Hydrometallurgy 134-135 (2013) 117–123

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Hydrometallurgy
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Citric acid as an alternative lixiviant for zinc oxide dissolution

R. Larba, I. Boukerche, N. Alane, N. Habbache, S. Djerad ⁎, L. Tifouti
Laboratory of Environmental Engineering, Department of Chemical Engineering, University of Annaba, P.O. Box 12, Annaba 23000, Algeria

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

Article history: The reactivity of ZnO during its dissolution by citric acid in different electrolytic environments was studied. It
Received 21 August 2012 was observed that at low concentration (0.05 mol/L) citric acid was able to dissolve 90.4% of ZnO after 1 h at
Received in revised form 8 November 2012 50 °C. The addition of chlorides, nitrates and sulfates enhanced the dissolution to 98%, 84% and 67% respec-
Accepted 11 February 2013
tively attained after 15 min at 40 °C. In the absence of citric acid, Cl−, NO3− and SO42− also reacted with the
Available online 15 February 2013
solid surface leading to dissolve 4.6%, 4.9% and 13.7% of ZnO respectively at 50 °C after 60 min of reaction.
Keywords:
The dissolution was controlled by surface chemical reaction in case of zinc dissolved by citric acid mixed
Zinc oxide with chloride and nitrate ions. When the dissolution was performed in the presence of citric acid alone
Acid leaching and citric acid mixed with sulfates, the chemical reaction in an initial stage and transport through the bound-
Citric acid ary layer in a second stage were the rate controlling steps.
Anions © 2013 Elsevier B.V. All rights reserved.
Reaction kinetics

1. Introduction Agatzini-Leonardou (1994) studied the dissolution of nickel and iron

Metals play an important part in industrial development and im-
proved living standards. Society can draw on metal resources from
Earth's crust as well as from metal discarded after use. New routes
for metals recycling are continually investigated not only for lowering
costs but also to prevent the environmental pollution. Zinc is among
the most prevalent and valuable metals used in industry. It is widely
used as oxide, sulfide, and chloride. The oxide is used in rubber tires,
white paint pigment, ceramic glaze, opaque base in cosmetics and in
catalysis (Chen and Tang, 2007; Evgenidou et al., 2007; Kim et al.,
1997; Srinivasan et al., 2006). At present, approximately 70% of the
zinc produced originates from mined ores and 30% from recycled or
secondary source. The level of recycling is increasing in step with
progress in zinc production and zinc recycling technologies. The wide-
ly used method to treat and recycle zinc involves hydrometallurgical
unit operations (Abdel-Aal, 2000; Chen et al., 2009; Feng et al., 2007;
He et al., 2010; Navidi Kashani and Rashdi, 2008; Shirin et al., 2006).
Mineral acids such as HCl, H2SO4 and HNO3 are commonly used as
leaching reagents and H2SO4 is the most preferred lixiviant (Dutra et
al., 2006; Fernandez-Olmo et al., 2007; Langova et al., 2009; Pecina
et al., 2008; Shanming et al., 2011; Spathis and Poulios, 1995). Howev-
er, mineral acids cause environmental pollution and may dissolve
undesired impurities. Organic acids are not usually used as leachants
due to their low dissolution efficiencies, but they are attractive
due to the ease of biodegradation. They can be used at mildly acidic
conditions (pH 3–5). The use of organic acids for the extraction
of metals has been studied by many researchers. Tzeferis and
⁎ Corresponding author. Tel.: +213 6 66 80 57 41; fax: +213 38 87 65 60.
E-mail address: s_djerad@hotmail.com (S. Djerad).
from nickel ferrous ores in mineral and organic acids. They observed
that among organic acids used (acetic, citric and oxalic acids) citric
acid was the most effective in nickel extraction and even more than
sulfuric acid over long time reaction. Marafi and Stanislaus (2011) in-
vestigated the recovery of valuable metals (Mo, V, Ni) from spent
hydroprocessing catalyst by using two acids, one inorganic (H2SO4)
and one organic (citric acid). Citric acid was found to be more active
than H2SO4. Furthermore, in the case of carbonaceous compounds,
using inorganic acids may lead to the formation of high CO2 pressure
due to the fast dissolution which may cause risks (Laçin et al., 2005).
Citric acid is a naturally occurring fruit acid, produced by microbial
fermentation. It is one of the world's largest-tonnage fermentation
products. In hydrometallurgical treatments, the ability to recover
metals or metal oxides depends on their chemical reactivities. When
the metal treated is known to be easily dissolved then it seems
more appropriate to use a less costly and more environmentally
friendly leachant such as citric acid.
The leaching of zinc oxide in citric acid has not been reported pre-
viously. This study investigates the dissolution of zinc from ZnO/
α-Al2O3 catalyst in citric acid solutions.
The acid concentration, stirring speed, temperature and the pres-
ence of anions were chosen as experimental parameters. The dissolu-
tion kinetics were examined according to the heterogeneous reaction
kinetic models.
2. Experimental
The sample used in this study was a 5%ZnO/α-Al2O3 (mol%); it
was characterized by SEM and XRD analyses (Fig. 1a and b). Scanning
electron microscopy (SEM) image was taken with (JEOL, Model

