3rd AMIREG International Conference (2009): Assessing the Footprint of 137

Resource Utilization and Hazardous Waste Management, Athens, Greece

Copper cementation from the waste effluents of primary copper industry

I. Giannopoulou and D. Panias

National Technical University of Athens, Greece

ABSTRACT
In this paper, the cementation of copper from
the waste effluents generated in the primary
copper pyrometallurgical production industry is
studied. These wastewaters are strongly acidic
aqueous solutions with high concentration of
copper, significant concentration of nickel and
minor contents of other metals, such as Pb, Zn,
Fe, As, Sb, Bi, etc. As cementing agent, zero-
valent iron in three different types (particles,
sponge and fillings) was used. The effect of the
specific surface area and excess of iron used, as
well as the solution pH and agitation rate, on the
cementation of copper was investigated, in order
to determine the optimum operating conditions
of the process. According to the experimental
results, cementation is an easily applied, cost-
effective and efficient method for the recovery
of copper from the waste effluents generated in
the pyrometallurgical production of copper. A
compromise of its main operating parameters is
necessary for the nearly total copper recovery.
The recovered copper can be recycled into the
smelting stage of the copper pyrometallurgical
plant.
1. INTRODUCTION
The pyrometallurgical processing of copper sul-
phide concentrates for the copper production in-
cludes mainly the stages of roasting, smelting,
converting, refining and electrorefining. Gener-
ally, an integrated industry of primary copper
production includes also a plant for the produc-
tion of sulphuric acid from the off-gases of the
roasting stage that contain SO2, as well as a
plant for the production of precious metals (Au,
Ag, Se, Te, etc.) from the anodic slime pro-
duced in the stage of copper electrorefining.
The most important waste effluents in the
whole pyrometallurgical production process of
copper sulphide concentrates originated from
the refining of copper, the regeneration of elec-
trolyte in copper electrorefining and the produc-
tion of precious metals. All these waste efflu-
ents are aqueous acidic solutions, due to the
high sulphuric acid concentration, with high
content of copper. They also contain significant
quantities of Ni and minor quantities of other
metals, such as Pb, Zn, Fe, As, Sb, Bi, Sn, Cr,
etc. According to the European legislation
(European Commission, 2000), the treatment of
these waste effluents is necessary before their
discharge into the environment. Additionally,
the high copper concentration in these effluents
raises an economic interest for its recovery, in
order to be recycled or re-used.
The most used methods for metal recovery
from industrial waste effluents with high metal-
lic content are the chemical precipitation, elec-
trolysis and cementation. Although chemical
precipitation is considered as the most efficient
and economic among these methods for the
treatment of waste effluents (Christiansen and
Delwiche, 1982; Ying et al., 1988; Tunay and
Kabdasli, 1994; Baltpurvins et al., 1996; Cha-
rerntanyarak, 1999; Giannopoulou and Panias,
2008), it has important drawbacks. It requires
extremely long setting times and results in a
bulky sludge that contains usually all the metals
of the treated waste effluents in the form of hy-
droxides or sulfides. In addition, this sludge
may contain hazardous and/or toxic metals and
thus, it is not easily handled. The waste cake
produced after the sludge dewatering and filter
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
pressing is not acceptable for the metallurgical
furnaces, due to the high water content (ap-
proximate 70-80%). Generally, its utilization is
limited, mainly in the manufacture of building
ceramics as colorizing admixture. Therefore,
this sludge has to be dumped on appropriate
