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Copper Removal from Industrial Wastewater: A Comprehensive Review

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 Journal of Industrial and Engineering Chemistry 56 (2017) 35–44

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Review

Copper removal from industrial wastewater: A comprehensive review

Sajeda A. Al-Saydeha , Muftah H. El-Naasa,* , Syed J. Zaidib
a
Gas Processing Center (GPC), Qatar University, Doha, Qatar
b
Center for Advanced Materials (CAM), Qatar University, Doha, Qatar

A R T I C L E I N F O A B S T R A C T

Article history:
Received 29 June 2017 Copper is one of the most valuable and prevalent metals used in the industry. There are many techniques
Received in revised form 18 July 2017 to treat different types of industrial wastewater that are contaminated with heavy metals such as copper.
Accepted 20 July 2017 This article focuses on reviewing the most advanced wastewater treatment techniques, including
Available online 27 July 2017 adsorption, membrane filtration, cementation and electrodialysis. The review examines the differences
among the treatment methods in terms of duration and overall efficiencies. The review outlines the
Keywords: current research in the area in terms of weaknesses and strengths, leading to future research prospective
Adsorption and pointing out gabs that need to be addressed in future research.
Cementation
© 2017 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Electrodialysis
reserved.
Heavy metals
Wastewater treatment

Contents

1Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2 Copper removal techniques . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.1Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.1.1Adsorption on modified natural material ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.1.2Adsorption on modified biopolymers . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.1.3Adsorption on industrial by-products . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.1.4Adsorption on low-cost biosorbents . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.1.5Adsorption on nanomaterials . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
2.2Cementation . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3Membrane filtration . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3.1Ultrafiltration . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3.2Nano filtration . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
2.3.3 Reverse osmosis . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.4Electrochemical methods . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
2.5Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3Comparison of copper removal processes . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
4Future prospective . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
5Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42

1 Introduction and if it is toxic or poisonous at low concentrations. Heavy metals

are non-biodegradable, toxic, and easy to accumulate at low
The metal can be classified as a heavy metal, if it has a relatively concentrations in living organisms in general and in the human
high density which is bigger than the density of water by five times body in specific; they can cause serious illnesses, such as cancer,
nervous system damage, and kidney failures and can be deadly at
high concentrations [1–6]. The most common heavy metals that
* Corresponding author. are often present in industrial wastewater include: nickel, zinc,
E-mail address: muftah@qu.edu.qa (M.H. El-Naas).