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http://dx.doi.org/10.1016/j.hydromet.2013.02.002
118 R. Larba et al. / Hydrometallurgy 134-135 (2013) 117–123

(a) Table 1
Reaction parameters used for the dissolution of ZnO by citric acid.

Parameter varied Constant parameters

Acid concentration 25 °C, l/s = 50 mL/g, 350 rpm

0.01, 0.05, 0.1, 0.5 mol/L
Stirring speed 25 °C, l/s = 50 mL/g, C = 0.05 mol/L
100, 350, 600, 850 rpm
Temperature l/s = 50 mL/g, C = 0.05 mol/L, 350 rpm
25, 30, 35, 40, 45, 50 °C
Effect of anions l/s = 50 mL/g, Canion = 0.05 mol/L,
NaCl, NaNO3, Na2SO4 Ccitric acid = 0.05 mol/L, 350 rpm
at 25, 30, 35, 40, 45, 50 °C

study was less than 3. Thus the reaction was carried out with respect
to Eq. (1).
After leaching process, the reaction mixtures were filtered and Zn2+
was analyzed by titration with EDTA using murexide as indicator. The
data presented are an average of two test replicates, with an error of 5%.
(b) The process conditions studied included the acid concentration
300 (0.01, 0.05, 0.1 and 0.5 mol/L), stirring speed (100, 350, 600 and
Al2O3 Al2O3 850 rpm) and temperature (25, 30, 35, 40, 45 and 50 °C). Three salts
250 NaCl (99.5%, Biochem), NaNO3 (99%, Fluka) and Na2SO4 (99%, Sigma-
Al2O3
Aldrich) were used to study the effect of anions (Cl −, NO3− and SO42−)
Al2O3
200
on the dissolution efficiency of zinc oxide by citric acid. During the ex-
Intensity

periments, the acidity of the solutions was followed using a pH meter

Boeco BT-600. The point of zero charge (pHPZC) of ZnO/α-Al2O3 was de-
150
Al2O3
termined by a method used elsewhere (León y León and Radovic, 1994;
Al2O3 Al2O3
Al2O3 Moreno-Castilla et al., 2000). This method consisted on mixing 1 g of
100 the solid with 20 mL of CO2-free distilled water. The sample was man-
ually agitated over a period of 48 h after which, the pH of the mixture
50 was taken as pHPZC. The pHPZC of the catalyst was 8.95.
ZnO Al2O3
ZnO ZnO

0
3. Results and discussion
10 20 30 40 50 60 70
2 Theta 3.1. Effect of acid concentration