waste landfills, increasing this way the final
treatment cost of the waste effluents (Ying
et al., 1988).
Electrolysis gains increasing attention during
the last years, as an efficient method for the
treatment of waste effluents containing metals.
However, it is effective when applied on the
treatment of waste effluents containing a limited
number of metals with high concentration (For-
nari and Abbruzzese, 1999; Juttner et al., 2000;
Janssen and Koene, 2002). Electrolysis requires
specific operating adjustments and controls,
which increase its maintenance and operating
cost. In addition, it necessitates specific reactors
and equipment that render often its application
uneconomical. Generally, the operating cost of
electrolysis is enormous, in comparison to the
other treatment methods, as it operates by con-
suming electric energy.
Cementation is considered as a reasonable
and simple method for the recovery of copper
from industrial wastewaters (Stefanowicz et al.,
1997; Donmez et al., 1999; Dib and Makhloufi,
2004; Mubarak et al., 2004; El-Batouti, 2005). It
is based on a heterogeneous electrochemical re-
action involving the spontaneous reduction of a
metal from ionic solutions and its precipitation
on another, more electropositive metal, which is
oxidized (“sacrificial metal”). Cementation has
several advantages, including recovery of met-
als in an essentially pure metallic form, simple
control requirements, low energy consumption,
high efficiency and low cost. Moreover, the re-
covered metallic sediments are suitable for met-
allurgical processing (Stefanowicz et al., 1997).
The main disadvantage of the process is related
to the consumption of the sacrificial metal, es-
pecially at low pH values (Dib and Makhloufi,
2004).
This paper deals with the application of the
cementation process for the treatment of the
waste effluents generated in the primary copper
pyrometallurgical plant at Bor, Serbia, in order
to recover the contained copper. In this plant, by
combining the wastewaters streams originated
from the processes of copper refining and pre-
138
cious metals production, a strongly acidic waste
effluent with a copper concentration of about 6
g/L was generated. Considering that the average
volumetric outflow of this effluent was equal to
16 m3/day almost 35 tons of copper are annually
lost, due to its improper treatment.
The present work aims at determining the op-
timum operating parameters of cementation
process, so as to be effective, reliable and viable
for the recovery of copper from the studied
waste effluent. Particularly, the effect of the ex-
cess and type of iron used as cementing agent,
as well as of the solution pH and agitation rate,
on the efficiency of cementation process was
studied.
2. EXPERIMENTAL
2.1 Materials
In order to simulate the waste effluent studied in
this work, a synthetic solution with the chemical
composition given in Table 1 was used in all the
cementation experiments. This solution was
prepared using chemical reagents of analytical
grade and distilled water and had pH= 0.4.
As cementing agent, zero-valent iron (ZVI)
in three different types (Table 2), namely
sponge (Alfa Aesar), granules (Alfa Aesar) and
fillings from the cast iron grit (Gotthert Maier
GmbH) was used.
2.2 Experimental procedure
All the experiments were carried out in batch
mode and at room temperature. For each ex-
periment, 100 mL of the synthetic solution was
added to a 250 mL conical flask containing the
appropriate amount of iron, so as to achieve the
pre-defined iron excess. Flasks were put on a
laboratory-scale shaking plate, which operated
Table 1: Chemical composition of the synthetic solution
simulating the studied waste effluents.
Element Concentration (g/L)
Cu 6,520
Ni 0,688
Pb 0,003
Fe 0,150
Zn 0,026
Sb 0,013
Bi 0,040
As 0,458
SO42- 81,571
3rd AMIREG International Conference (2009): Assessing the Footprint of 139
Resource Utilization and Hazardous Waste Management, Athens, Greece