http://dx.doi.org/10.1016/j.jiec.2017.07.026
1226-086X/© 2017 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
36 S.A. Al-Saydeh et al. / Journal of Industrial and Engineering Chemistry 56 (2017) 35–44
silver, lead, iron, chromium, copper, arsenic, cadmium and
uranium [7–10]. However, copper is usually found at high
concentrations in wastewater, because it is considered as the
most valuable and commonly used metal in many industrial
applications, such as metal finishing, electroplating, plastics, and
etching [11–15]. Moreover, copper is a very toxic metal even at low
concentration and copper-contaminated wastewater must be
treated before discharging it to the environment [16–20]. The
permissible limit of copper ions in industrial effluents was
reported by the United State Environmental Protection Agency
(USEPA) to be 1.3 mg/L while it was stated by World Health
Organization that copper ions content in drinking water should not
exceed 2 mg/l [21–23]. Over the past few years, there have been
numerous new methods and techniques that were developed for
the removal of copper ions from industrial wastewater, such as
adsorption [24–27], cementation [16,28], membrane filtration
[29–31], electrodialysis [32,33] and photocatalysis [34,35].
This main objective of this paper is to review the key options
available for copper removal and hence offer a good start to guide
new researchers who want to fill research gaps in the area and
improve the conventional copper removal methods. Although
there are few similar review papers dealing with the removal of
heavy metals, they all seem to be too general, considering other
metal ions or concentrating on a specific treatment method. To the
best of the authors’ knowledge, there are no comprehensive
reviews published in the open literature that focus on the removal
of copper in spite of its importance as a major water contaminant.
Copper removal techniques are discussed in the following sections
and compared in terms of removal efficiency, practicality,
environmental friendliness and process economics.
2 Copper removal techniques
2.1 Adsorption
The word “adsorption” describes the process of mass transfer,
where the material is transferred from the liquid phase directly to
the surface of the solid phase, after that it is bounded with
chemical and/or physical interactions [36]. Davarnejad and Panahi
[37] reported that the adsorption method is considered to be the
most common process used to remove different copper ions from
industrial wastewater. Further, it provides many advantages
compared to the other treatment techniques because of the
simplicity in design and its ability to involve low investment in
terms of initial cost as reported by Hidalgo-Vázquez et al. [38,39].
On the other hand, Abdel Salam et al. [40–42] reported some
disadvantages of this process, such as its limited applications to
certain concentrations of copper ions. There are many different
low-cost adsorbents that have been developed for the removal of
copper ions from metal-contaminated wastewater [43]. These
adsorbents have been derived from natural material, modified
biopolymers, biological wastes, industrial by-products, and nano-
materials.
2.1.1 Adsorption on modified natural material
Natural zeolites are the most studied natural materials for the
adsorption of heavy metals due to their valuable properties, such
as effective ion exchange capability [44]. Ali and YaŞAr [45] proved
that the clinoptilolite is considered as one of the most important
natural zeolite, since it can be found worldwide. Also, it shows high
selectivity for copper ions. Barakat [46] studied the effect of pH in
this process, in which the pH is playing a main role in the selective
adsorption of varies copper ions:
1. At natural pH, the NaA zeolite is used to remove Cu(III).
2. A4 zeolite is used to adsorb Cu(II) at natural and alkaline pH.
3. The adsorption of Cu(VI) is achieved at acidic pH using
A4 zeolite.
Clay–polymer composites consist of natural clay minerals,
which can be supported with polymeric material to improve their
capability of removing copper ions from aqueous solutions as
reported by Azzam et al. [47]. Activated phosphate with nitric acid,
zirconium phosphate, and calcined phosphate at 900
C are
considered as phosphates, which have been studied as a new
type of adsorbents to remove copper from wastewater by Francis
et al. [13,48].
2.1.2 Adsorption on modified biopolymers
Using modified biopolymers adsorbents is industrially attrac-
tive because they have some advantages [49]. For instance, they
can reduce the copper concentrations in water to sub parts per
billion concentrations, they can be widely available, and they are
environmentally safe. The most attractive feature of biopolymers is
that they contain different functional groups, such as amines and
hydroxyls, which can increase the separation efficiency of heavy
metal ions and make the chemical loading possibility reach the
maximum. Polysaccharide-based-materials are good example of
modified biopolymers, which can be used as adsorbents. Crini [50]
reported that there are two different ways to prepare an adsorbent
that contains polysaccharide-based-materials, which are:
1. Crosslinking reactions, which is the reaction that occurs
between the hydroxyl groups or amino of the chains with a
coupling agent to form the crosslinked networks (gels), which
are water insoluble.
2. Immobilize the polysaccharides on some insoluble supports by
some reactions to give hybrid materials.
2.1.3 Adsorption on industrial by-products
Fly ash [51,52], iron slags, hydrous titanium oxide, and waste
iron are industrial by-products, which can be chemically modified
to improve their removal ability for copper ions from industrial
wastewater. Iron slag was successfully utilized to remove Cu(II)
ions at a pH range of 3.5–8.5 [13], while Luo et al. [53] studied the
performance of fly ash, from the coal-burning, for the removal of
Cu(II) from aqueous solutions. Hydrous titanium oxide has been
tested by Barakat et al. [54,55] to adsorb Cu(II) and Cu(VI), where
the Cu(II) adsorption mechanism is achieved by surface hydrolysis
reaction as pH increases. TiO–Cu(OH)3 and TiO–CuOH+ species
are examples of Cu(II) complexes, which are considered as the
main products of the surface hydrolysis reaction (Fig. 1).
Fig. 1. The adsorption of Cu(II) on TiO2 [54].
 S.A. Al-Saydeh et al. / Journal of Industrial and Engineering Chemistry 56 (2017) 35–44 37