Fig. 1. SEM image (a) and X-ray diffraction pattern (b) of ZnO/α-Al2O3 catalyst.
JEOL-5410) and the X-ray diffraction pattern was obtained with a
Siemens D-500 powder X-ray diffractometer using Cu Kα radiation
(λ = 1.5406 Å) in step mode between 10° and 70°, using a step size
of 0.02 step/s. Citric acid monohydrate (99.5%, Riedel de Haën) was
used as the leaching reagent. Experiments for determining the disso-
lution rate of zinc oxide in citric acid at the desired liquid/solid ratio
(10 mL/0.2 g) were conducted with the same equipment used in a
previous study (Habbache et al., 2009). The effect of parameters on
the dissolution of zinc oxide was investigated using the conditions
given in Table 1.
The reaction steps between zinc oxide and citric acid can be writ-
ten as follows (Demir et al., 2006):
þ −
C6 H8 O7ðsÞ þ H2 OðlÞ ↔H3 OðaqÞ þ C6 H7 O7 ðaqÞ
The effect of acid concentration on the extent of zinc reacted (%) as a
function of time is shown in Fig. 2. The zinc dissolution was largely in-
creased when citric acid concentration was increased from 0.01 to
0.05 mol/L and slightly increased thereafter. The concentration of
0.05 mol/L was selected to investigate the effect of the other parameters.
3.2. Effect of stirring speed
Fig. 3 shows that the increase in agitation from 100 to 350 rpm im-
proved the dissolution efficiency of zinc. A further increase in stirring to
600 and 850 rpm decreased the dissolution efficiency. This behavior
100
90
80
ð1Þ
Zinc dissolved (%)

70
60
− þ 2− 50
C6 H7 O7 ðaqÞ þ H2 OðlÞ ↔H3 OðaqÞ þ C6 H6 O7 ðaqÞ ð2Þ
40
30
0.01M
2− þ 3−
20 0.05M
C6 H6 O7 ðaqÞ þ H2 OðlÞ ↔H3 OðaqÞ þ C6 H5 O7 ðaqÞ ð3Þ 0.1M
10
0.5M
0
0 10 20 30 40 50 60 70
2þ 3−
3ZnOðsÞ þ 2C6 H8 O7ðaqÞ →3Zn þ 2C6 H5 O7 ðaqÞ þ 3H2 OðlÞ : ð4Þ t (min)

The pKa values found in the literature (Dean, 1972) are pK1 = 3.128, Fig. 2. Effect of citric acid concentration on zinc dissolution. Operation conditions:
pK2 = 4.761, and pK3 = 6.396. The pH value of citric acid used in this 25 °C, l/s = 50 mL/g, 350 rpm.
 R. Larba et al. / Hydrometallurgy 134-135 (2013) 117–123 119

100
at 25 °C, it increased up to 37.3% at 50 °C after the same period of
90 time. The highest dissolution efficiency was 90.4% attained after
80 60 min of reaction at 50 °C. Alpha alumina dissolution was checked
during the experiments. No detectable dissolution occurred. This result
Zinc dissolved (%)

70
60 agrees with that reported in the literature (Al-Mansi and Monem,
50 2002). In fact α-alumina is formed after calcination of a precursor
such as aluminum nitrate of hydroxide at high temperature ~ 1200 °C
40
which makes it very stable under aggressive conditions such as strong
30 100rpm acids (HCl, H2SO4 or HNO3). Since in this study mildly conditions were
20 350rpm
600rpm used it is evident that alpha alumina remained unattacked.
10 850rpm
0
0 10 20 30 40 50 60 70 3.4. Effect of anions
t (min)
The effect of anions was tested by adding NaCl, NaNO3 and
Fig. 3. Effect of stirring speed on zinc dissolution with citric acid. Operation conditions: Na2SO4 to citric acid solutions. The results shown in Fig. 4b–d indi-
25 °C, 0.05 mol/L, l/s = 50 mL/g. cate that the dissolution of zinc with citric acid in the presence of
the three anions was effectively enhanced compared to the results
was due to the mechanochemical effect of the magnetic stirrer. In fact, it in their absence (Fig. 4a). Higher effects were observed in the pres-
was observed that at low speed condition, the powder sample in the so- ence of chlorides and nitrates. In fact, in the case of the mixtures of
lution remained at the bottom of the glass flask. The powder might be citric acid with chloride, nitrate and sulfate, the leaching efficiencies
ground in this case leading to improve the dissolution efficiency. At at 40 °C after 15 min were 98%, 84% and 67%, respectively. The effi-
higher speed condition, the powder was well dispersed so that the ciency of the mixture containing sulfates was slightly better than
mechanochemical effect became less important and as a result, the de- that of citric acid alone since the latter dissolved only 64% after the
crease in the dissolution efficiency was observed. The value of 350 rpm same period of time at 40 °C.
was kept for further use in this study. In order to determine whether ZnO dissolved in the presence of
different anions without citric acid, the same experiments were
conducted by using aqueous solutions of the three salts.
3.3. Effect of temperature Fig. 5 shows that the zinc dissolutions in different anion media after
60 min were 13.7% in sulfate, 4.6% in chloride and 4.9% in nitrate. These
Fig. 4a shows that zinc dissolution increased with increasing the dissolution efficiencies in the three cases remained very low compared
temperature. In fact, after 2 min of reaction 7.2% of zinc was dissolved to the results obtained with citric acid alone (Fig. 4a). Thus, it can be

