Int. J. Miner. Process.

82 (2007) 80 – 85
www.elsevier.com/locate/ijminpro

A kinetic study of copper cementation with zinc in aqueous solutions

Nizamettin Demirkıran, Ahmet Ekmekyapar, Asım Künkül, Ahmet Baysar ⁎
Department of Chemical Engineering, Faculty of Engineering, Inonu University, Malatya 44280, Turkey
Received 5 June 2006; received in revised form 13 October 2006; accepted 13 October 2006
Available online 28 November 2006

Abstract

Cementation of copper from zinc containing copper solutions using metallic zinc was studied in this work. The effect of copper,
zinc and ammonium chloride concentration, stirring speed, pH and temperature on the cementation of copper was determined.
Cementation rate increased with initial copper concentration, stirring speed and temperature. pH variation from 1 to 4 increased the
cementation rate but at higher pH, the rate was not significantly effected. The cementation rate of copper increased with Zn2+ ion
concentration. However, the rate of this rise was slightly less compared to the rise that occurred in the Zn2+ ions free copper
solution.
The cementation reaction followed first order kinetics. It was observed that the reaction progressed with consecutive surface
reaction and diffusion controlling steps. The activation energy and pre exponential factors for each step were calculated and a
model describing the process was proposed.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Copper; Zinc; Cementation; Kinetics

1. Introduction with strong acids may contain more impurities. Low

Today, high-grade copper reserves have been dimin-
ished and the remaining reserves contain low-grade
copper. As a result, pyrometallurgical copper production
methods are replaced by hydrometallurgical production
processes.
Copper ores are generally found in sulfide and ox-
idized form in nature. Copper may be directly transferred
to the aqueous phase by leaching oxidized ores but
leaching of sulfide copper ores is more difficult. The
composition and purity of the resulting leaching solu-
tion depend on the structure of the ore and the type of
reactants used for leaching. Leaching solutions obtained
⁎ Corresponding author. Tel.: +90 505 310 2213; fax: +90 422 341
0690.
E-mail address: abaysar@inonu.edu.tr (A. Baysar).
0301-7516/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2006.10.005
impurity containing leaching solutions may be obtained
with weak acids, bases and salts. These reactants are
highly selective for copper dissolution (Kordosky, 1981;
Chase, 1980; Künkül et al., 1994).
It is reported that when oxidized copper ores are
leached with ammonium salts, iron dissolved from the ore
matrix precipitates as iron III hydroxide (Ekmekyapar
et al., 1988, 2003). As a result, ions left in the leaching
solution as impurities are mainly zinc and aluminum.
Cementation is the process of precipitating a metal ion in a
solution with a more active metal. This process is widely
applied in mineral industry. Generally, iron is used for
cementation of copper (Nadkarni and Wadsworth, 1967).
However, during cementation of copper with iron, the
recovery of economically valued metals such as zinc from
the solution is difficult since the solution contains high
iron concentration. Therefore, the recovery of zinc as a
 N. Demirkıran et al. / Int. J. Miner. Process. 82 (2007) 80–85 81