2.1.4 Adsorption on low-cost biosorbents
During the past few years, a considerable amount of research
has been devoted to the removal of heavy metals from industrial
wastewater using adsorbents that are derived from agriculture
wastes. Such process is often referred to as bio-sorption [13].
Zeraatkar et al. [56] reported that bio-sorption is often considered
as one of the most innovative technology for the removal of heavy
metal ions using non-active biomass and non-living algae.
Anastopoulos and Kyzas [57] proved that acidic pH, between
2 to 6, is the most effective range to remove heavy metals by
adsorbents derived from modified biological wastes. Further, it was
found that the dead algae may have higher uptake of heavy metal
ions as compared to live algae by Ref. [58].
2.1.5 Adsorption on nanomaterials
During the past few years, carbonaceous nanofibers (CNFs) and
graphene oxide (GO) have been used to remove copper from
industrial wastewater. CNFs can be produced via hydrothermal
carbonization (HTC) using any precursor such as glucose [59]. The
CNFs attracted the interest of many researchers because it showed
different advantages such as excellent mechanical stability, good
hydrophilic nature and high surface area [60]. Ding et al. [61]
studied the performance of CNFs for removing copper ions in
multi-component conditions, where copper ion was successfully
adsorbed on CNFs at acidity pH. The maximum sorption capacity
for Cu2+ was found to be 204 mg/g at pH 5.5  0.2. Recently,
graphene oxides (GOs) and GO-based nanomaterials have received
considerable attention for the removal of organic and inorganic
pollutants from wastewater due to their unique properties such as
high surface area, large pore volume structure, chemically stability,
and abundant O2-containing functional groups (i.e. hydroxide and
carboxyl groups) [27,62–67]. Yu et al. [68] discussed the removal of
copper ion using GO-based nanomaterial in different composi-
tions, where the maximum copper ion sorption capacity was found
to be 45.2 mg/g on pure GO.
After discussing the different types of adsorbents, which can be
derived from natural material, modified biopolymers, industrial
by-products, and modified biological wastes, the uptake rates at
different operating conditions for each adsorbent have been
presented in Table 1. These adsorbents include modified fly ash,

Table 1
Cu(II) removal by using different low-cost adsorbents.