(a) (b)
100 100
90 90
80 80
Zinc dissolved (%)

Zinc dissolved (%)

70 70
60 60
50 50
40 40
25o C
30 30o C 30 25o C
35o C 30o C
20 40o C 20 35o C
10 45o C
50o C 10 40o C
0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
t (min) t (min)
(c) (d)
100 100
90 90
80 80
Zinc dissolved (%)

Zinc dissolved (%)

70 70
60 60
50 50
40 25o C 40 25o C
30 30o C 30 30o C
35o C 35o C
20 40o C 20 40o C
45o C 45o C
10 50o C 10 50o C
0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
t (min) t (min)

Fig. 4. Effect of temperature on zinc dissolution with citric acid alone (a) and citric acid mixed with Cl− (b), NO3− (c) and SO42− (d). Operation conditions: l/s= 50 mL/g, 350 rpm,
citric acid concentration = 0.05 mol/L, anion concentration = 0.05 mol/L.
120 R. Larba et al. / Hydrometallurgy 134-135 (2013) 117–123

(a) 5
The following expressions can be used to describe the dissolution
25 °C kinetics of the process:
4.5 30 °C
35 °C
4 40 °C For liquid film diffusion control : x ¼ kt ð5Þ
Zinc dissolved (%)

45 °C
3.5 50 °C

3 For film diffusion control through product layer : ð6Þ

2.5 2=3
1−3ð1−xÞ þ 2ð1−xÞ ¼ kt
2
1.5 1=3
For surface chemical reaction control : 1−ð1−xÞ ¼ kt ð7Þ
1
0.5 where x is the fractional conversion of zinc at time t and k is the ap-
0 parent rate constant. The overall rate of dissolution is controlled by
0 10 20 30 40 50 60 70 the slowest of these sequential steps.
t (min) Fig. 6 shows good linear correlations, based on Eq. (7) for the dis-
(b) solution of zinc by citric acid in the presence of chlorides and nitrates
6
25 °C during the whole reaction times. This indicates a chemical controlled
30 °C
35 °C dissolution process in these cases. In case of zinc dissolved by citric
5 40 °C
acid alone and citric acid mixed with sulfates, chemical reaction
Zinc dissolved (%)

45 °C

4
50 °C (Eq. (7)) controlled the processes in range (0–5 min) while diffusion
through a porous solid layer (Eq. (6)) controlled the processes in
3 range (10–60 min).
From the slopes of the straight lines in Fig. 6 the apparent rate
2 constants k were evaluated. Arrhenius equation k = k · e −Ea/RT was
plotted as lnk vs. (1/T) for each temperature and the activation ener-
1 gies were calculated from the slopes − Ea/RT. The following values of
Ea were determined:
0
0 10 20 30 40 50 60 70 EaðZnOþcitricÞ ¼ 45:7 kJ=mol for rangeð0–5 minÞ and
t (min) 12:25 kJ=mol for the range ð10−60 minÞ:
(c)
16 EaðZnOþcitricþsulfatesÞ ¼ 37:0 kJ=mol for range ð0–5 minÞ and
25 °C
14 30 °C 23:15 kJ=mol for range ð10−60 minÞ:
35 °C
Zinc dissolved (%)