side product from zinc rich oxidized copper ores with Table 1
weak character leaching reactants such as ammonium Experimental parameter variation intervals for the copper cementation
reaction
salts may be important.
The objective of this work was to precipitate copper Parameter Value
from zinc containing copper solutions using metallic zinc Copper chloride 0.01 0.025 0.05 0.1
and investigate the kinetics of this cementation process. concentration (mol/L)
Stirring speed (rpm) 200 300 400 500
Copper cementation has been extensively studied
pH 1 2 3 4 (free) 4.5
and this subject is still widely investigated (Strickland Temperature (K) 308 313 318 323 328
and Lawson, 1970; MacKinnon and Ingraham, 1970; NH4Cl concentration 0.25 0.5 1
Rickard and Fuerstenau, 1968; Nadkarni et al., 1967; (mol/L)
Stefanowicz et al., 1997; Dönmez et al., 1999; Gamboa Zinc chloride concentration 0.01 0.025 0.05 0.1
(mol/L)
et al., 2005; Karavasteva, 2005). Nadkarni et al. (1967)
and Nadkarni and Wadsworth (1967) studied the
kinetics of copper cementation on iron from cupric
sulfate solutions at various concentrations and stirring from the samples and precipitated copper amount was
speeds. The cementation was reported to follow first calculated from the experimental results.
order kinetics. Depending on the stirring speed precip-
itated copper formed spongy layer to colloidal mass. The 3. Results and discussion
reaction was reported to reach a limiting value and a
theoretical model based on diffusion through a limiting 3.1. Effect of parameters
boundary film was proposed.
Copper cementation on aluminum disks as a function The concentration of copper ions was set at 0.01,
of copper concentration, temperature, pH and periph- 0.025, 0.05 and 0.1 mol/l. During the experiments the
eral velocity was studied by MacKinnon and Ingraham temperature and stirring speed were kept constant and at
(1970). Depending on the temperature of the cementing 313 K and 500 rpm, respectively. The cemented fraction
solution, the rate of deposition was either ionic diffusion of copper was plotted versus time at initial copper
or surface reaction controlled. Strickland and Lawson concentrations mentioned above. It was observed that
(1970) investigated the kinetics of copper cementation the precipitation rate of metallic copper increases as the
on rotating zinc disks. Deposition reaction was first order concentration of copper ions is increased.
and a diffusion boundary layer formed. The degree of The effect of stirring speed was tested at 200, 300, 400
agitation was found to affect the reaction rate. and 500 rpm values. Experiments were conducted at
0.05 mol/l Cu2+ concentration and the temperature was
2. Experimental kept at 313 K. The cemented fraction of copper increased
with the stirring speed.
Cementation experiments were carried out in a tem- The effect of pH was investigated at pH of 1, 2, 3, 4.5
perature controlled and mechanically stirred 400 ml and free pH (pH of 0.05 mol/l Cu2+ solution). Ammonia
glass reactor. A 45-mm-diameter Teflon stirring blade and hydrochloric acid solutions were used as pH con-
was used for stirring. The pH of the cementation solution trolling agent. The effect of pH is shown in Fig. 1. It is
was continuously monitored during the experiments. clear that maximum cementation rate is obtained at pH
Process variables were copper concentration, tempera- of 3. The yield obtained at free pH (∼ 4, this is the
ture, stirring speed, pH, and zinc concentration. Table 1 natural pH of the copper chloride solution) is close to the
shows the variation interval for these parameters. yield at pH of 3. At higher pH values, a decrease in the
Chemical reagents CuCl2.2H2O, ZnCl2 and granular yield is observed.
zinc (5 ± 0.5 mm diameter particles) from Merck The effect of temperature on copper cementation was
(Germany) were used for the experiments. Experiments investigated at 308, 313, 318, 323 and 328 K. The
were carried out as described below. Copper (Cu2+) concentration of Cu2+ ions and stirring speed for tem-
containing solution was brought to the reaction temper- perature effects were 0.05 mol/l and 500 rpm, respec-
ature and 1.5 times of stoichiometrically required zinc tively. The results showed that the cemented fraction of
granules were added to the reactor. The pH of the copper increases with temperature.
solution was not buffered and set free except for the The effect of zinc chloride on the cementation of
experiments for which the effect of pH was investigated. copper in zinc containing solutions was investigated.
At preset times, Cu2+ ions concentration was determined Equimolar concentrations of Zn2+ and Cu2+ mixtures
82 N. Demirkıran et al. / Int. J. Miner. Process. 82 (2007) 80–85
Fig. 1. The effect of pH on the copper cementation rate.
(0.01, 0.025, 0.05 and 0.1 mol/l) were prepared. For these
experiments, the temperature was kept at 313 K and the
stirring speed was set at 500 rpm. Fig. 2 clearly shows that
the cementation rate of copper increases with increased
Zn2+ ion concentration. However, the rate of copper
cementation in Zn2+ ions containing solution was slightly
lower compared to the rate that occurred in the Zn2+ ions
free copper solution.
The dissolution of copper ores with ammonium salts
has been reported in literature (Bingol et al., 2005;
Ekmekyapar et al., 2003; Oudenne and Olson, 1983). To
determine the effect of ammonium chloride on the
cementation rate in copper and zinc containing solutions
Fig. 2. The effect of zinc chloride concentration on the copper ce-
mentation rate.
Fig. 3. The effect of ammonium chloride concentration on the copper
cementation rate.
was also investigated. The concentration of ammonium
