You are on page 1of 11

See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/318751630

Copper Removal from Industrial Wastewater: A Comprehensive Review

Article · July 2017


DOI: 10.1016/j.jiec.2017.07.026

CITATIONS READS

17 1,474

3 authors, including:

Muftah El-Naas Javaid Zaidi


Qatar University Qatar University
98 PUBLICATIONS   2,139 CITATIONS    57 PUBLICATIONS   618 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Solid-state Supercapacitors View project

Modified Composite Membranes and alloy catalyst for Proton Exchange Membrane/Direct Methanol Fuel Cell View project

All content following this page was uploaded by Javaid Zaidi on 08 April 2018.

The user has requested enhancement of the downloaded file.


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

Contents lists available at ScienceDirect

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 3. The adsorption of Cu(VI) is achieved at acidic pH using
uranium [7–10]. However, copper is usually found at high A4 zeolite.
concentrations in wastewater, because it is considered as the
most valuable and commonly used metal in many industrial Clay–polymer composites consist of natural clay minerals,
applications, such as metal finishing, electroplating, plastics, and which can be supported with polymeric material to improve their
etching [11–15]. Moreover, copper is a very toxic metal even at low capability of removing copper ions from aqueous solutions as
concentration and copper-contaminated wastewater must be reported by Azzam et al. [47]. Activated phosphate with nitric acid,
treated before discharging it to the environment [16–20]. The zirconium phosphate, and calcined phosphate at 900  C are
permissible limit of copper ions in industrial effluents was considered as phosphates, which have been studied as a new
reported by the United State Environmental Protection Agency type of adsorbents to remove copper from wastewater by Francis
(USEPA) to be 1.3 mg/L while it was stated by World Health et al. [13,48].
Organization that copper ions content in drinking water should not
exceed 2 mg/l [21–23]. Over the past few years, there have been 2.1.2 Adsorption on modified biopolymers
numerous new methods and techniques that were developed for Using modified biopolymers adsorbents is industrially attrac-
the removal of copper ions from industrial wastewater, such as tive because they have some advantages [49]. For instance, they
adsorption [24–27], cementation [16,28], membrane filtration can reduce the copper concentrations in water to sub parts per
[29–31], electrodialysis [32,33] and photocatalysis [34,35]. billion concentrations, they can be widely available, and they are
This main objective of this paper is to review the key options environmentally safe. The most attractive feature of biopolymers is
available for copper removal and hence offer a good start to guide that they contain different functional groups, such as amines and
new researchers who want to fill research gaps in the area and hydroxyls, which can increase the separation efficiency of heavy
improve the conventional copper removal methods. Although metal ions and make the chemical loading possibility reach the
there are few similar review papers dealing with the removal of maximum. Polysaccharide-based-materials are good example of
heavy metals, they all seem to be too general, considering other modified biopolymers, which can be used as adsorbents. Crini [50]
metal ions or concentrating on a specific treatment method. To the reported that there are two different ways to prepare an adsorbent
best of the authors’ knowledge, there are no comprehensive that contains polysaccharide-based-materials, which are:
reviews published in the open literature that focus on the removal
of copper in spite of its importance as a major water contaminant. 1. Crosslinking reactions, which is the reaction that occurs
Copper removal techniques are discussed in the following sections between the hydroxyl groups or amino of the chains with a
and compared in terms of removal efficiency, practicality, coupling agent to form the crosslinked networks (gels), which
environmental friendliness and process economics. are water insoluble.
2. Immobilize the polysaccharides on some insoluble supports by
2 Copper removal techniques some reactions to give hybrid materials.