12 40 °C
45 °C EaðZnOþcitricþnitratesÞ ¼ 71:5 kJ=mol
50 °C
10

8 EaðZnOþcitricþchloridesÞ ¼ 96:9 kJ=mol:

6
High activation energies were obtained for the dissolution reaction
4 of zinc oxide by citric acid in the presence of chlorides and nitrates.
2 Such values indicate that chemical reaction strongly controlled the dis-
solution processes. In the case of citric acid alone and citric acid mixed
0 with sulfates, the chemical reaction controlled the processes only in
0 10 20 30 40 50 60 70
the first 5 min followed by a longer controlling step through the porous
t (min) layer. Lower activation energies were obtained in these cases compared
to those obtained with nitrates and chlorides.
Fig. 5. Effect of the presence of Cl− (a), NO3− (b) and SO42− (c) on zinc dissolution in the
absence of citric acid. Operation conditions: anion concentration: 0.05 mol/L, l/s=50 mL/g,
350 rpm. 3.6. pH and point of zero charge

Zinc dissolution was affected by some parameters such as the

concluded that both H + and anions are involved in the rate controlling
step where the anions have a catalytic effect.
3.5. Kinetic study
Kinetic study of a leaching reaction is required for the design of an
efficient leaching reactor used in a hydrometallurgical plant. In het-
erogeneous reaction systems, most reactions follow a shrinking
core model (SCM) which approximates the dissolution of real parti-
cles (Levenspiel, 1999). The particles of the solid treated in this study
were almost spherical in shape with particle size of about 70 μm as
shown in Fig. 1a. In this model, the overall leaching process may be
controlled by intrinsic chemical reaction or by external mass
transfer.
acidity of the solution, temperature and the presence of anions.
The effect of anions was observed when the solid was contacted
with solutions of NaCl, NaNO3 and Na2SO4. The fact that ZnO was
dissolved in the absence of H+ was due to the special characteristics
of this metal oxide. In fact, it was reported that in water suspension of
zinc oxide, the solid surface was in equilibrium with the solution
containing several species such as Zn2+, Zn(OH)2(aq), Zn(OH)+(aq),
[Zn4(OH)4]4+(aq) and [Zn(OH)]3+(aq) (Degen and Kosec, 2000). Anions
when present with ZnO in water may react with these species
depending on their affinity and their concentration. The results
obtained after the contact of ZnO with chlorides, nitrates and sulfates
were not the same indicating three different features in the interaction
of the anions with these species. On the other hand, citric acid is a
tricaboxylic acid which can undergo different degrees of deprotonation
forming various chelated complexes with zinc surface (Yoo and James,
2003). This may complicate the prediction of the mechanism of zinc
 R. Larba et al. / Hydrometallurgy 134-135 (2013) 117–123 121

0.4 y = 0.0678x + 0.0028 0.6 y = 0.0056x + 0.2256

R² = 0.9995
25oC Citric acid R² = 0.9991
Citric acid 30oC
0.35 25oC
y = 0.0606x - 0.0078 0.5 35oC y = 0.005x + 0.1899
30oC
R² = 0.9972 40oC R² = 0.9967
35oC

1-3(1-X)2/3+2(1-X)
0.3 45oC
40oC
y = 0.0482x - 0.0053 0.4 50oC
45oC y = 0.0048x + 0.148
0.25 R² = 0.998
1-(1-X)1/3

50oC R² = 0.9986
y = 0.0344x - 0.0037 0.3
0.2 R² = 0.9976 y = 0.0044x + 0.0705
R² = 0.9951
0.15 y = 0.029x - 0.0053 0.2
R² = 0.9949 y = 0.004x + 0.0486
0.1 R² = 0.9866
y = 0.0155x - 0.0028 0.1 y = 0.0038x - 0.012
0.05 R² = 0.9938
R² = 0.9953