Type of adsorbent Operating condition Uptake (mg/g) References

Activated carbon prepared from Phaseolus aureus hulls (ACPAH) pH = 7 20.00 [69]
Activated carbon prepared from Ceiba pentandra hulls pH = 6 21.00 [70]
Modified fly ash pH = 6.4 21.50 [71]
Zeolite derived from fly ash pH = 3.5 147.7 [72]
T = 310 K
Waste slurry pH = 3 20.97 [73]
Ag nanoparticle-loaded activated carbon (Ag-NP-AC) pH = 4.7 60 [74]
Carbonaceous nanofibers T = 5.5  0.2 204.00 [61]
Live yeast pH = 6.4 204.10 [75]
(Y. lipolytica)
HCl-treated clay pH = 5 83.30 [76]
Graphene oxide pH = 5 45.20 [68]
Graphene oxide/Fe3O4 pH = 5.3 18.26 [77]
T = 20
C
Treated fly ash with NaOH solution pH = 6.2 64.00 [78]
T = 40
C
kaolinite-supported zerovalent iron nanoparticles pH = 6.0 49.00 [79]
Bare NZVI (FeCl24H2O + NaBH4) pH = 6.5 250.00 [80]
MWCNT-reinforced nanofibrous matssupported NZVI pH = 5.5 107.80 [81]
Ecklonia maxima — marine alga pH = 6 90.00 [82]
T = 20
C
Spirogyra (green alga) pH = 5 133.00 [83]
T = 22  2
C
Pecan shells activated carbon pH = 4.8 31.70 [84]
Amino-functionalization of PAA-coated Fe3O4 nanoparticles pH = 5 12.00 [85]
Oligotrophic peat pH = 6.7 12.07 [86]
pH = 5 06.41 [87]
Eutrophic peat pH = 6.7 12.07 [86]
pH = 5 19.56 [87]
Iron oxide coated eggshell powder pH = 6 44.00 [88]
Immobilized nanometer TiO2 pH between 8–9 06.70 [89]
Nanometer TiO2 pH = 8 07.00 [90]
Rose waste biomass pH = 5 56.00 [91]
T = 303 K
Valonia tannin resin pH = 5 44.00 [92]
T = 298 K
Granular activated carbon pH = 3 0.79 [93]
Date pits pH = 5.8  0.5 07.40 [94]
Chlorella vulgaris pH between 4–5 01.52 [95]
Chitosan pH = 4.5 88.43 [96]
pH = 5 87.99 [97]
Non-crosslinked chitosan pH = 5 85.00 [98]
T = 20
C
Crosslinked chitosan (EPI) pH = 5 62.40 [50]
Crosslinked chitosan (TPP) pH between 5–6 200.00 [99]
Steel-making-by-product pH = 6 40.00 [100]
Scolecite pH = 6 04.20 [101]
38 S.A. Al-Saydeh et al. / Journal of Industrial and Engineering Chemistry 56 (2017) 35–44
zeolite derived from fly ash, treated fly ash with NaOH solution,
calcinated fly ash, iron oxide coated eggshell powder, granular
activated carbon, etc.
2.2 Cementation
Cementation is a general term used to describe the heteroge-
neous process in which the copper ions in the copper’s salt solution
(i.e., CuSO4), are reduced to zero valence at the interface of iron by
spontaneous electrochemical reduction to reach the copper
metallic state, with consequent oxidation of the iron and the
dissolved iron species present more in the aqueous solution as
illustrated in Fig. 2 [102,103]. The cementation process is
considered as the most economic and effective technique to
remove valuable and/or toxic metals from industrial wastewater
[17]. During the past ten years, this method has been widely used in
different industries as a purification process of industrial waste
solutions [16]. Aktas et al. [16,104,105] studied the advantages of
using this technique, such as its comparatively low cost process
due to consuming low energy and recovering the metals in pure
metallic form with high efficiency. Also, it is easy to control and it
has relatively simple operation. On the other hand, DemirkIRan _ space requirement smaller.
and Künkül [106] mentioned the main disadvantage of cementa-
tion technique, which is the excess sacrificial metal consumption.
Wu et al. [107] proved that the iron and zinc are the most common
cementation agents used in the industrial applications because
they have strong reductive ability. However, it seems that the Cu
cementation using a scrap of iron, is the simplest and most
reasonable method for Cu recovery [108]. Therefore, it produces
metallic copper sediments, which are suitable for metallurgical
processes. The oxidation/reduction reactions are presented below
[108]:
Fe ! Fe2+ + 2e
Cu2+ + 2e ! Cu
The overall reaction:
CuSO4 + Fe ! FeSO4 + Cu
2.3 Membrane filtration
Membrane filtration has received considerable attention in
recent years for treating copper-contaminated industrial waste-
water, since it is applicable to remove suspended solid, organic,
and inorganic compounds (i.e. heavy metals) [13]. Furthermore,