2.1 Adsorption
2.1.3 Adsorption on industrial by-products
The word “adsorption” describes the process of mass transfer, Fly ash [51,52], iron slags, hydrous titanium oxide, and waste
where the material is transferred from the liquid phase directly to iron are industrial by-products, which can be chemically modified
the surface of the solid phase, after that it is bounded with to improve their removal ability for copper ions from industrial
chemical and/or physical interactions [36]. Davarnejad and Panahi wastewater. Iron slag was successfully utilized to remove Cu(II)
[37] reported that the adsorption method is considered to be the ions at a pH range of 3.5–8.5 [13], while Luo et al. [53] studied the
most common process used to remove different copper ions from performance of fly ash, from the coal-burning, for the removal of
industrial wastewater. Further, it provides many advantages Cu(II) from aqueous solutions. Hydrous titanium oxide has been
compared to the other treatment techniques because of the tested by Barakat et al. [54,55] to adsorb Cu(II) and Cu(VI), where
simplicity in design and its ability to involve low investment in the Cu(II) adsorption mechanism is achieved by surface hydrolysis
terms of initial cost as reported by Hidalgo-Vázquez et al. [38,39]. reaction as pH increases. TiO–Cu(OH)3 and TiO–CuOH+ species
On the other hand, Abdel Salam et al. [40–42] reported some are examples of Cu(II) complexes, which are considered as the
disadvantages of this process, such as its limited applications to main products of the surface hydrolysis reaction (Fig. 1).
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. 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 different advantages such as excellent mechanical stability, good
During the past few years, a considerable amount of research hydrophilic nature and high surface area [60]. Ding et al. [61]
has been devoted to the removal of heavy metals from industrial studied the performance of CNFs for removing copper ions in
wastewater using adsorbents that are derived from agriculture multi-component conditions, where copper ion was successfully
wastes. Such process is often referred to as bio-sorption [13]. adsorbed on CNFs at acidity pH. The maximum sorption capacity
Zeraatkar et al. [56] reported that bio-sorption is often considered for Cu2+ was found to be 204 mg/g at pH 5.5  0.2. Recently,
as one of the most innovative technology for the removal of heavy graphene oxides (GOs) and GO-based nanomaterials have received
metal ions using non-active biomass and non-living algae. considerable attention for the removal of organic and inorganic
Anastopoulos and Kyzas [57] proved that acidic pH, between pollutants from wastewater due to their unique properties such as
2 to 6, is the most effective range to remove heavy metals by high surface area, large pore volume structure, chemically stability,
adsorbents derived from modified biological wastes. Further, it was and abundant O2-containing functional groups (i.e. hydroxide and
found that the dead algae may have higher uptake of heavy metal carboxyl groups) [27,62–67]. Yu et al. [68] discussed the removal of
ions as compared to live algae by Ref. [58]. copper ion using GO-based nanomaterial in different composi-
tions, where the maximum copper ion sorption capacity was found
2.1.5 Adsorption on nanomaterials to be 45.2 mg/g on pure GO.
During the past few years, carbonaceous nanofibers (CNFs) and After discussing the different types of adsorbents, which can be
graphene oxide (GO) have been used to remove copper from derived from natural material, modified biopolymers, industrial
industrial wastewater. CNFs can be produced via hydrothermal by-products, and modified biological wastes, the uptake rates at
carbonization (HTC) using any precursor such as glucose [59]. The different operating conditions for each adsorbent have been
CNFs attracted the interest of many researchers because it showed 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, membrane method, such as energy saving, no phase change, cost
calcinated fly ash, iron oxide coated eggshell powder, granular effectiveness, easy to scale up, high efficiency in separation, and
activated carbon, etc. environmentally safe. Several types can be used to remove copper
ions from wastewater, which are classified based on the particle
2.2 Cementation size that can be removed, such as ultrafiltration, nanofiltration, and
reverse osmosis. However, Elimelech and Phillip [112] mentioned
Cementation is a general term used to describe the heteroge- that further developments are needed to improve the membrane
neous process in which the copper ions in the copper’s salt solution filtration technologies by reducing the energy consumption and
(i.e., CuSO4), are reduced to zero valence at the interface of iron by lowering the required thermodynamics operation conditions.
spontaneous electrochemical reduction to reach the copper
metallic state, with consequent oxidation of the iron and the 2.3.1 Ultrafiltration
dissolved iron species present more in the aqueous solution as Ultrafiltration (UF) is a promising membrane technique to
illustrated in Fig. 2 [102,103]. The cementation process is remove copper ions from industrial wastewater at low transmem-
considered as the most economic and effective technique to brane pressures. UF has a pore size between 5 and 20 nm and the
remove valuable and/or toxic metals from industrial wastewater MW of the separated particles should be within the range (1000–
[17]. During the past ten years, this method has been widely used in 100,000 Da) [113,114]. Gunatilake [113] proved that, based on the
different industries as a purification process of industrial waste characteristics of the membrane, UF membrane can achieve a good
solutions [16]. Aktas et al. [16,104,105] studied the advantages of removal efficiency (around 90%) for initial copper concentrations
using this technique, such as its comparatively low cost process ranging from 10 to 160 mg/L, where the best pH range is from 5.5 to
due to consuming low energy and recovering the metals in pure 6 and at an operating pressure between 2 to 5 bars. An important
metallic form with high efficiency. Also, it is easy to control and it advantage of UF is due to the high packing density which makes the
has relatively simple operation. On the other hand, DemirkIRan _ space requirement smaller.
and Künkül [106] mentioned the main disadvantage of cementa- Polymer enhanced ultrafiltration (PEUF) has also been evaluat-
tion technique, which is the excess sacrificial metal consumption. ed during the last few years [113]. PEUF has been proposed as a
Wu et al. [107] proved that the iron and zinc are the most common suitable method to remove copper ions from industrial wastewater
cementation agents used in the industrial applications because (Table 2). Water-soluble polymer is the main type of polymer that
they have strong reductive ability. However, it seems that the Cu is used in PEUF process to convert the heavy metal ions to
cementation using a scrap of iron, is the simplest and most macromolecular complexes, which have a molecular weight that is
reasonable method for Cu recovery [108]. Therefore, it produces higher than the membrane’s molecular weight cut off [115]. There
metallic copper sediments, which are suitable for metallurgical are many parameters that play a key role in effecting the PEUF
processes. The oxidation/reduction reactions are presented below process, such as the metal to polymer ratio, polymer type, and pH
[108]: values. Finding the most suitable polymer that can be used in PEUF
process has been the main focus of many researchers during the
Fe ! Fe2+ + 2e
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
Cu2+ + 2e ! Cu
acid, polyacrylic acid (PAA), and diethylaminoethyl cellulose.
The overall reaction: Molinari et al. [116] proved the high efficiency of polyethylenei-
mine (PEI) in removing Cu(II) from contaminated wastewater,
CuSO4 + Fe ! FeSO4 + Cu 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
2.3 Membrane filtration process has many advantages including high binding selectivity
and high removal efficiency. Although there has been considerable
Membrane filtration has received considerable attention in amount of research and many publications in this area, PEUF still
recent years for treating copper-contaminated industrial waste- has not reached wide industrial applications [117].
water, since it is applicable to remove suspended solid, organic,
and inorganic compounds (i.e. heavy metals) [13]. Furthermore, 2.3.2 Nano filtration
Escobar et al. [110–112] highlighted the main advantages of using 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
Fig. 2. Copper cementation on iron [109]. 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– [128]. The RO membranes often have a thick barrier layer in the
500 Da. There are many different membrane processes, which polymer matrix where most of the separation process occurs. The
were developed for the selective separation to make the initial cost RO process can be used to remove various types of ions and
lower and to mitigate the increasing concerns associated with molecules from different types of contaminated water, including
heavy metals contaminated wastewater [114,126]. Kotrappanavar industrial scale applications. However, the RO process consists
et al. [127] examined the components of most NF membranes, mainly of diffusive mechanisms; therefore, the efficiency of the
which consist of thin film composites made of different artificial separation depends heavily on water flux rate, pressure, and solute
polymers that contain the charged groups. These groups can concentration [113]. RO brine usually contains large amounts of
increase the polymers efficiency in the removal of charged heavy highly toxic heavy metals (i.e. Mo, Cu, Ni) and other less toxic heavy
metal ions from wastewater. Further, the separation in NF achieved metals (i.e. Zn and Fe) [128]. Tran et al. [128] reported that hybrid
by electro migration as well as sieving, the Donnan effect, solution systems, which consist of electrodialysis and a pellet reactor is the
diffusion, and dielectric exclusion, which makes the NF mem- best way for increasing the recovery of RO by treating its
branes useful for the removal of both uncharged and charged concentrate, where the pellet reactor removes scaling potential
organic and/or inorganic particles. Al-Rashdi et al. [120] reported then the contaminated wastewater is treated by the electrodialy-
that the NF membrane can recover almost 100% of copper ions in sis. Many researchers investigated the efficiency of the RO process
1000 mg/L copper solution within a range of pressure between for copper removal and found that high separation efficiency was
3 and 5 bar and pH values between 1.50 and 5, which shows that achieved within a range between 70–99.9%. Dialynas and
the suitability of NF membranes for copper ions rejection. Diamadopoulos [129] tried to combine the bioreactor system
However, the ability of NF membranes for copper ions rejection and RO membranes together in a pilot scale and found that copper
is decreased when the concentration of copper increased and ions removal efficiency was very high. A summary of Cu(II) removal
reached 2000 mg/L. A comparison of Cu(II) removal using using appropriate RO systems with different operation conditions
appropriate NF systems at different operation conditions is is given in Table 3.
presented in Table 3.
2.4 Electrochemical methods
2.3.3 Reverse osmosis
Reverse osmosis (RO) is a separation process, which uses In general, the electrochemical removal methods have been
applied pressure to force the contaminated wastewater to go widely used in the metallurgy and metal finishing to separate the
through the membrane that rejects the contaminants on one side metal ions (i.e. Zinc, Copper, Silver, Lead) [114,135,136]. The most
and allows the pure solution to go to the other side (Fig. 3) [113]. important electrochemical methods used for heavy metal ions
During the past decade, RO has become one of the best separation removal are electrocoagulation and electrodialysis. Electrodialysis
technology for industrial wastewater treatment for water reuse 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
Fig. 3. Reverse osmosis mechanism [113]. (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 41