chloride was chosen as 0.25, 0.5 and 1 mol/l. It was
observed that the ammonium chloride concentration did
not affect the cementation rate at 313 K, 500 rpm stirring
speed and 0.5 mol/l equal concentrations of Cu2+ and
Zn2+ ions (Fig. 3).
3.2. Cementation kinetics
Copper cementation occurs according to the follow-
ing reaction:
Cu2þ þ Zn→Zn2þ þ Cu
The progress of the reaction was followed by the
measurement of free Cu2+ ions in the solution. It is
reported that cementation reactions mostly follow first
order kinetics (Nadkarni et al., 1967; Ornales et al.,
1998; Sedzimir, 2000; El Batouti, 2003; Strickland and
Lawson, 1970; Hiskey and Lee, 2003). We also assumed
first order kinetics for the cementation reaction
investigated in this work. The model for the first order
reaction is
lnð1  X Þ ¼ –kt ð1Þ
where X is the cemented copper fraction at time t.
Cementation reactions are basically heterogeneous and
it was thought that parameters such as concentration,
temperature and stirring speed may have effect on the
reaction rate. Hence the effect of these parameters on the
rate was investigated. Reaction data were used to obtain
 N. Demirkıran et al. / Int. J. Miner. Process. 82 (2007) 80–85
Fig. 4. Plot of ln(1 − X) versus time for various initial copper
concentrations.
ln (1 − X) versus time graphs to examine the effect of
initial Cu concentration, temperature and stirring speed.
Figs. 4, 5 and 6 indicate linear relationship. Apparent
rate constants were determined from the slope of the
lines. Experimental results exhibit a good fit to Eq. (1).
The following model was envisioned.
lnð1  X Þ ¼ –ko C a W b eE=RT t ð2Þ
where ko is pre exponential factor, C is initial copper
chloride concentration, W is the stirring speed, E ac-
tivation energy and T is absolute temperature. The
constants a and b were determined as 0.85 and 1.50,
respectively. Assuming Arrhenius type relation, ln k
versus 1/T graph should give a straight line. As seen in
Fig. 7, two straight lines are obtained. First region shows
Fig. 5. Plot of ln(1 − X) versus time for various stirring speeds.
83
Fig. 6. Plot of ln(1 − X) versus time for various temperatures.
the variation between 303–318 K and the second region
between 318–328 K.
MacKinnon and Ingraham (1970) and Miller (1973)
reported that a shift in the activation energy probably
was a result of the change in the reaction mechanism. It
may be assumed that two consecutive processes are
controlling the rate. At low temperatures, the rate con-
trolling step is the surface reaction. This is verified by
the value of the activation energy. As a matter of fact, the
overall reaction controlling step is surface reaction for
processes that are highly sensitive to temperature and
for which the activation energy is above 10 kcal/mol
(Habashi, 1969). Above 318 K, rate is controlled by the
diffusion. In diffusion controlled processes the activa-
tion energy is mostly below 10 kcal/mol.
For the first region (303–318 K) the activation
energy and the pre exponential factor were calculated as
12.7 kcal/mol and 3.75 × 104 min− 1, respectively. For
Fig. 7. Arrehenius plot for copper cementation.
84 N. Demirkıran et al. / Int. J. Miner. Process. 82 (2007) 80–85
Fig. 8. Plot of experimental and predicted cemented copper fractions.
the second region (318–328 K) these values were cal-
culated as 5.4 kcal/mol and 0.37 min− 1, respectively.
Eq. (2) may be written for the two regions:
1:50 6400=T
lnð1  X Þ ¼ –3:75  10 C 4 0:85
W e t ð3Þ
lnð1  X Þ ¼ –0:37C 0:85 W 1:50 e2710=T t ð4Þ
To test the models, theoretical and experimental
conversions were plotted in Fig. 8. It is clear that the
proposed models appropriately represent a first order
cementation reaction. The reaction rate is proportional
with the 3/2 order of stirring speed. However, at higher
stirring speeds (N 500 rpm) the rate did not change. This
indicates that at lower stirring speeds the reaction rate is
diffusion controlled. At 500 rpm stirring speed and
temperatures below 318 K the reaction is completely
controlled by surface reaction. When the effect of the
other parameters was examined, the stirring speed was
set at 500 rpm. At 500 rpm stirring speed and above
318 K, the reaction changed the mechanism and shifted
to diffusion controlled regime.
4. Conclusion
In this work, we have investigated the cementation of
copper using zinc granules in Cu2+, Zn2+ and Cl−
containing solutions. It was observed that the reaction
rate increased with initial copper concentration, stirring
speed and temperature. pH variation (1–4) increased the
rate but at higher pH the rate was not significantly
effected. The cementation reaction obeys first order
kinetics and may be represented by the model given in
Eq. (2) and this relationship is experimentally confirmed.
Many investigators (Karavasteva, 2005) reported that
the cementation of copper by zinc is more effective than
cementation with iron and aluminum. The oxidation
potential of iron is lower then that of zinc. Hence, zinc is
a better cementation metal. Although aluminum has a
higher oxidation potential then zinc, an oxidation layer
forms on the surface of aluminum during the cementa-
tion (Karavasteva, 2005). Thus, the yield with alumi-
num is lower.
During the leaching process of zinc containing copper
ores, the leaching solution contains significant amount
of zinc ion. Thus, the cementation of copper from the
solution with zinc will facilitate the recovery of zinc as a
side product in the later stages. As a matter of fact, by
using zinc only, the solution will not be contaminated
with a third ion. Therefore, the cementation of copper
with zinc becomes an important process.
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