0 0
0 1 2 3 4 5 6 0 10 20 30 40 50 60 70
t (min) t (min)

0.7 y = 0.0057x + 0.2502

0.4 y = 0.0722x + 0.0043
Citric acid+SO42- R² = 0.9959 Citric acid+SO42- R² = 0.9929
25oC
0.35 0.6
25oC y = 0.0589x + 0.0068 30oC
y = 0.0053x + 0.2008
30oC R² = 0.9914 35oC R² = 0.9855

1-3(1-X))2/3+2(1-X)
0.3 35oC 0.5 40oC
40oC y = 0.0499x + 0.0009 45oC y = 0.0044x + 0.1606
0.25 45oC R² = 0.9998 50oC
1-(1-X)1/3

0.4 R² = 0.9861
50oC
y = 0.0381x - 0.0025
0.2 y = 0.0038x + 0.1319
R² = 0.9962 0.3 R² = 0.9932
0.15 y = 0.0306x - 0.0012
y = 0.0032x + 0.0976
R² = 0.9996 0.2
0.1 R² = 0.9873
y = 0.0224x + 0.0011 y = 0.0029x + 0.0784
0.05 0.1
R² = 0.998 R² = 0.9886

0 0
0 1 2 3 4 5 6 0 10 20 30 40 50 60 70
t (min) t (min)

1 25oC y = 0.0968x + 0.0166

1 30oC
25oC Citric acid+Cl - 0.9 R² = 0.9908
y = 0.0481x + 0.0052 35oC
0.9 30oC 40oC
35oC
R² = 0.9933 0.8 45oC
0.8 y = 0.0624x + 0.0216
40oC 50oC
0.7 R² = 0.981
0.7
1-(1-X)1/3

y = 0.0159x + 0.0662 0.6

1-(1-X)1/3

0.6 y = 0.0317x + 0.0225

R² = 0.9847
0.5 R² = 0.9859
0.5
0.4 y = 0.0209x + 0.0036
0.4
y = 0.0118x + 0.0286 R² = 0.9836
0.3 R² = 0.9888 0.3
y = 0.0158x + 0.0034
0.2 0.2 R² = 0.9929
y = 0.0066x + 0.0087 Citric acid+NO3- y = 0.0105x + 0.0107
0.1 R² = 0.991 0.1
R² = 0.9934
0 0
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70
t (min) t (min)

Fig. 6. Fit of shrinking core model to the experimental data.

