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and NO
3
). The following reactivity order
was observed by the study with respect to the acid anion:
HCl HNO
3
< HClO
4
< H
2
SO
4
H
3
PO
4
and they sug-
gested that the difference in the reactivity order is in a function
of the complex afnity for the zinc ion.
3.1.4. Effect of liquid/solid ratio
The effect of liquid/solid ratio (L/S) on the recovery of Zn(II)
and Cu(II) was investigated in the range 3/18/1 with leaching
by 30% H
2
SO
4
for 10 min at 35C with an agitation rate of
150 rpm. The recovery percent was found to increase and
0 20 40 60 80 100
0
20
40
60
80
100
Zn
Cu
R
e
c
o
v
e
r
y
(
%
)
Leaching Time, min.
Figure 2 Effect of leaching time on the recovery of zinc and
copper from the brass slag. L/S = 5, [H
2
SO
4
] = 30%,
temp. = 35 C, agitation rate = 150 rpm.
0 10 20 30 40 50
0
20
40
60
80
100
[H
2
SO
4
], %
Zn
Cu
R
e
c
o
v
e
r
y
(
%
)
Figure 3 Effect of acid concentration on the recovery of zinc and
copper leaching time = 10 min, L/S = 5, temp. = 35 C, agita-
tion rate = 150 rpm.
2 3 4 5 6 7 8
0
5
10
40
60
80
100
Zn
Cu
R
e
c
o
v
e
r
y
(
%
)
Liquid : solid ratio, mL : gm dust
Figure 4 Effect of liquid: solid ratio on the recovery of zinc and
copper from brass slag. [H
2
SO
4
] = 30%, leaching time = 10 min,
temp. = 35 C, agitation rate = 150 rpm.
Leaching and recovery of zinc and copper from brass slag by sulfuric acid 3
Please cite this article in press as: Ahmed, I.M. et al., Leaching and recovery of zinc and copper from brass slag by sulfuric acid.
Journal of Saudi Chemical Society (2012), http://dx.doi.org/10.1016/j.jscs.2012.11.003
reached a maximum of 93% and 9%, at liquid/solid mass ratio
5/1 for Zn and Cu, respectively, Fig. 4.
3.1.5. Effect of temperature
The effect of leaching temperature upon zinc and copper disso-
lution was studied in the range 1070C while the other leach-
ing parameters were xed at 30% H
2
SO
4
and L/S mass ratio of
5, Fig. 5.
It can be observed from the results obtained that the values
of the dissolution rate for zinc and copper increase with
increasing temperature till 35C for Zn and 70C for Cu.
The low recovery amounts at low temperature is due to the
low reactivity of slag, while as the temperature increases, the
non-matching of zinc and copper recovery is due to partial
hydrolysis of slag till 35C but increasing the temperature to
70C seriously decreases zinc recovery due to possible poly-
merization and hydrolysis.
3.1.6. Identication of the reaction mechanism
To identify the reaction mechanism of the leaching process of
zinc, the so-called reduced time plots were used. The leaching
rates of zinc were analyzed with the shrinking core model for
reaction control under the assumption that the slag is a homo-
geneous spherical solid phase (Levenspiel, 1972).
For the zinc leaching kinetic, two established kinetic models
were used, and expressed by the following equations:
1 1 a
1=3
Mk
c
C
A
t=dr k
1
t 1
1 21 a 31 a
2=3
6uMDC
A
t=dr
2
k
2
t 2
Eq. (1) is applicable to chemically controlled processes and
Eq. (2) to diffusion controlled processes through the porous
product layer. where k
c
is the rst-order rate constant
(m min
1
), M is the molecular weight of the solid reactant
(kg mol
1
), C
A
is the acid concentration (mol m
3
), D is the
diffusion coefcient (m
3
min
1
), d is the density of the particle
(kg m
3
), r is the initial radius of the particle in (m), a is the
fraction reacted at time t (min), k
1
(m min
1
) and k
2
(m
2
min
1
) are the overall rate constants, and u is the stoichi-
ometric coefcient
To determine which of the kinetic equations mentioned
above are applicable, the data presented in Fig. 5 are plotted
according to Eqs. (1) and (2), respectively. The plots of the
above kinetic equations as a function of time showed that only
Eq. (1) gives perfectly straight lines from 0 to 10 min for zinc,
but Eq. (2) does not, indicating that the dissolution reaction of
Zn is controlled by the chemical reaction taking place on the
surface of the slag and H
2
SO
4
. Plots of the function
1(1 a)
1/3
vs. time at the leaching temperatures as shown
in Fig. 6 indicate that the dissolution rates of zinc in the range
035C is chemically controlled according to Eq. (1) This im-
plies that, during the initial periods, the reaction uid can pen-
etrate freely within the cracked and porous particles and the
leaching reaction is not restricted to the core/product interface.
40 0 20 60 80
0
20
40
60
80
100
Zn
Cu
R
e
c
o
v
e
r
y
(
%
)
Temperature,
o
C
Figure 5 Effect of temperature on the recovery of zinc and
copper from brass slag [H
2
SO
4
] = 30%, leaching time = 10 min,
L/S = 5.
0 2 4 6 8 10 12
0.0
0.2
0.4
0.6
Temperature R
2
10
o
C 0.988
15
o
C 0.933
20
o
C 0.994
25
o
C 0.995
35
o
C 0.993
1
-
(
1
-
)
1
/
3
Time (hr)
Figure 6 Plots of 1(1a)
1/3
vs. time for zinc dissolution at
various temperature in 30% H
2
SO
4
.