Escobar et al. [110–112] highlighted the main advantages of using
Fig. 2. Copper cementation on iron [109].
membrane method, such as energy saving, no phase change, cost
effectiveness, easy to scale up, high efficiency in separation, and
environmentally safe. Several types can be used to remove copper
ions from wastewater, which are classified based on the particle
size that can be removed, such as ultrafiltration, nanofiltration, and
reverse osmosis. However, Elimelech and Phillip [112] mentioned
that further developments are needed to improve the membrane
filtration technologies by reducing the energy consumption and
lowering the required thermodynamics operation conditions.
2.3.1 Ultrafiltration
Ultrafiltration (UF) is a promising membrane technique to
remove copper ions from industrial wastewater at low transmem-
brane pressures. UF has a pore size between 5 and 20 nm and the
MW of the separated particles should be within the range (1000–
100,000 Da) [113,114]. Gunatilake [113] proved that, based on the
characteristics of the membrane, UF membrane can achieve a good
removal efficiency (around 90%) for initial copper concentrations
ranging from 10 to 160 mg/L, where the best pH range is from 5.5 to
6 and at an operating pressure between 2 to 5 bars. An important
advantage of UF is due to the high packing density which makes the
Polymer enhanced ultrafiltration (PEUF) has also been evaluat-
ed during the last few years [113]. PEUF has been proposed as a
suitable method to remove copper ions from industrial wastewater
(Table 2). Water-soluble polymer is the main type of polymer that
is used in PEUF process to convert the heavy metal ions to
macromolecular complexes, which have a molecular weight that is
higher than the membrane’s molecular weight cut off [115]. There
are many parameters that play a key role in effecting the PEUF
process, such as the metal to polymer ratio, polymer type, and pH
values. Finding the most suitable polymer that can be used in PEUF
process has been the main focus of many researchers during the
past few years. Fu et al. [114,116] evaluated different types of
polymers, which showed a selective separation of copper ions with
low energy consumption, such as polyethyleneimine (PEI), humic
acid, polyacrylic acid (PAA), and diethylaminoethyl cellulose.
Molinari et al. [116] proved the high efficiency of polyethylenei-
mine (PEI) in removing Cu(II) from contaminated wastewater,
where the best results were found when the pH value was above
6 and the metal to polymer mass ratio was around 3. Using PEUF
process has many advantages including high binding selectivity
and high removal efficiency. Although there has been considerable
amount of research and many publications in this area, PEUF still
has not reached wide industrial applications [117].
2.3.2 Nano filtration
The utilization of nanofiltration (NF) for the removal of heavy
metals has been rapidly increasing in recent years, since it provides
some critical solutions for certain problems associated with the
conventional removal methods [120]. Al-Rashdi et al. [121] proved
the successful application of NF membrane for heavy metal ions
removal. The NF is considered to be a pressure driven process,
which has a pore size between the ultrafiltration (UF) and reverse
osmosis (RO), and most of NF membrane are charged with either
negative or positive charge [110]. In addition, NF membrane has
unique separation mechanisms, which are Donnan exclusion
(charge repulsion) and size exclusion [110,122,123]. NF membrane
has many advantages compared to the other types of membrane,
where it has higher rejection to the multivalent copper ions than
the UF membrane [124]. Further, compared to RO membrane, NF
membrane has higher water permeability with relatively high
rejection and much lower operating pressure. Therefore, NF
membrane process is considered as an energy-saving process that
is very effective for heavy metal ions removal [111]. Mohammad
et al. [125] reported that the pore size of the NF membranes is
 S.A. Al-Saydeh et al. / Journal of Industrial and Engineering Chemistry 56 (2017) 35–44 39