are accumulated at the feed section. However, the separated heavy process to remove around 80% of Cu(II) [160,161]. Moreover,
metal ions are transported from the feed section to the concentrate Barakat et al. [162] conducted an experiment on the photocatalytic
section by electromigration [137]. degradation using UV-irradiated TiO2 suspension for the removal
Many researchers [144–146] have reported that electrocoagu- of copper and destroying the complex cyanide. The obtained
lation is a suitable technology for heavy metals removal, including results show that copper with initial concentration = 102 M was
Cu, from industrial wastewater streams. Electrocoagulation is one completely removed within 3 h. Wahyuni et al. [163] studied the
of the electrochemical approaches, which can use electrical photocatalytic removal of Cu(II), where the process was carried out
current to remove copper ions from industrial wastewater [147]. with an initial concentration of 10 mg/L using TiO2 with UV lamp
It is based on the generation of coagulant in situ by dissolving a having a wavelength within a range of 290–390 nm. The maximum
metal anode from Al, Fe or hybrid Al/Fe electrodes [148]. The photocatalytic efficiency was reached when using 50 mg of TiO2 at
generation of metal ions takes place at the anode, while hydrogen pH 5; about 45.56% of the copper ions were removed.
gas is released from the cathode, which can help to float the
particles that are flocculated out of the water. Electrocoagulation 3 Comparison of copper removal processes
has many advantages over other treatment methods; it is fast,
simple, inexpensive, easy to operate and environmentally safe Generally, many different methods have been studied by larger
[149,150]. The current density is the most important parameter in number of researchers to remove copper ions from industrial
the electrocoagulation process, in which it can determine many wastewater. These treatment methods can be classified as
factors such as the bubble production rate, the coagulant dosage chemical, physical, and biological, and they are often selected
rate, and the size and growth of the flocs; the efficiency of based on many advantages such as high selective separation,
electrocoagulation can be affected by these factors. The anode simplicity in control, and lower space requirement. Physico-
dissolution rate is often increased when the current density chemical treatments can be considered to be the most suitable
increases, which leads to increasing in the number of copper treatment methods for the removal of copper ions from industrial
hydroxide flocs that results in increasing in copper removal wastewater. However, they still suffer from high operating cost due
efficiency [151,152]. The effects of the operation mode (batch or to the high cost associated with the chemicals used and high
continuous), electrode material, current or current density, energy consumption. Since metal-contaminated wastewater may
optimum pH, conductivity of the solutions, energy consumption contain some inorganic and organic matters, photocalatysis is a
on the copper removal efficiency in the electrocoagulation process promising method for the removal of organic and inorganic
are shown in Table 4. contaminants together. Overall, each treatment method has its
In spite of the considerable amount of research and process own advantages and limitations. Table 5 summarizes the main
developments in electrocoagulation technology over the past advantages and disadvantages of the different physico-chemical
decade, further research is still needed to study the effect of cell treatments, which have been discussed in this review.
design and electrode geometry on the efficiency of heavy metal
removal. Further, most of the current studies have been carried out 4 Future prospective
at the laboratory scale, and hence more efforts should be made to
evaluate the electrocoagulation process at pilot plant scale. Water treatment for the removal of heavy metals has seen
considerable success in recent years and witnessed vast develop-
2.5 Photocatalysis ment in applications and technologies. However, more research is
still needed. Future studies on copper removal should focus on the
Photocatalysis is a promising method for the treatment of interaction mechanism, especially on the molecular level such as
several types of industrial wastewater. In this process, the X-ray photoelectron spectroscopy (XPS), X-ray absorption fine
electron–hole pairs (e/h+) can be continuously generated from structure (XAFS), transmission electron microscopy (TEM), X-ray
semiconducting under solar radiation. Many different semi- diffraction (XRD), and Fourier transform infrared spectroscopy (FT-
conductors have been used such as ZnS, ZnO, TiO2, CdS, and IR) [167–169]. Recently, these methods have been applied in order
CeO2 [159]. Different studies have been reported in the literature to to investigate and study the adsorption mechanism [170]. XAFS
find the most suitable semiconductor for copper removal. Mahdavi spectroscopy, including X-ray absorption near edge structure
et al. [160] reported that TiO2 is the most widely used because of its (XANES) spectroscopy and extended X-ray absorption fine
high photocatalytic activity, high stability, nontoxicity, and structure (EXAFS) spectroscopy, has the ability to provide the
excellent dielectric properties. The photocatalysis process to microstructure information of radionuclides [171,172]. Bond
remove Cu(II), using TiO2 as a semiconductor and a 254 nm UV- distances, oxidation state, and coordination numbers, which are
C lamp at different experimental conditions, has been reported the main examples of microstructures of copper ions that have
[161]. The best results for the removal of Cu(II) was achieved at pH been adsorbed on the adsorbent surfaces at molecular level, can be
within a range 3.5–4.5 and TiO2 mass between 0.5 and 0.75 g. The calculated from the measurement and analysis of EXAFS spectros-
results indicate that the TiO2 can be used in the photocatalysis copy [173]. The interaction mechanism can then be estimated from