3.1 3.2 3.3 3.4 3.5 3.6
-5.5
-5.0
-4.5
-4.0
-3.5
-3.0
-2.5
l
n
K
( 1/T ) x 10
3
,
o
k
Figure 7 Arrhenius plot for Zn dissolution in 30% sulfuric acid
solution.
4 I.M. Ahmed et al.
Please cite this article in press as: Ahmed, I.M. et al., Leaching and recovery of zinc and copper from brass slag by sulfuric acid.
Journal of Saudi Chemical Society (2012), http://dx.doi.org/10.1016/j.jscs.2012.11.003
After that, the leaching of non-porous core of particles pro-
gressed slowly and the kinetics appear to be limited by diffu-
sion through the product layer.
3.1.7. Estimation of activation energy
The relation between the overall rate constant from Eq. (1) and
temperature may be expressed by the Arrhenius equation:
k AexpE
a
=RT 3
where k is the overall rate constant (m min
1
), A is the fre-
quency factor (min
1
), E
a
is the activation energy (J mol
1
),
R is the universal gas constant (8.314 J K
1
mol
1
) and T is
the reaction temperature (K).
Rate constants for different temperatures were then plotted
against the corresponding temperatures according to the
Arrhenius equations (Fig. 7). The apparent value of activation
energy (E) for the leaching of slag by H
2
SO
4
was calculated
from the slope of the obtained straight line and found to be
about 59.0 2.7 kJ mol
1
for zinc. The value of the activation
energy supports the proposed chemically controlled mecha-
nism. This value is similar to those obtained by Terry and
Monhemius (1983), that found 49.2 kJ/mol
1
and 39.0 kJ/mol
1
for the dissolution of natural and synthetic willemite samples
in sulfuric acid solution (pH = 1.9), respectively. Similarly,
Teresa Pecina et al. (2008) found an activation energy of
50.0 kJ/mol. for the dissolution of zinc in sulfuric acid.
3.2. Cementation step
Zinc dust and slag were used in stoichiometric ratio as cement-
ing agents to remove copper from the leaching solution, within
10 min at 25C where >99% of copper was removed. Copper
cementation occurs according to the following reaction:
Cu
2
Zn !Zn
2
Cu
The progress of the reaction was followed by the measure-
ment of free Cu
2+
ions in the solution. It is reported that
cementation reactions mostly follow rst order kinetics (R).
3.3. Process ow sheet
The sequence of operations for the separation of zinc, copper
from the studied slag is shown in Fig. 8. Using 30% (V/V)
H
2
SO
4
for selective leaching of zinc, the pH of the solution
was adjusted at 3.5 using NH
4
OH, whereas iron and aluminum
were precipitated as hydroxides in addition to silica gel. Zinc
solution can be subjected to crystallization to obtain zinc sul-
fate heptahydrate. Zinc can be precipitated as zinc carbonate
at pH = 6.5 by adding Na
2
CO
3
. The copper residue is leached
with hydrochloric acid to obtain cupric acid solution that can
be crystallized to get cupric chloride dihydrate.
Mineralogical analysis of the slag before and after the
leaching process was determined by XRD as in Fig. 9. XRD
analysis for the slag before the leaching process indicated that
it contained two main constituents; namely zinc minerals
(Zn
2
SiO
4
and ZnO), and copper oxide (CuO) with small
amounts of quartz (SiO
2
) and aluminum (Al
2
O
3
SiO
2
). How-
ever, iron and other elements were present in trace amounts.
The analysis of the residue (slag sample after leaching process)
indicated that it contained only quartz (SiO
2
) as the main
constituent.
4. Conclusions
Leaching of brass slag to recover zinc and copper in sulfuric
acid solutions was studied. It was found that the zinc
Brass smelter slag (100.0 g) (Zn, Cu, Fe, Al, )
Leaching with 30% H
2
SO
4,
10 min.
Copper residue
( Zn, Cu, Al, Fe), solution
Leaching with HCl Adjust the pH to 3.5 by NH
4
OH
CuCl
2
.2 H
2
O
( 25.3 g ) Zn, Cu (soln) Fe(OH)
3
and Al(OH)
3
Cementation by zinc dust (1.2 g)
ZnSO
4
.7H
2
O Spongy Copper
(Crystals), (250.0 g) (Powder), (1.1 g)
Figure 8 Proposed ow sheet for the sequential separation of zinc, copper, iron and aluminum from the brass smelter slag.
Figure 9 XRD pattern of the slag before and after the leaching
process.
Leaching and recovery of zinc and copper from brass slag by sulfuric acid 5
Please cite this article in press as: Ahmed, I.M. et al., Leaching and recovery of zinc and copper from brass slag by sulfuric acid.
Journal of Saudi Chemical Society (2012), http://dx.doi.org/10.1016/j.jscs.2012.11.003
extraction was fast and increased with sulfuric acid concentra-
tion. The shrinking core model with chemical control tted the
experimental results. The use of the grain model, which suc-
cessfully described the dissolution of zinc analysis of the zinc
silicate particles, is suggested because there was no reaction
product on the particle surfaces. The activation energy was
found to be 59.0 2.7 kJ/mol.
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6 I.M. Ahmed et al.
Please cite this article in press as: Ahmed, I.M. et al., Leaching and recovery of zinc and copper from brass slag by sulfuric acid.
Journal of Saudi Chemical Society (2012), http://dx.doi.org/10.1016/j.jscs.2012.11.003