at a pre-defined stirring rate (from 0 to 250 rpm) granules fillings sponge

for an appropriate time (from 0.5 to 6 hours). 100
Thereinafter, the solution was filtered and 80

Cu cemented, %
analyzed in order to determine the concentration
of the contained metals according to the Atomic 60
Absorption Spectrophotometry method (Perkin
40
Elmer 2100). The resulted solid phase was dried
and weighed. All the solid phases taken after the 20
cementation experiments were analyzed by X-
Ray Diffractometry (Siemens, D 5000, CuKα 0
radiation, λ=1.5418 Å, 40 kV and 30 mA), in 0 1 2 3 4 5 6
order to define the mineralogical phases that Time, h
were cemented. Figure 1: Cemented copper versus time and type of ZVI
used. Experimental conditions: pH=0.43, stirring
rate=100 rpm, Fe/Cu mass ratio=0.879.
3. RESULTS AND DISCUSSIONS
ing agent, the highest the rate of metal cementa-
3.1 Effect of iron type and excess tion on it.
Copper is less electropositive in respect to iron, According to Table 2, the specific surface
and thus, the following chemical reactions were area of the granules type of ZVI was extremely
expected to occur during cementation treatment lower than that of fillings and sponge types,
of the studied acidic waste effluent (Dib and which had quite similar specific surface areas.
Makhloufi, 2004): Thus, the high specific surface area of fillings
and sponge ZVI types enhanced the copper ce-
Cu2+ + Fe(s) → Fe2+ + Cu(s) (1) mentation rate and the process was completed
very fast, almost in the first hour. At this time,
2H+ + Fe(s) → Fe2+ + H2(g) (2) about 72% and 80% of copper was cemented
Since iron was also contained in the studied using the fillings and sponge types of ZVI, re-
effluent, the following side reactions were also spectively, while only 30% of copper was ce-
expected to occur. mented using the granules ZVI type.
Except for copper, bismuth, antimony, lead
2Fe3+ + Fe(s) → 3Fe2+ (3) and arsenic were also recovered during the
treatment of the waste effluent (Fig. 2). In oppo-
2Fe3+ + Cu(s) → 2Fe2+ + Cu2+ (4) site, neither nickel nor zinc cementation took
In addition, the reduction of other metals, place.
which were contained in the studied effluent and The excess of iron improved the efficiency of
are less electropositive in respect to iron (such copper cementation process (Fig. 3), for all the
as Bi, Sb, As, Pb), was expected to take place. ZVI types used.
According to Equation (1), the stoichiometric The solid phases taken at the end of each ce-
iron demand for the reduction of copper is equal mentation experiment were red-brown, due to
to 0.879 g/g. The fraction of cemented copper as the copper cemented. According to the X-Ray
a function of time for all the types of ZVI used Diffraction analysis performed in these solid
in this work is presented in Figure 1. As shown phases, copper was cemented as Cu and CuO,
in Figure 1, for the sponge and fillings types of when the granules type of ZVI was used, while
ZVI used, the copper reduction reaction (Eq. 1) it was also cemented as Cu2O, when fillings and
reached the equilibrium in the first hour of the Table 2: Characteristics of the used zero-valent iron
process. In opposite, when the granules type of Particle Specific sur-
ZVI was used, the reduction of copper was per- Fe form 0
% Fe size face area
formed with substantially lower rate (Fig. 1). (mm) (m2/g)
Given that the reaction of metal cementation oc- Granules 99.8 1.0-2.0 0.0014
curs on the surface of the cementing agent, the Fillings 92.03 0.2-1.2 0.0482
highest the specific surface area of the cement- Sponge 99.8 0.14-0.29 0.0502
 3rd AMIREG International Conference (2009): Assessing the Footprint of 140
Resource Utilization and Hazardous Waste Management, Athens, Greece

80 Pb Sb As Bi
1
1. Cu 4. Cu2O
4 2. CuO 5. AsCu3
2
Metals recovery, %

60 35 3. Fe
4 1
4 4

Intension, cps
sponge
40
fillings
20
granules
0
20 30 40 50 60 70
0 1 2 3 4 5 6
2θ, degrees
Time, h
Figure 4: XRD diagrams of the solid phases taken after
Figure 2: Metals recovery versus time for the fillings ZVI the experiments, where 20% excess of iron was used, for
type. Experimental conditions: pH=0.43, stirring rate=100 all the ZVI types.
rpm, Fe/Cu mass ratio=0.879.