Table 4
Different systems for Cu(II) removal by electrocoagulation process.

Reactor Current density Conductivity (mS/cm) Energy consumption Optimum pH Electrode materials Removal efficiency References
Continuous 4.8 A/dm2 – – 4 Al–Al 99% [153]
5A – 10.99 kWh/Kg 0.64 Ss–Ti 98.8% [154]

Batch 5A 1.600 35.63 kWh/g 7 Fe–Fe 99.99% [155]


5A 1.600 35.06 kWh 7 Al–Al 99.9% [150]
0.3 A 0.634 – 5 RO–Ti–Ss 99% [156]
100 A/m2 2 10.07 kWh/m3 3 Fe–Al 100% [157]
33 A/m2 20 – 9 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 Disadvantages References


Adsorption using low-cost  Low initial cost  limited to certain concentrations of copper ions [36,37]
adsorbents  Simple design

Cementation  Low cost process  Excess sacrificial metal consumption [16,113]


 Consumes low energy
 Easy to control with simple operation

Membrane Filtration  Small space requirement  High operating cost [164]


 Low operating pressure
 Highly selective separation

Electrochemical methods  Highly selective separation  High operating cost [165]


 Eco-friendly in nature  High energy consumption

Photocatalysis  Removal of organic and metals contaminants together  The duration time is long [166]
 Produces less toxic by-products  It has limited applications