Table 2
Cu(II) removal by PEUF membrane.

UF type Membrane type Surfactant agent Initial conc. Optimum pH Removal efficiency Reference
PEUF Polyethersulfone PEI 50 mg/L pH > 6 94% [116]
PEUF Polyethersulfone Carboxy methyl cellulose 10 mg/L pH = 7 97.6% [118]
PEUF Ceramic Poly(acylic acid) sodium 160 mg/L pH = 5.5 98-99.5% [119]

Table 3
Cu(II) removal by using UF, NF, RO, and NF + RO.

Type of membrane Initial concentration Removal efficiency Operation conditions References

NF 0.01 M 47–66% Transmembrane pressure 1–3 bars [121,130]
NF 0.47 M 96–98% Pressure = 20 bars [131]
RO 7.86  103 M 98–99.5% Pressure = 5 bars [128]
RO Between 4.7  104 and 1.57  103 M 70–90% Low pressure RO [132]
RO + NF 2M More than 95% Pressure = 35 bars [133]
RO + NF 0.015 M 95–99% Pressure = 3.8 bars [134]

typically 1 nm that corresponds to MW cut-off (MWCO) of 300–
500 Da. There are many different membrane processes, which
were developed for the selective separation to make the initial cost
lower and to mitigate the increasing concerns associated with
heavy metals contaminated wastewater [114,126]. Kotrappanavar
et al. [127] examined the components of most NF membranes,
which consist of thin film composites made of different artificial
polymers that contain the charged groups. These groups can
increase the polymers efficiency in the removal of charged heavy
metal ions from wastewater. Further, the separation in NF achieved
by electro migration as well as sieving, the Donnan effect, solution
diffusion, and dielectric exclusion, which makes the NF mem-
branes useful for the removal of both uncharged and charged
organic and/or inorganic particles. Al-Rashdi et al. [120] reported
that the NF membrane can recover almost 100% of copper ions in
1000 mg/L copper solution within a range of pressure between
3 and 5 bar and pH values between 1.50 and 5, which shows that
the suitability of NF membranes for copper ions rejection.
However, the ability of NF membranes for copper ions rejection
is decreased when the concentration of copper increased and
reached 2000 mg/L. A comparison of Cu(II) removal using
appropriate NF systems at different operation conditions is
presented in Table 3.
2.3.3 Reverse osmosis
Reverse osmosis (RO) is a separation process, which uses
applied pressure to force the contaminated wastewater to go
through the membrane that rejects the contaminants on one side
and allows the pure solution to go to the other side (Fig. 3) [113].
During the past decade, RO has become one of the best separation
technology for industrial wastewater treatment for water reuse
Fig. 3. Reverse osmosis mechanism [113].
[128]. The RO membranes often have a thick barrier layer in the
polymer matrix where most of the separation process occurs. The
RO process can be used to remove various types of ions and
molecules from different types of contaminated water, including
industrial scale applications. However, the RO process consists
mainly of diffusive mechanisms; therefore, the efficiency of the
separation depends heavily on water flux rate, pressure, and solute
concentration [113]. RO brine usually contains large amounts of
highly toxic heavy metals (i.e. Mo, Cu, Ni) and other less toxic heavy
metals (i.e. Zn and Fe) [128]. Tran et al. [128] reported that hybrid
systems, which consist of electrodialysis and a pellet reactor is the
best way for increasing the recovery of RO by treating its
concentrate, where the pellet reactor removes scaling potential
then the contaminated wastewater is treated by the electrodialy-
sis. Many researchers investigated the efficiency of the RO process
for copper removal and found that high separation efficiency was
achieved within a range between 70–99.9%. Dialynas and
Diamadopoulos [129] tried to combine the bioreactor system
and RO membranes together in a pilot scale and found that copper
ions removal efficiency was very high. A summary of Cu(II) removal
using appropriate RO systems with different operation conditions
is given in Table 3.
2.4 Electrochemical methods
In general, the electrochemical removal methods have been
widely used in the metallurgy and metal finishing to separate the
metal ions (i.e. Zinc, Copper, Silver, Lead) [114,135,136]. The most
important electrochemical methods used for heavy metal ions
removal are electrocoagulation and electrodialysis. Electrodialysis
is considered to be as an electrochemical process to separate
copper ions from industrial wastewater, where copper ions
exchange through the membranes under the electric field [32].
Further, the electric field starts when the reactions at the surface of
the electrode produce hydroxyl ions at the cathode and protons at
the anode. The heavy metal ions have high affinity to be desorbed
and transferred toward the cathode through the electromigration
where the reason is that the ionic transformation of the protons is
much higher compared to that of hydroxyl ions [137]. Ur Rahman
et al. [138] invented an approach to reach an efficient and cost
effective electrolytic–electrodialytic apparatus and process for
metal ions recovery from wastewater streams. Fig. 4 represents the
continuous flow of metal-contaminated wastewater, which can be
treated in flow battery of single integrated cells. Each single cell
consists of three main sections, which are catholyte section (101),
metal-contaminated wastewater section (102), and anolyte section
(103). The metal-contaminated wastewater stream (100) will be
40 S.A. Al-Saydeh et al. / Journal of Industrial and Engineering Chemistry 56 (2017) 35–44

Fig. 4. The principle of electrodialysis cell used in continuous process [138].