granules fillings sponge increase of the stirring rate from 0 to 250 rpm
resulted in increasing the cemented copper frac-
100
tion, almost linearly. At the higher applied stir-
Cu cemented, %

ring rate of 250 rpm, about 99% and 86% of the

80 copper contained in the solution was cemented
using ZVI sponge and fillings types, respec-
60 tively. By comparing these copper cemented
fractions with the respective achieved after 6
40 hours cementation under the stirring rate of 100
rpm (Fig. 1), it is obvious that the intense stir-
0 10 20
ring rate improved the efficiency of copper ce-
Iron excess, % mentation.
Figure 3: Cemented copper versus iron excess for all the Generally, stirring of the cementing agent or
ZVI types used. Experimental conditions: pH=0.43, circulation of the solution shortens the metals
time=2 h, stirring rate=100 rpm. cementation time and favors the efficiency of
the process (Stefanowicz et al., 1997). The in-
sponge types of ZVI were used (Fig. 4).
tense and continuous motion of ZVI provided
In addition, the mineralogical phase AsCu3
the maximum contact of copper ions with the
was detected, in the case of using the sponge
iron surface. Thus, high efficiency of copper
ZVI type (Fig. 4). Excluding copper, arsenic
cementation was achieved in a shorter time.
was contained in the waste effluent with the
Moreover, the iron surface was continuously re-
highest concentration among the other cemented
newed through the mechanical friction created
metals and its recovery exceeded 95%, when the
(Stefanowicz et al., 1997), improving the effi-
sponge type of ZVI was used.
100
3.2 Effect of stirring rate
Cu cemented, %

80
The effect of the solution stirring rate on the re-
covery of copper was studied by applying dif- 60
ferent stirring rates on the laboratory shaking sponge
plate used for the cementation experiments. The 40
duration of these experiments was 30 min, while fillings
20% iron excess of sponge and fillings ZVI 20
types was used. The stirring rates of 0, 100 and 0 50 100 150 200 250
250 rpm were applied. Stirring rate, rpm
The fraction of cemented copper versus stir-
Figure 5: Cemented copper versus stirring rate for the
ring rate, for both sponge and fillings ZVI types, sponge and fillings ZVI types used. Experimental condi-
is presented in Figure 5. According to Figure 5, tions: pH=0.43, time=30min, iron excess=20%.
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
70
Metals recovery, %
60
50
40
30
20
0,4 0,8 1,2 1,6
pH
Figure 6: Recovery of metals versus pH for the fillings
ZVI type. Experimental conditions: time=30min, iron ex-
cess=20%, stirring rate=100rpm.
ciency of the process.
3.3 Effect of pH
The effect of the solution pH on the efficiency
of copper cementation was investigated for the
pH vales of 0.43, 0.79, 1.18 and 1.57. In this
experimental series, cementation time, excess of
iron and stirring rate were maintained at 30 min,
20% and 100 rpm, respectively. The fillings
type of ZVI was only used in this experimental
series, taking into account that it is a by-product
generated in the process of cast iron gritting and
thus, is cheaper than iron sponge.
According to Figure 6, cementation process
was favored in the solution pH range from 0.8
to 1.2, for all the metals recovered. Generally,
the pH values between 1 and 1.5 are considered
as optimum for efficient copper cementation.
At pH < 1, a compact copper deposit or a fine
oxide film is formed on iron surface
(Karavasteva, 2005) inhibiting the dissolution of
iron, as well as the cementation of copper (Ste-
fanowicz et al., 1997; Karavasteva, 2005). At
pH values higher than 1.5, hydrolysis of iron
and antimony contained in the solution may be
occurred (Giannopoulou and Panias, 2008) re-
sulting in the deposition of hydroxide precipi-
tates on the iron reacting surface (Stefanowicz
et al., 1997; Karavasteva, 2005). Under these
conditions, iron dissolution and copper cemen-
tation are inhibited.
4. CONCLUSIONS
Cementation treatment of the strongly acidic
waste effluents generated in the primary copper
pyrometallurgical industry can effectively re-
141
cover the contained copper, by using iron as
cementing agent. The process is easily applied
Cu
As
and may be cost-effective, taking into account
that iron scrap or by-products can be used as
Bi cementing agents. A compromise of the main
Sb process operating parameters can achieve nearly
Pb total copper recovery from the waste effluents.
The specific surface area and the excess of
iron were proved as crucial parameters affecting
the rate of copper cementation. By using iron
with high specific surface area, copper cementa-
tion was completed after 60 min, under inter-
mediate conditions of solution stirring rate and
pH.
Increase of the solution stirring rate shortens
the time of copper cementation and increases its
rate. Besides, the process is favored at solution
pH values between 0.8 and 1.2.
Except for copper, lead, arsenic, bismuth,
and antimony contained in the waste effluent are
also cemented on iron. Copper was cemented as
pure metal, as well as cupric and cuprous ox-
ides, while it also co-deposits with arsenic. The
cemented copper, along with the other cemented
metals, can be recycled into the smelting stage
of the primary copper pyrometallurgical plant.
REFERENCES
Baltpurvins, K.A., R.C. Burns and G.A. Lawrance, 1996.
Heavy metals in wastewater: modeling of hydroxide
precipitation of copper (II) from wastewater using
lime as the precipitant, Waste Management 16 (8):
717-725.
Charerntanyarak, L., 1999. Heavy metals removal by
chemical coagulation and precipitation, Water Science
and Technology 39 (10): 135-138.
Christiansen, E.R. and J.T. Delwiche, 1982. Removal of
heavy metals from electroplating rinsewaters by pre-
cipitation, flocculation and ultrafiltration, Water Re-
sources 16: 729-737.
Dib, A. and L. Makhloufi, 2004. Cementation treatment
of copper in wastewater: mass transfer in a fixed bed
of iron spheres, Chemical Engineering and Processing
43: 1265-1273.
Donmez, B., F. Sevim and H. Sarac, 1999. A kinetic
study of the cementation of copper from sulphate solu-
tions onto a rotating aluminium disc, Hydrometallurgy
53: 145-154.
European Commission, 2000. Commission Decision of 3
May 2000 replacing Decision 94/3/EC establishing a
list of wastes pursuant to Article 1(a) of Council Di-
rective 75/442/EEC on waste and Council Decision
94/904/EC establishing a list of hazardous waste pur-
suant to Article 1(4) of Council Directive 91/689/EEC
on hazardous waste. Official Journal of European
3rd AMIREG International Conference (2009): Assessing the Footprint of 142
Resource Utilization and Hazardous Waste Management, Athens, Greece