the information of the bond distances and coordination number, [6] E.A. Dil, M. Ghaedi, A. Asfaram, S. Hajati, F. Mehrabi, A. Goudarzi, Ultrason.
which can be obtained from EXAFS. Sonochem. 34 (2017) 677.
[7] M. Jaishankar, T. Tseten, N. Anbalagan, B.B. Mathew, K.N. Beeregowda,
Interdiscip. Toxicol. 7 (2014) 60.
5 Conclusions [8] M. Rajabi, A. Rezaie, M. Ghaedi, RSC Adv. 5 (2015) 89204.
[9] E.A. Dil, M. Ghaedi, A. Asfaram, Ultrason. Sonochem. 34 (2017) 792.
[10] W. Cheng, C. Ding, Q. Wu, X. Wang, Y. Sun, W. Shi, T. Hayat, A. Alsaedi, Z. Chai,
The removal of heavy metals in general and copper from X. Wang, Environ. Sci. Nano 4 (2017) 1124.
industrial wastewater is a very important part of most of the [11] L. Trakal, R. Šigut, H. Šillerová, D. Faturíková, M. Komárek, Arab. J. Chem. 7
current research in the environmental field, due to the harmful (2014) 43.
[12] S. Ruyters, P. Salaets, K. Oorts, E. Smolders, Sci. Total Environ. 443 (2013) 470.
effects of heavy metals on the human health and living organisms [13] M.A. Barakat, Arab. J. Chem. 4 (2011) 361.
in the environment. Different treatment methods such as physical, [14] F.N. Azad, M. Ghaedi, K. Dashtian, A. Jamshidi, G. Hassani, M. Montazer-
chemical and biological methods have been discussed in this ozohori, S. Hajati, M. Rajabi, A.A. Bazrafshan, RSC Adv. 6 (2016) 19780.
[15] Y. Zou, X. Wang, A. Khan, P. Wang, Y. Liu, A. Alsaedi, T. Hayat, X. Wang, Environ.
review paper, which considered studies encompassing the past
Sci. Technol. 50 (2016) 7290.
fifteen years. These methods include adsorption, cementation, [16] E. Nassef, Y.A. El-Taweel, J. Chem. Eng. Process Technol. 6 (2015) 214.
membrane filtration, electrodialysis, and photocatalysis. However, [17] I.M. Ahmed, Y.A. El-Nadi, J.A. Daoud, Hydrometallurgy 110 (2011) 62.
it is important to note that the selection of the most suitable [18] J.-L. Gong, X.-Y. Wang, G.-M. Zeng, L. Chen, J.-H. Deng, X.-R. Zhang, Q.-Y. Niu,
Chem. Eng. J. 185–186 (2012) 100.
method depends on some parameters such as economic parameter [19] S. Yang, X. Ren, G. Zhao, W. Shi, G. Montavon, B. Grambow, X. Wang, Geochim.
(i.e. operation cost), environmental impact, initial concentration of Cosmochim. Acta 166 (2015) 129.
the copper ions, pH values, and the overall performance of the [20] M. Ghaedi, A. Shokrollahi, F. Ahmadi, H.R. Rajabi, M. Soylak, J. Hazard. Mater.
150 (2008) 533.
method compared to the other methods. Finally, more research [21] H. Aydın, Y. Bulut, C. Yerlikaya, J. Environ. Manage. 87 (2008) 37.
work is still needed for each method to improve it and make it [22] E.S.Z. El-Ashtoukhy, N.K. Amin, O. Abdelwahab, Desalination 223 (2008) 162.
more efficient. For the adsorption method, using biosorbents to [23] E. Eren, J. Hazard. Mater. 159 (2008) 235.
[24] S. Andrejkovi9 cová, A. Sudagar, J. Rocha, C. Patinha, W. Hajjaji, E.F. da Silva, A.
treat wastewater is a relatively new process and studies in this area Velosa, F. Rocha, Appl. Clay Sci. 126 (2016) 141.
are limited; therefore, new types of biosorbents are needed to be [25] M. Matouq, N. Jildeh, M. Qtaishat, M. Hindiyeh, M.Q. Al Syouf, J. Environ.
tested to reach the maximum efficiency. In cementation, the Chem. Eng. 3 (2015) 775.
[26] Z. Kong, X. Li, J. Tian, J. Yang, S. Sun, J. Environ. Manage. 134 (2014) 109.
current cementation agents take time to reduce higher copper ions [27] X. Wang, S. Yu, J. Jin, H. Wang, N.S. Alharbi, A. Alsaedi, T. Hayat, X. Wang, Sci.
from the wastewater; therefore, future research in the areas should Bull. 61 (2016) 1583.
be focused on testing new cementation agents that can reduce the [28] F. Gros, S. Baup, M. Aurousseau, Hydrometallurgy 106 (2011) 127.
[29] O. Ferrer, O. Gibert, J.L. Cortina, Water Res. 103 (2016) 256.
process time. Further, the effect of pressure as an operating
[30] Y.-N. Su, W.-S. Lin, C.-H. Hou, W. Den, J. Water Process Eng. 4 (2014) 149.
parameter has not been evaluated. For membrane filtration, [31] Y.C. Xu, Z.X. Wang, X.Q. Cheng, Y.C. Xiao, L. Shao, Chem. Eng. J. 303 (2016) 555.
innovative techniques are needed for the development of [32] S. Caprarescu, M.C. Corobea, V. Purcar, C.I. Spataru, R. Ianchis, G. Vasilievici, Z.
inexpensive, easily available, superior and long lasting membranes. Vuluga, J. Environ. Sci. 35 (2015) 27.
[33] Y. Dong, J. Liu, M. Sui, Y. Qu, J.J. Ambuchi, H. Wang, Y. Feng, J. Hazard. Mater.
As for electrodialysis, the development of new designs is necessary 321 (2017) 307.
to improve the separation efficiency. Finally, more studies on the [34] D. Kanakaraju, S. Ravichandar, Y.C. Lim, J. Environ. Sci. 55 (2017) 214.
effect of temperature are needed in the photocatalysis method. [35] S. Satyro, R. Marotta, L. Clarizia, I. Di Somma, G. Vitiello, M. Dezotti, G. Pinto, R.
F. Dantas, R. Andreozzi, Chem. Eng. J. 251 (2014) 257.
Development of catalysts for a high photo-efficiency process that [36] T.A. Kurniawan, A Research Study on Cr(VI) Removal from Contaminated
can utilize wider solar spectra is needed. Wastewater Using Chemically Modified Low Cost Adsorbents and Commer-
cial Activated Carbon, Environmental Technology Program, Sirindhorn
International Institute of Technology, Thammasat University, 2003.
References [37] R. Davarnejad, P. Panahi, Sep. Purif. Technol. 158 (2016) 286.
[38] A.R. Hidalgo-Vázquez, R. Alfaro-Cuevas-Villanueva, L. Márquez-Benavides, R.
[1] M. Visa, Powder Technol. 294 (2016) 338. Cortés-Martínez, J. Appl. Sci. Environ. Sanit. 6 (2011) 447.
[2] H. Dieter, Drinking Water Toxicology in Its Regulatory Framework A2, 1st ed., [39] K.P. Patel, S.K. Tank, K.M. Patel, P. Patel, APCBEE Procedia 5 (2013) 141.
in: P. Wilderer (Ed.), Treatise on Water Science, vol. 3, Publisher: Elsevier Ltd., [40] O.E. Abdel Salam, N.A. Reiad, M.M. ElShafei, J. Adv. Res. 2 (2011) 297.
Academic Press, 2011, pp. 377–416 Chapter: 3.14. [41] X. Wang, C. Wang, Colloid Surf. A Physicochem. Eng. Asp. 500 (2016) 186.
[3] P. Häyrynen, J. Landaburu-Aguirre, E. Pongrácz, R.L. Keiski, Sep. Purif. Technol. [42] S.N.A. Abas, M.H.S. Ismail, M.L. Kamal, S. Izhar, World Appl. Sci. J. 28 (2013)
93 (2012) 59. 1518.
[4] A. Asfaram, M. Ghaedi, G.R. Ghezelbash, RSC Adv. 6 (2016) 23599. [43] A. Maleki, B. Hayati, F. Najafi, F. Gharibi, S.W. Joo, J. Mol. Liq. 224 (Part A)
[5] A. Asfaram, M. Ghaedi, A. Goudarzi, M. Rajabi, Dalton Trans. 44 (2015) 14707. (2016) 95.
S.A. Al-Saydeh et al. / Journal of Industrial and Engineering Chemistry 56 (2017) 35–44 43