divided into many streams that will enter all cells from (108) and
will leave from (109). The metal ions will be received by the anolyte
section through (110) and the produced oxygen from the anode
will leave from (112) while the produced hydrogen from the
cathode will leave from (113). All effluent wastewater will be
combined in stream (114). Nasef et al. [135,139] reported that the
properties of the membrane used in the electrodialysis process
should be taken into consideration, because these properties
determine the degree of copper ions separation. Furthermore,
Caprarescu et al. [140] studied the requirement of the used
membrane in electrodialysis process, which should possess good
chemical and thermal stability, where the separation process can
be carried out at high temperatures, in a solution that has a very
high or low pH values.
Recently, the studies of electrodialysis process were mainly
focused on the lab scale using a 3-sections design (Fig. 5A), which
consists of a central section that contains the metal contaminated
wastewater and two neighboring sections where the electrolytes
are continually circulated. The experimental parameters, such as
remediation time and current density of the contaminated
wastewater, play a big role to have a good efficiency of heavy
metal ions removal [137]. At The University of Denmark, a new
design of electrodialysis lab scale experiments has been developed,
which consists of a 2-sections cell (Fig. 5B). Ebbers et al. [141]
indicated that the use of 2-sections cell in electrodialysis
remediation showed less performance compared to the use of
3-sections cell. However, the acidification time was significantly
reduced, the final pH value was lower as well as the voltage values
were lower in the 2-sections cell compared to the 3-sections cell.
Furthermore, the direct introduction of protons to the suspension
was a reason to make the conductivity higher in the 2-sections cell.
Jensen et al. [142] introduced new design of bench-scale
electrodialysis process, which is electrodialysis remediation
(EDR) stack design to improve the efficiency of the heavy metals
contaminated wastewater by reducing their leachability. The stack
design consists of concentrate and feed sections, which have been
designed based on the principles of the 3-sections cell to make the
design suitable to scale up the process to pilot plant [143]. The
contaminated wastewater is continually circulated within the feed
section, where the concentrate liquid is circulated through the
concentrate section. As shown in (Fig. 5C), the concentrate and
feed sections are separated by the ion exchange membranes, which
play an important role in controlling the transfer of ions between
both sections. The acidification of the contaminated wastewater is
Fig. 5. EDR designs: A) 3-sections cell design B) 2-sections cell design C) EDR stack
done by the splitting of water at the membrane, where the protons design [107].
 S.A. Al-Saydeh et al. / Journal of Industrial and Engineering Chemistry 56 (2017) 35–44
are accumulated at the feed section. However, the separated heavy
metal ions are transported from the feed section to the concentrate
section by electromigration [137].
Many researchers [144–146] have reported that electrocoagu-
lation is a suitable technology for heavy metals removal, including
Cu, from industrial wastewater streams. Electrocoagulation is one
of the electrochemical approaches, which can use electrical
current to remove copper ions from industrial wastewater [147].
It is based on the generation of coagulant in situ by dissolving a
metal anode from Al, Fe or hybrid Al/Fe electrodes [148]. The
generation of metal ions takes place at the anode, while hydrogen
gas is released from the cathode, which can help to float the
particles that are flocculated out of the water. Electrocoagulation
has many advantages over other treatment methods; it is fast,
simple, inexpensive, easy to operate and environmentally safe
[149,150]. The current density is the most important parameter in
the electrocoagulation process, in which it can determine many
factors such as the bubble production rate, the coagulant dosage
rate, and the size and growth of the flocs; the efficiency of
electrocoagulation can be affected by these factors. The anode
dissolution rate is often increased when the current density
increases, which leads to increasing in the number of copper
hydroxide flocs that results in increasing in copper removal
efficiency [151,152]. The effects of the operation mode (batch or
continuous), electrode material, current or current density,
optimum pH, conductivity of the solutions, energy consumption
on the copper removal efficiency in the electrocoagulation process
are shown in Table 4.
In spite of the considerable amount of research and process
developments in electrocoagulation technology over the past
decade, further research is still needed to study the effect of cell
design and electrode geometry on the efficiency of heavy metal
removal. Further, most of the current studies have been carried out
at the laboratory scale, and hence more efforts should be made to
evaluate the electrocoagulation process at pilot plant scale.
2.5 Photocatalysis
Photocatalysis is a promising method for the treatment of
several types of industrial wastewater. In this process, the
electron–hole pairs (e/h+) can be continuously generated from
semiconducting under solar radiation. Many different semi-
conductors have been used such as ZnS, ZnO, TiO2, CdS, and
CeO2 [159]. Different studies have been reported in the literature to
find the most suitable semiconductor for copper removal. Mahdavi
et al. [160] reported that TiO2 is the most widely used because of its
high photocatalytic activity, high stability, nontoxicity, and
excellent dielectric properties. The photocatalysis process to
remove Cu(II), using TiO2 as a semiconductor and a 254 nm UV-
C lamp at different experimental conditions, has been reported
[161]. The best results for the removal of Cu(II) was achieved at pH
within a range 3.5–4.5 and TiO2 mass between 0.5 and 0.75 g. The
results indicate that the TiO2 can be used in the photocatalysis
Table 4
