = − ZnO ZnO ð2Þ
Sc dt
particle. This situation is shown in Fig. 1b and the model is called
“Shrinking Core–Constant Particle Size”. It has been used by researchers
The rate of zinc oxide disappearance can be expressed as:
such as Liu et al. (2006), Liddell (2005) and Szubert et al. (2006). Fig. 1c
demonstrates schematic of a model called “Shrinking Core–Shrinking dnZnO ρ GS dr
Particle”. In this case as the reaction proceeds, the unreacted core of = Ore c c ð3Þ
dt MZnO dt
particle shrinks while a gelatinous silica layer forms around the core.
However, since this layer is soft, it breaks apart when the particles It has been shown in several references that the rate of reaction for
collide. Nevertheless, a thin layer of silica remains around the core. The dissolution of zinc oxide, Rr, is first order with respect to the
silica layer creates a resistance during acid transfer from the solution to concentration of the solvent (e.g., Espiari et al., 2006; Monhemius
the surface of the core. In the present work, the last model was and Terry, 1983):
considered as the base kinetic model since the silica product does not
dissolve completely in the acid solution. Therefore, the internal diffusion kCA
Rr = ð4Þ
through the gel film should be taken into account. MZnO

2.1. Assumptions Therefore, the rate of shrinkage can be expressed as:

The assumptions of the model are as follows: drc kCA

=− ð5Þ
dt ρOre G
• The particles are spherical.
• During the process, the particle shrinks uniformly, thus, it maintains The acid concentration, CA, used in Eq. (5) should be evaluated at
its spherical shape. the surface of the core. To find the acid concentration at reaction

Fig. 1. Schematics of different mechanisms of leaching.

 V. Safari et al. / Int. J. Miner. Process. 93 (2009) 79–83 81

surface, mass balances should be written for both the liquid film layer It is worth mentioning that in all previous investigations on
and the gelatinous layer. In both cases, mass transfer occurs only in kinetics of leaching of zinc with sulfuric acid, different rate constants
radial direction and the mass transfer equation becomes: were reported (e.g., Espiari et al., 2006; Abdel-Aal, 2000). However,

 since in all these investigations the effect of gelatinous layer was not
1 d 2 dCA taken into account, the reported rate constant is in fact a combination
2 dr
r =0 ð6Þ
r dr of reaction rate constant and dispersion coefficient of acid in the
gelatinous layer. In the present study, the effect of gelatinous layer is
The boundary conditions are: separated from the reaction. Therefore, only dissolution of pure zinc
oxide in sulfuric acid was considered on the surface of the ore. Of
dCA course, based on the assumptions listed above, effect of other
r = rc + δ hD ðCA0  CA Þ = Dg ð7Þ
dr substances in the ore, on the dissolution kinetic of zinc oxide was
neglected in this work.
dCA
r = rc Dg = kCA ð8Þ The mass transfer coefficient was calculated from (Ranz and
dr
Marshall, 1952):
Considering that the process is in quasi-steady-state conditions,
1 = 3

1=3 1=2 μ dp up 1 = 2
the rate of reaction at the surface of the core would be equal to the rate Sh = 2 + 0:6Sc Re = 2 + 0:6 ð16Þ
ρD μ
of mass transfer to and through the gel film:

hD ðCA0  CA j rc + δÞ = kCA j rc ð9Þ Evaluation of mass transfer coefficient from Eq. (16) requires
estimation of viscosity, density and diffusion coefficient of the acid
solution. These properties are not simple functions of their composi-
Solving the differential Eq. (6) with boundary conditions (7) and tions. There can be found several equations for viscosity, density and
(8) and then solving Eq. (9) for finding CA(rc) would result in diffusion coefficient of the mixture in this process in various
obtaining CA: literatures. In the present study, the following correlations of Guerra
2 Dg
3 and Bestetti (2006) were used:
krc2
 r1  1r
CA = CA0 4 D c
Dg
5 ð10Þ
g
krc2
+ 1
rc r 1
+ δ + hD ðrc + δÞ2 μ = ð0:4332344  4:998831 × 103 T + 2:174276 × 105 T 2  4:216447 × 108 T 3
c

+ 3:072309 × 1011 T 4 Þ × expð0:6182½ZnSO4  + 0:1801½H2 SO4 

Therefore, the dissolution rate of zinc oxide can be expressed as: ð17Þ
2 3
kCA j r = rc CA0 1
Rr = = 4   5 ð11Þ 2+ 2+
MZnO MZnO rc rc rc2 ρ = 1153:82 + 66748½H2 SO4  + 181:436½Zn  + 158:354½Fe 
1
k
+ Dg 1r + δ + hD ðrc + δÞ2
c
3+
+ 396:312½Fe   0:55T
ð18Þ
or in form of the shrinkage rate:
2 3
drc CA0
4 1 5 DZnSO4 = ½8:083  7:496ð½ZnSO4  + 0:296½H2 SO4 Þ0:5 + 4:105½ZnSO4 
=−   ð12Þ
dt ρOre G 1 + rc
1r rc
+ rc2
k Dg c + δ hD ðrc + δÞ2 + 3:924½H2 SO4   0:739ð½ZnSO4  + 1:615½H2 SO4 Þ1:5  × 1010