[44] Y. Yu, J.G. Shapter, R. Popelka-Filcoff, J.W. Bennett, A.V. Ellis, J. Hazard. Mater. _
[106] N. DemirkIRan, A. Künkül, Trans. Nonferrous Metals Soc. China 21 (2011)
273 (2014) 174. 2778.
[45] Mustafa Korkmaz, Cengiz özmetin, Baybars Ali Fil, Yeliz Yaşar, J. Inst. Sci. [107] L.-K. Wu, J. Xia, Y.-F. Zhang, Y.-Y. Li, H.-Z. Cao, G.-Q. Zheng, RSC Adv. 6 (2016)
Technol. 3 (2013) 47. 70832.
[46] M.A. Barakat, Res. J. Environ. Sci. 2 (2008) 13. [108] Y.A. Eltaweel, E.M. Nassef, R.A. Hazza, World Environ. 4 (2014) 199.
[47] E.M.S. Azzam, G. Eshaq, A.M. Rabie, A.A. Bakr, A.A. Abd-Elaal, A.E. El Metwally, [109] Elsa Metal Technology: Cementation, The Physical Reaction (2015). Available
S.M. Tawfik, Int. J. Biol. Macromol. 89 (2016) 507. at: http://www.elsametal.com/innovations/cementation-the-physical-reac-
[48] A.A. Francis, M.K. Abdel Rahman, J. Clean. Prod. 137 (2016) 1432. tion/ (accessed July 1, 2017).
[49] A. Tripathi, M. Ranjan, J. Biorem. Biodegr. 6 (2015) 315. [110] I. Escobar, B. Van der Bruggen, Modern Application in Membrane Science and
[50] G. Crini, Prog. Polym. Sci. 30 (2005) 38. Technology, American Chemical Society, 2011.
[51] P. Duan, C. Yan, W. Zhou, D. Ren, Ceram. Int. 42 (2016) 13507. [111] W.-P. Zhu, S.-P. Sun, J. Gao, F.-J. Fu, T.-S. Chung, J. Membr. Sci. 456 (2014) 117.
[52] M.S. Al-Harahsheh, K. Al Zboon, L. Al-Makhadmeh, M. Hararah, M. Mahasneh, [112] M. Elimelech, W.A. Phillip, Science 333 (2011) 712.
J. Environ. Chem. Eng. 3 (2015) 1669. [113] S.K. Gunatilake, Methods 1 (2015).
[53] J. Luo, H. Shen, H. Markström, Z. Wang, Q. Niu, J. Miner. Mater. Charact. Eng. 10 [114] F. Fu, Q. Wang, J. Environ. Manage. 92 (2011) 407.
(2011) 561. [115] Y. Huang, Applications of Polyvinylamine in Removal of Heavy Metals from
[54] M.A. Barakat, J. Colloid Interf. Sci. 291 (2005) 345. Wastewater by Polymer-Enhanced Ultrafiltration and Adsorption, UWspace,
[55] A. Georgaka, N. Spanos, Global Nest J. 12 (2010) 239. 2016.
[56] A.K. Zeraatkar, H. Ahmadzadeh, A.F. Talebi, N.R. Moheimani, M.P. McHenry, J. [116] R. Molinari, T. Poerio, P. Argurio, Chemosphere 70 (2008) 341.
Environ. Manage. 181 (2016) 817. [117] A. Figoli, J. Hoinkis, J. Bundschuh, Membrane technologies for water
[57] I. Anastopoulos, G.Z. Kyzas, J. Mol. Liq. 209 (2015) 77. treatment: removal of toxic trace elements with emphasis on arsenic,
[58] S.K. Mehta, J.P. Gaur, Crit. Rev. Biotechnol. 25 (2005) 113. fluoride and uranium, CRC Press, 2016.
[59] H.-S. Qian, S.-H. Yu, L.-B. Luo, J.-Y. Gong, L.-F. Fei, X.-M. Liu, Chem. Mater. 18 [118] M.A. Barakat, E. Schmidt, Desalination 256 (2010) 90.
(2006) 2102. [119] R. Camarillo, J. Llanos, L. García-Fernández, Á. Pérez, P. Cañizares, Sep. Purif.
[60] H.W. Liang, X. Cao, W.J. Zhang, H.T. Lin, F. Zhou, L.F. Chen, S.H. Yu, Adv. Funct. Technol. 70 (2010) 320.
Mater. 21 (2011) 3851. [120] B.A.M. Al-Rashdi, D.J. Johnson, N. Hilal, Desalination 315 (2013) 2.
[61] C. Ding, W. Cheng, X. Wang, Z.-Y. Wu, Y. Sun, C. Chen, X. Wang, S.-H. Yu, J. [121] B. Al-Rashdi, C. Somerfield, N. Hilal, Sep. Purif. Rev. 40 (2011) 209.
Hazard. Mater. 313 (2016) 253. [122] I. Soroko, Y. Bhole, A.G. Livingston, Green Chem. 13 (2011) 162.
[62] N. Seselj, C. Engelbrekt, J. Zhang, Sci. Bull. 60 (2015) 864. [123] C.-V. Gherasim, J. Cuhorka, P. Mikulášek, J. Membr. Sci. 436 (2013) 132.
[63] Y. Zhao, Sci. Bull. 60 (2015) 1962. [124] J. Duan, Q. Lu, R. Chen, Y. Duan, L. Wang, L. Gao, S. Pan, Carbohydr. Polym. 80
[64] Q. Hua-Jun, L. Li, W. Yu, Sci. Bull. 61 (2016) 443. (2010) 436.
[65] C. Sun, B. Wen, B. Bai, Sci. Bull. 60 (2015) 1807. [125] A.W. Mohammad, Y.H. Teow, W.L. Ang, Y.T. Chung, D.L. Oatley-Radcliffe, N.
[66] M. Zeng, H. Wang, C. Zhao, J. Wei, W. Wang, X. Bai, Sci. Bull. 60 (2015) 1426. Hilal, Desalination 356 (2015) 226.
[67] S. Yu, X. Wang, X. Tan, X. Wang, Inorg. Chem. Front. 2 (2015) 593. [126] W. Fang, L. Shi, R. Wang, J. Membr. Sci. 430 (2013) 129.
[68] S. Yu, X. Wang, Y. Ai, Y. Liang, Y. Ji, J. Li, T. Hayat, A. Alsaedi, X. Wang, Environ. [127] N.S. Kotrappanavar, A.A. Hussain, M.E.E. Abashar, I.S. Al-Mutaz, T.M.
Sci. Nano 3 (2016) 1361. Aminabhavi, M.N. Nadagouda, Desalination 280 (2011) 174.
[69] M.M. Rao, D.K. Ramana, K. Seshaiah, M.C. Wang, S.W.C. Chien, J. Hazard. [128] A.T.K. Tran, Y. Zhang, N. Jullok, B. Meesschaert, L. Pinoy, B. Van der Bruggen,
Mater. 166 (2009) 1006. Chem. Eng. Sci. 79 (2012) 228.
[70] M. Madhava Rao, A. Ramesh, G. Purna Chandra Rao, K. Seshaiah, J. Hazard. [129] E. Dialynas, E. Diamadopoulos, Desalination 238 (2009) 302.
Mater. 129 (2006) 123. [130] A.L. Ahmad, B.S. Ooi, Chem. Eng. J. 156 (2010) 257.
[71] I.J. Alinnor, Fuel 86 (2007) 853. [131] K. Oh-sik, Removal of Heavy Metals in Wastewater Using a Nano-filtration
[72] T. Mishra, S.K. Tiwari, J. Hazard. Mater. 137 (2006) 299. membrane Technology, Korea Environmental Industry and Technology
[73] S.M. Lee, A.P. Davis, Water Res. 35 (2001) 534. Institute, 2011.
[74] S.A.R. Shahamirifard, M. Ghaedi, M.R. Rahimi, S. Hajati, M. Montazerozohori, [132] L. Zhang, Y. Wu, X. Qu, Z. Li, J. Ni, J. Environ. Sci. 21 (2009) 764.
M. Soylak, Adv. Powder Technol. 27 (2016) 426. [133] E. Cséfalvay, V. Pauer, P. Mizsey, Desalination 240 (2009) 132.