Communities (6/9/2000) L226: 3-24.

El-Batouti, M., 2005. Removal of copper metal by cemen-
tation using a rotating iron cylinder, Journal of Colloid
and Interface Science 238: 123-129.
Fornari, P. and C. Abbruzzese, 1999. Copper and nickel
selective recovery by electrowinning from electronic
and galvanic industrial solutions, Hydrometallurgy 52:
209-222.
Giannopoulou, I. and D. Panias, 2008. Differential pre-
cipitation of copper and nickel from acidic polymetal-
lic aqueous solutions, Hydrometallurgy 90 (2-4): 137-
146.
Janssen, L.J.J. and L. Koene, 2002. The role of electro-
chemistry and electrochemical technology in envi-
ronmental protection, Chemical Engineering Journal
85: 137-146.
Juttner, K., U. Galla and H. Schmieder, 2000. Electro-
chemical approaches to environmental problems in the
process industry, Electrochemica Acta 45: 2575-2594.
Karavasteva, M., 2005. Kinetics and deposit morphology
of copper cementation onto zinc, iron and aluminium,
Hydrometallurgy 76: 149-152.
Mubarak, A.A., A.H. El-Shazly and A.H. Konsowa, 2004.
Recovery of copper from industrial waste solution by
cementation on reciprocating horizontal perforated
zinc disc, Desalination 167: 127-133.
Stefanowicz, T., M. Osinska and S. Napieralska-Zagorda,
1997. Copper recovery by cementation method, Hy-
drometallurgy 47: 69-90.
Tunay, O. and N.I. Kabdasli, 1994. Hydroxide precipita-
tion of complex metals, Water Resources 28 (10):
2117-2124.
Ying, W.C., R.R. Bonk and M.E. Tucker, 1988. Precipita-
tion treatment of spent electroless nickel plating, Jour-
nal of Hazardous Materials 18: 69-89.