dissolution when the three components (zinc oxide+ anion + citric
acid) are present in the same solution.
Fig. 4a and d shows that a retardation of zinc dissolution rate started
around 10–15 min in both cases. This was not the case when chlorides
and nitrates were present with citric acid where the dissolution of zinc
was found to increase almost regularly up to 60 min of reaction. The pH
of the solutions containing anions at 0.05 mol/L without citric acid was
measured at 25 °C. The values were 5.99 for the solution of Na2SO4 and
5.83 for both NaCl and NaNO3 solutions. The pHPZC of the solid was 8.95
and the initial pH value of citric acid solution at 0.05 mol/L was 2.20.
Thus, these conditions promoted the formation of positively charged
solid surface when citric acid solution reacted with the catalyst. Conse-
quently, the surface of the solid was ready to adsorb and/or react with
negative species like anions during the dissolution reactions.
Fig. 7 shows the variation of pH of the different solutions used in
this study during the dissolution reactions of zinc oxide at 25 °C.
The initial pH values of both mixtures (citric acid + Cl −) and (citric
acid + NO3−) were the same (2.13), while those of citric acid and the
mixture (citric acid + SO42−) were 2.20 and 2.36 respectively. Thus,
the presence of anions also affected the initial pH value of citric acid
solution. After 60 min of reactions, the pH values increased up to
2.68 (citric acid + Cl − and NO3−), 2.71(citric acid) and 2.77 (citric
acid + SO42−). These values remained lower than the pKa of citric
acid (3.128) which may accelerate the processing of the dissolution
of zinc.
It is worth noting that an increase in pH values of the solutions in
the first 20 min was clearly observed in all cases indicating an impor-
tant consummation of H + ions (Fig. 7). After 20 min the pH values
122 R. Larba et al. / Hydrometallurgy 134-135 (2013) 117–123
2.9
2.8
2.7
pH of the solution
2.6
2.5
2.4
2.3 citric acid + chlorides
citric acid + nitrates
2.2
citric acid
2.1 citric acid + sulfates
2
0 10 20 30 40 50
t(min)
Fig. 7. Variation of pH values during zinc oxide dissolution by citric acid. Operation
conditions: 25 °C, citric acid concentration = 0.05 mol/L, anion concentration:
0.05 mol/L, l/s= 50 mL/g, 350 rpm.
registered almost a plateau suggesting no more (or a very slight)
contribution of H + ions in the dissolution reactions. However,
Fig. 4 shows that the dissolution reactions were still in progress
after 20 min in all cases. These observations indicate that at the be-
ginning of the reactions H + ions were strongly involved in the disso-
lution reactions, but with the processing of the dissolutions they
played a less important role. Thus, it can be concluded that the re-
sults of the dissolution obtained after 20 min of reaction were main-
ly due to the interactions of anions with the solid surface. Since the
affinity of each anion to the solid surface was different it affected
thus the final result of the dissolution. Zinc oxide dissolution was
probably accomplished by a complex formation mechanism in all
cases. We do not know however whether anions contributed to the
dissolution in the presence of citric acid from the beginning of the re-
actions. Other investigations are needed to better clarify these
results.
3.7. Comparison with other oxides
In the absence of citric acid at ambient temperature, no dissolution
reaction of zinc occurred as the reactions started in the presence of
anions, but with increasing reaction time or temperature different be-
haviors were observed. In fact, nitrates reacted first with the solid
surface followed by chlorides and then sulfates respectively. It
seems however that the affinity of the surface to the three anions
changed when H + was present. In fact, the efficiency of the mixture
(citric acid + chlorides) in zinc dissolution was greater than that of
the mixture (citric acid + nitrates) while the mixture (citric
acid + sulfates) registered the lowest dissolution efficiency in this
case. These results indicated that anions were not inert towards the
solid surface. On the other hand, it was observed that citric acid
when used alone as leachant, the dissolution was controlled by both
chemical reaction and diffusion through boundary layer. When chlo-
rides and nitrates were added to citric acid, chemical reaction became
the unique controlling process over the whole reaction time. It can be
speculated that the addition of both anions accelerated the diffusion
process. The addition of sulfate ions on the contrary did not lead to
change the rate controlling steps observed with citric acid. Thus, the
addition of anions affected the kinetic and the mechanism of the dis-
solution reaction. In our previous studies (Boukerche et al., 2010;
Habbache et al., 2009) conducted on CuO/α-Al2O3 and CoO/α-Al2O3
it was observed that each metal oxide had its own behavior in the
presence of acids. In fact, it was concluded from the results obtained
that cobalt oxide was a hard dissolving compound since it needed
drastic operation conditions (high temperature (85 °C), high stirring
speed (850 rpm), high acid concentration (2 mol/L) and high liquid
to solid ratio (100 mL/g) to be dissolved by inorganic acids. On the