Eq. (12) can be expressed in terms of advancement of the reaction. ð19Þ

The conversion can be determined based on the residual volume of
particle as follows: 3. Results and discussion


r ðtÞ 3 Performance of the proposed model was examined using the
XðtÞ = 1  c ð13Þ
r0 experimental data reported by Espiari et al. (2006) for leaching of zinc
from a zinc-rich oxide silicate tailing with sulfuric acid. Their XRF
Therefore, the final differential equation, from which the extent of analysis results showed that the sample contained 37% zinc oxide and
dissolution of particles as a function of time can be obtained, can be 23.7% silica. The leaching data reported by Espiari et al. (2006) are
then achieved by combining Eqs. (12) and (13): available as zinc recovery vs. time at various temperatures. Eq. (14)
was solved for different operating conditions reported by Espiari et al.
dX 3CA 1 (2006). In this equation, thickness and diffusion coefficient of the gel
=    
dt ρOre Gr03 1 ð1XÞ2 = 3 r02 ð1XÞ2 = 3 r02 layer were considered as fitting parameters and their values at
k
+ Dg
1
r0 ð1−XÞ1 = 3
r 1
ð1XÞ1 = 3 + δ
+ hD ðr0 ð1XÞ1 = 3 + δÞ2
0
different temperatures were determined by fitting the equation to the
ð14Þ experimental data.
Fig. 2 illustrates a sample solution of the model as well as the
2.3. Chemical and physical properties corresponding experimental data. This figure shows the conversion of
the ore as a function of time in the batch system. It can be seen in Fig. 2
The only chemical reaction considered in this work on the surface that the model fits satisfactorily to the experimental data (Espiari
of the core is dissolution of zinc oxide by sulfuric acid. Reaction rate et al., 2006). Prediction of the conversion when the effect of the gel
constant for dissolution of pure zinc oxide in sulfuric acid is calculated film was neglected (only zinc oxide reaction with acid and liquid film
from the following equation (Kristovnikov and Davydovskaya, 1936): resistance was considered) is also shown in the same figure. As it can
be seen, the particles dissolved very fast if the effect of gel film

 formation is neglected. However, the trend of the experimental data
−4 13634:96 suggests that the leaching process is not as fast as dissolution of zinc
k = 6:028 × 10 exp  ðm = sÞ ð15Þ
RT oxide in sulfuric acid. Slower reaction can be justified by adding the
82 V. Safari et al. / Int. J. Miner. Process. 93 (2009) 79–83
Fig. 2. Model verification with and without gelatinous layer.
resistance of the gel film which is modeled in the present study.
Therefore, it is not possible to neglect the effect of the gel film because
its effect on the leaching is substantial.
Espiari et al. (2006) reported conversion vs. time at various
temperatures. Using these experimental data it was found that the
thickness of the layer is almost constant in the range of temperature
considered in this work and its average was determined to be 1.2 μm
with standard deviation of 0.8 μm. However, diffusion coefficient is a
strong function of temperature. The Arrhenius plot of diffusion
coefficient of the gel against temperature is shown in Fig. 3 from
which temperature dependency of diffusion coefficient was found to
be:
28; 167:83
ln Dg =  12:92 
RT
There are three terms in the denominator of Eq. (14) which
correspond to resistances due to chemical reaction, diffusion through
gel film and mass transfer in the liquid film, respectively. Resistance of
the liquid film is negligible as compared to the other two resistances
for the operating conditions considered in this work. Therefore, in
order to investigate the effect of temperature on the leaching rate,
only chemical reaction and diffusion through the gel were considered.
Fig. 4 demonstrates the reaction and internal diffusion resistances as a
function of temperature. It can be seen in this figure that both of the
resistances decrease by increasing the temperature. At low tempera-
tures, reaction resistance is negligible and kinetic mechanism would
be reduced to gel diffusion control. Increasing the temperature has a
Fig. 3. Gel diffusivity versus temperature.
Fig. 4. Comparing reaction and gel diffusion resistances.
significant effect on both reaction and mass transfer rates. At high
temperatures these two rates are of the same order of magnitude as
shown in Fig. 4. Therefore, at high temperature, the process is con-
trolled by both chemical reaction and diffusion though the gelatinous
layer.
4. Conclusion
A mathematical model was developed for leaching of zinc from a
zinc ore containing silica. It was shown that considering only the
chemical reaction of zinc dissolution is not sufficient for estimating
the leaching time of the ore. A thin gelatinous layer was considered to
ð20Þ cover the reacting core of the ore in order to correct the model
prediction. Adding the mass transfer resistance of this layer to the
model considerably improved the predictions. It was shown that the
thickness of the gel is almost constant but the diffusion coefficient of
the gel decreases with temperature. At low temperatures, the reaction
rate is significantly lower than the rate of mass transfer through this
layer which alters the mechanism to diffusion controlled. At high
temperatures, both chemical reaction and mass transfer control the
dissolution rate of the zinc ore particles containing silica.
Acknowledgement
The authors would like to thank Professor Fathi Habashi from the
University of Laval, Canada, for his valuable comments during the
work.
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X: volumetric conversion
Glossary

CA: acid concentration at the surface of the core (kg m− 3) Greek letters
CA0: acid concentration in the bulk (kg m− 3)
dp: particle diameter (m) δ: gelatinous layer thickness (m)
Dg: diffusivity of gel (m2 s− 1) µ: viscosity of solution (kg m− 1 s− 1)
DZnSO4: diffusion coefficient of zinc sulfate in solution (m2 s− 1) ρOre: density of zinc ore (kg m− 3)
G: zinc oxide grade ρ: density of solution (kg m− 3)
hD: mass transfer coefficient (m s− 1)