[75] E.A. Dil, M. Ghaedi, G.R. Ghezelbash, A. Asfaram, M.K. Purkait, J. Ind. Eng. [134] P.S. Sudilovskiy, G.G. Kagramanov, V.A. Kolesnikov, Desalination 221 (2008)
Chem. 48 (2017) 162. 192.
[76] T. Vengris, R. Binkien, A. Sveikauskait, Appl. Clay Sci. 18 (2001) 183. [135] M.M. Nasef, O. Güven, Prog. Polym. Sci. 37 (2012) 1597.
[77] J. Li, S. Zhang, C. Chen, G. Zhao, X. Yang, J. Li, X. Wang, ACS Appl. Mater. [136] J. Li, X. Wang, H. Wang, S. Wang, T. Hayat, A. Alsaedi, X. Wang, Environ. Sci.
Interfaces 4 (2012) 4991. Nano 4 (2017) 1114.
[78] S. Wang, M. Soudi, L. Li, Z.H. Zhu, J. Hazard. Mater. 133 (2006) 243. [137] K.B. Pedersen, L.M. Ottosen, P.E. Jensen, T. Lejon, Electrochim. Acta 181 (2015)
[79] Ç. Üzüm, T. Shahwan, A.E. Erog lu, K.R. Hallam, T.B. Scott, I. Lieberwirth, Appl. 48.
Clay Sci. 43 (2009) 172. [138] S. Ur Rahman, N.S. Abo-Gander, S.J. Zaidi, US Patent Application 2006/
[80] D. Karabelli, C.a.r. Üzüm, T. Shahwan, A.E. Eroglu, T.B. Scott, K.R. Hallam, I. 0219574 A1, 2006.
Lieberwirth, Ind. Eng. Chem. Res. 47 (2008) 4758. [139] J.-H. Chang, A.V. Ellis, C.-H. Tung, W.-C. Huang, J. Membr. Sci. 361 (2010) 56.
[81] S. Xiao, H. Ma, M. Shen, S. Wang, Q. Huang, X. Shi, Colloid Surf. A Physicochem. [140] S. Caprarescu, V. Purcar, D.-I. Vaireanu, Sep. Sci. Technol. 47 (2012) 2273.
Eng. Asp. 381 (2011) 48. [141] B. Ebbers, L.M. Ottosen, P.E. Jensen, Chemosphere 125 (2015) 122.
[82] D. Feng, C. Aldrich, Hydrometallurgy 73 (2004) 1. [142] P.E. Jensen, C.M.D. Ferreira, H.K. Hansen, J.-U. Rype, L.M. Ottosen, A.
[83] V.K. Gupta, A. Rastogi, V.K. Saini, N. Jain, J. Colloid Interface Sci. 296 (2006) 59. Villumsen, J. Appl. Electrochem. 40 (2010) 1173.
[84] R.R. Bansode, J.N. Losso, W.E. Marshall, R.M. Rao, R.J. Portier, Bioresour. [143] G.M. Kirkelund, P.E. Jensen, A. Villumsen, L.M. Ottosen, J. Appl. Electrochem.
Technol. 89 (2003) 115. 40 (2010) 1049.
[85] S.-H. Huang, D.-H. Chen, J. Hazard. Mater. 163 (2009) 174. [144] D. Lakshmanan, D.A. Clifford, G. Samanta, Water Res. 44 (2010) 5641.
[86] T. Gosset, J.-L. Trancart, D.R. Thévenot, Water Res. 20 (1986) 21. [145] F. Akbal, S. Camcı, Chem. Eng. Technol. 33 (2010) 1655.
[87] X.-H. Chen, T. Gosset, D.R. Thévenot, Water Res. 24 (1990) 1463. [146] G.J. Rincón, E.J. La Motta, J. Environ. Manage. 144 (2014) 42.
[88] R. Ahmad, R. Kumar, S. Haseeb, Arab. J. Chem. 5 (2012) 353. [147] F. Jack, J. Bostock, D. Tito, B. Harrison, J. Brosnan, J. Inst. Brew. 120 (2014) 60.
[89] Y. Liu, P. Liang, L. Guo, Talanta 68 (2005) 25. [148] G. Chen, Sep. Purif. Technol. 38 (2004) 11.
[90] P. Liang, Y. Qin, B. Hu, T. Peng, Z. Jiang, Anal. Chim. Acta 440 (2001) 207. [149] P. Cañizares, F. Martínez, C. Jiménez, C. Sáez, M.A. Rodrigo, J. Chem. Technol.
[91] A.R. Iftikhar, H.N. Bhatti, M.A. Hanif, R. Nadeem, J. Hazard. Mater. 161 (2009) Biotechnol. 84 (2009) 702.
941. [150] J. Nouri, A.H. Mahvi, E. Bazrafshan, Int. J. Environ. Res. 4 (2010) 201.
_
[92] I.A. Şengil, M. Özacar, H. Türkmenler, J. Hazard. Mater. 162 (2009) 1046. [151] A.A. Bukhari, Bioresour. Technol. 99 (2008) 914.
[93] J.P. Chen, X. Wang, Sep. Purif. Technol. 19 (2000) 157. [152] E.A. Vik, D.A. Carlson, A.S. Eikum, E.T. Gjessing, Water Res. 18 (1984) 1355.
[94] N.M. Hilal, I.A. Ahmed, R.E. El-Sayed, ISRN Phys. Chem. 2012 (2012). [153] N. Adhoum, L. Monser, N. Bellakhal, J.-E. Belgaied, J. Hazard. Mater. 112 (2004)
[95] F.A.A. Al-Rub, M.H. El-Naas, I. Ashour, M. Al-Marzouqi, Process Biochem. 41 207.
(2006) 457. [154] C. Ahmed Basha, N.S. Bhadrinarayana, N. Anantharaman, K.M. Meera Sheriffa
[96] N. Prakash, S. Arungalai Vendan, Int. J. Biol. Macromol. 83 (2016) 198. Begum, J. Hazard. Mater. 152 (2008) 71.
[97] N. Prakash, S. Latha, P.N. Sudha, N.G. Renganathan, Environ. Sci. Pollut. Res. 20 [155] E. Bazrafshan, A.H. Mahvi, M.A. Zazouli, Asian J. Chem. 23 (2011) 5506.
(2013) 925. [156] A. Khelifa, S. Moulay, A.W. Naceur, Desalination 181 (2005) 27.
[98] R. Schmuhl, H.M. Krieg, K. Keizer, Water SA 27 (2001) 1. [157] F. Akbal, S. Camcı, Desalination 269 (2011) 214.
[99] Z. Cao, H. Ge, S. Lai, Eur. Polym. J. 37 (2001) 2141. [158] I. Heidmann, W. Calmano, J. Hazard. Mater. 152 (2008) 934.
[100] F.A. López, M.I. Martı’n, C. Pérez, A. López-Delgado, F.J. Alguacil, Water Res. 37 [159] P. Chowdhury, A. Elkamel, A.K. Ray, Photocatalytic processes for the removal
(2003) 3883. of toxic metal ions, in: Sanjay Sharma (Ed.), Heavy Metals in Water: Presence,
[101] S.T. Bosso, J. Enzweiler, Water Res. 36 (2002) 4795. Removal and Safety, The Royal Society of Chemistry, 2014, pp. 25–43 Chapter
[102] H.H. Abdel Rahman, E.M. Abdel Wahed, Hydrometallurgy 129–130 (2012) 2.
111. [160] S. Mahdavi, M. Jalali, A. Afkhami, Chem. Eng. Commun. 200 (2013) 448.
[103] E.S.Z. El-Ashtoukhy, M.H. Abdel-Aziz, Int. J. Miner. Process. 121 (2013) 65. [161] M.C. Yeber, C. Soto, R. Riveros, J. Navarrete, G. Vidal, Chem. Eng. J. 152 (2009)
[104] S. Aktas, Int. J. Miner. Process. 114–117 (2012) 100. 14.
[105] S. Aktas, Hydrometallurgy 106 (2011) 71. [162] M.A. Barakat, Y.T. Chen, C.P. Huang, Appl. Catal. B: Environ. 53 (2004) 13.
44 S.A. Al-Saydeh et al. / Journal of Industrial and Engineering Chemistry 56 (2017) 35–44