contrary, copper oxide was found to be easily dissolved by inorganic
acids under moderate conditions (ambient temperature and without
stirring). However copper oxide was slightly dissolved by citric acid
compared to zinc oxide. In fact, citric acid at 0.5 mol/L was not able
to dissolve CuO at temperature lower than 40 °C and liquid to solid
ratio lower than 40 mL/g. At 40 °C, for example 32% of CuO were
extracted after 4 h of leaching time. At 60 °C, 76% were dissolved
after the same period of time. In case of ZnO, a low citric acid concen-
tration (0.05 mol/L) was enough to dissolve 62% of zinc at 25 °C after
1 h. On the other hand, the dissolution of CuO by citric acid was con-
60
trolled by the surface reaction over the whole reaction time while the
dissolution of ZnO by the same leachant was controlled by both
chemical reaction and diffusion process. It should be noted however
that the kinetic studies were conducted with different parameters
such as the metal oxide content (10% CuO/Al2O3 and 5% ZnO/Al2O3),
the concentration of citric acid (0.5 mol/L with CuO and 0.05 mol/L
with ZnO) and liquid/solid ratio (40 mL/g with CuO and 50 mL/g
with ZnO). Only particle size was the same in both cases.
Thus, despite the fact that both CuO and ZnO are considered as
easily dissolving compounds, each metal has its own behavior
depending on the affinity of the surface to the electrolytic environ-
ment. In all cases (CoO, CuO and ZnO) it was observed that the pres-
ence of chlorides in the form of acid (HCl) or salt (NaCl) enhanced
effectively the dissolution rate of metal oxides regardless of their na-
ture. This was explained in the case of CuO by the fact that chlorides
have the tendency to form stable chloro-complexes (Cu(OH)Cl)ad
adsorbed on the solid surface leading to accelerate the rate of dissolu-
tion (Senanayake, 2007). In our study it was observed that sulfates
when present without acid promoted the dissolution rate of zinc
oxide at 50 °C. This behavior was probably due to the high affinity
of the surface to sulfate ions.
In the literature, the surface affinity of ZnO to sulfates was explained
by the fact that in the solution, sulfate ions gave a multivalent conjugate
bases of sulfuric acid (pK = −3, pK= 1.9). The strong surface adsorp-
tion which occurred was a result of high negative charge density associ-
ated with this multivalent acid (Degen and Kosec, 2000). Thus, it can be
suggested that the explanation given by Senanayake (2007) concerning
chlorides with CuO may be applied to sulfates contacted with ZnO.
However, this explanation cannot be used when H+ ions are present
with sulfates. According to Senanayake chloro-complexes are formed
in the presence of hydrochloric acid. It seems in the case of zinc oxide
that sulfate complexes are destructed in the presence of acidic media
which explain the low dissolution efficiency obtained in this case.
There is still a lack of the detailed knowledge about the reaction mech-
anisms and other investigations are needed to clarify these behaviors.
4. Conclusion
The results of this study have shown that the dissolution of ZnO
with citric acid depends on the interaction with the electrolytic envi-
ronment. In fact, citric acid dissolved 90.4% of ZnO after 1 h at 50 °C
of reaction. This efficiency was increased in the presence of chlo-
rides and nitrates respectively while a slight effect was observed
when sulfates were added. On the other hand, it was observed
that the solutions containing chlorides and nitrates have the same
pH value while their efficiencies in zinc dissolution were different.
This indicates that the dissolution reaction was influenced by the
behavior of anions with the solid surface rather than by the overall
acidity. Furthermore, the fact that the dissolution kinetic of zinc
oxide was governed by chemical reaction when leachants were
(citric acid + Cl −) and (citric acid + NO3−), and by both chemical
reaction and diffusion through boundary layer when leachants
were citric acid and (citric acid + SO42 −) indicates that the electro-
lytic environment has an important effect on the mechanism of the
dissolution of zinc oxide. It is difficult to predict the mechanism of
 R. Larba et al. / Hydrometallurgy 134-135 (2013) 117–123
the dissolution reactions when all components were present. It
seems however that the combination of the complexation reaction
of zinc oxide by citric acid added to the interaction of anions with
different hydrolyzed species of ZnO led to solubilize zinc oxide
more effectively.
Citric acid is a natural acid with low molecular weight, it is also con-
sidered as non-persistent biodegradable organic product (Römkens et
al., 2002) and its half life in soil suspension is close to 8 days
(Brynhildsen and Rosswall, 1997). These characteristics are considered
as advantageous since alone and at low concentration (0.05 mol/L) it
can dissolve effectively zinc oxide without the risk of pollution or
post-treatment. This makes it as a good choice for a more ecological
treatment of zinc.
Acknowledgment
The authors acknowledge thankfully the financial assistance of the
General Directorate for Scientific Research and Technological Devel-
opment of Algeria (PNR Project No. 27/58).
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