Different systems for Cu(II) removal by electrocoagulation process.
Reactor Current density Conductivity (mS/cm) Energy consumption
Continuous 4.8 A/dm2 – –
5A – 10.99 kWh/Kg
Batch 5A 1.600 35.63 kWh/g
5A 1.600 35.06 kWh
0.3 A 0.634 – 5
100 A/m2 2 10.07 kWh/m3
33 A/m2 20 – 9
41
process to remove around 80% of Cu(II) [160,161]. Moreover,
Barakat et al. [162] conducted an experiment on the photocatalytic
degradation using UV-irradiated TiO2 suspension for the removal
of copper and destroying the complex cyanide. The obtained
results show that copper with initial concentration = 102 M was
completely removed within 3 h. Wahyuni et al. [163] studied the
photocatalytic removal of Cu(II), where the process was carried out
with an initial concentration of 10 mg/L using TiO2 with UV lamp
having a wavelength within a range of 290–390 nm. The maximum
photocatalytic efficiency was reached when using 50 mg of TiO2 at
pH 5; about 45.56% of the copper ions were removed.
3 Comparison of copper removal processes
Generally, many different methods have been studied by larger
number of researchers to remove copper ions from industrial
wastewater. These treatment methods can be classified as
chemical, physical, and biological, and they are often selected
based on many advantages such as high selective separation,
simplicity in control, and lower space requirement. Physico-
chemical treatments can be considered to be the most suitable
treatment methods for the removal of copper ions from industrial
wastewater. However, they still suffer from high operating cost due
to the high cost associated with the chemicals used and high
energy consumption. Since metal-contaminated wastewater may
contain some inorganic and organic matters, photocalatysis is a
promising method for the removal of organic and inorganic
contaminants together. Overall, each treatment method has its
own advantages and limitations. Table 5 summarizes the main
advantages and disadvantages of the different physico-chemical
treatments, which have been discussed in this review.
4 Future prospective
Water treatment for the removal of heavy metals has seen
considerable success in recent years and witnessed vast develop-
ment in applications and technologies. However, more research is
still needed. Future studies on copper removal should focus on the
interaction mechanism, especially on the molecular level such as
X-ray photoelectron spectroscopy (XPS), X-ray absorption fine
structure (XAFS), transmission electron microscopy (TEM), X-ray
diffraction (XRD), and Fourier transform infrared spectroscopy (FT-
IR) [167–169]. Recently, these methods have been applied in order
to investigate and study the adsorption mechanism [170]. XAFS
spectroscopy, including X-ray absorption near edge structure
(XANES) spectroscopy and extended X-ray absorption fine
structure (EXAFS) spectroscopy, has the ability to provide the
microstructure information of radionuclides [171,172]. Bond
distances, oxidation state, and coordination numbers, which are
the main examples of microstructures of copper ions that have
been adsorbed on the adsorbent surfaces at molecular level, can be
calculated from the measurement and analysis of EXAFS spectros-
copy [173]. The interaction mechanism can then be estimated from
Optimum pH Electrode materials Removal efficiency References
4 Al–Al 99% [153]
0.64 Ss–Ti 98.8% [154]
7 Fe–Fe 99.99% [155]
7 Al–Al 99.9% [150]
RO–Ti–Ss 99% [156]
3 Fe–Al 100% [157]
Al–Al >50% [158]
42 S.A. Al-Saydeh et al. / Journal of Industrial and Engineering Chemistry 56 (2017) 35–44
Table 5
Advantages and disadvantages of different treatment methods.
Removal method Advantages
Adsorption using low-cost  Low initial cost
adsorbents  Simple design
Cementation  Low cost process
 Consumes low energy
 Easy to control with simple operation
Membrane Filtration  Small space requirement
 Low operating pressure
 Highly selective separation
Electrochemical methods  Highly selective separation
 Eco-friendly in nature
Photocatalysis  Removal of organic and metals contaminants together
 Produces less toxic by-products
the information of the bond distances and coordination number,
which can be obtained from EXAFS.
5 Conclusions
The removal of heavy metals in general and copper from
industrial wastewater is a very important part of most of the
current research in the environmental field, due to the harmful
effects of heavy metals on the human health and living organisms
in the environment. Different treatment methods such as physical,
chemical and biological methods have been discussed in this
review paper, which considered studies encompassing the past
fifteen years. These methods include adsorption, cementation,
membrane filtration, electrodialysis, and photocatalysis. However,
it is important to note that the selection of the most suitable
method depends on some parameters such as economic parameter
(i.e. operation cost), environmental impact, initial concentration of
the copper ions, pH values, and the overall performance of the
method compared to the other methods. Finally, more research
work is still needed for each method to improve it and make it
more efficient. For the adsorption method, using biosorbents to
treat wastewater is a relatively new process and studies in this area
are limited; therefore, new types of biosorbents are needed to be
tested to reach the maximum efficiency. In cementation, the
current cementation agents take time to reduce higher copper ions
from the wastewater; therefore, future research in the areas should
be focused on testing new cementation agents that can reduce the
process time. Further, the effect of pressure as an operating
parameter has not been evaluated. For membrane filtration,
innovative techniques are needed for the development of
inexpensive, easily available, superior and long lasting membranes.
As for electrodialysis, the development of new designs is necessary
to improve the separation efficiency. Finally, more studies on the
effect of temperature are needed in the photocatalysis method.
Development of catalysts for a high photo-efficiency process that
can utilize wider solar spectra is needed.
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