[163] E.T. Wahyuni, N.H. Aprilita, H. Hatimah, A.M. Wulandari, M. Mudasir, Am. [169] S. Yu, J. Wang, S. Song, K. Sun, J. Li, X. Wang, Z. Chen, X. Wang, Sci. Chin. Chem.
Chem. Sci. J. 5 (2015) 194. 60 (2017) 415.
[164] T.A. Kurniawan, G.Y.S. Chan, W.-H. Lo, S. Babel, Chem. Eng. J. 118 (2006) 83. [170] Y. Sun, X. Wang, W. Song, S. Lu, C. Chen, X. Wang, Environ. Sci. Nano 4 (2017)
[165] E. Oztekin, S. Altin, Turk. Online J. Sci. Technol. 6 (2016) 91. 222.
[166] R.K. Gautama, S.K. Sharma, S. Mahiyab, M.C. Chattopadhyaya, Contamination [171] S. Yu, X. Wang, S. Yang, G. Sheng, A. Alsaedi, T. Hayat, X. Wang, Sci. Chin. Chem.
of Heavy Metals in Aquatic Media: Transport, Toxicity and Technologies for (2017) 1.
Remediation, (2014) . [172] Y. Sun, Z.-Y. Wu, X. Wang, C. Ding, W. Cheng, S.-H. Yu, X. Wang, Environ. Sci.
[167] J. Wang, Y. Liang, Q. Jin, J. Hou, B. Liu, X. Li, W. Chen, T. Hayat, A. Alsaedi, X. Technol. 50 (2016) 4459.
Wang, ACS Sustain. Chem. Eng. 5 (2017) 5550. [173] Y. Chen, W. Zhang, S. Yang, A. Hobiny, A. Alsaedi, X. Wang, Sci. Chin. Chem. 59
[168] Y. Zou, Y. Liu, X. Wang, G. Sheng, S. Wang, Y. Ai, Y. Ji, Y. Liu, T. Hayat, X. Wang, (2016) 412.
ACS Sustain. Chem. Eng. 5 (2017) 3583.

View publication stats