Electrochimica Acta 132 (2014) 583–597

Contents lists available at ScienceDirect

Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrodeionization: Principles, Strategies and Applications

Lucía Alvarado 1 , Aicheng Chen ∗,1
Department of Chemistry, Lakehead University, 955 Oliver Road, Ontario, Thunder Bay, P7B 5E, Canada

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

Article history: Electrodeionization is an ionic separation technology that initially emerged ∼50 years ago. In an early
Received 2 March 2014 application, it was utilized to remove metallic species from radioactive wastewater; however, a poor
Received in revised form 28 March 2014 understanding of its functional kinetics has slowed its development and applications. Steadily increasing
Accepted 29 March 2014
research efforts have focused on the elucidation of detailed operational mechanisms, thereby enabling the
Available online 6 April 2014
extension of its applications to other fields. To date, electrodeionization has been proven to be an excellent
environmentally compatible purification, separation and concentration method. Novel materials have
Keywords:
been continuously developed toward the improvement and maturation of this technology, which may
Electrodeionization
Electrodialysis
lead to enormous environmental and economic benefits on a global scale. This comprehensive review
Membranes examines the inception, precursor techniques and historic evolution of electrodeionization, as well as
Ion exchange its underlying principles, advantages and promising applications in wastewater treatment and water
Water purification purification.
© 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 583
2. Principles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
2.1. Electrodialysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 584
2.2. Ion exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
2.3. Electrodeionization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
3. Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
4. Experimental set-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 591
5. Development of new materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 592
6. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
6.1. Heavy metals removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
6.1.1. Chromium removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 594
6.1.2. Removal of Copper, Cadmium and Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
6.1.3. Cobalt removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
6.1.4. Removal of other ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
6.2. Organic compounds separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
6.3. High purity water production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
7. Conclusions and future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 595
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 596
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 596

1. Introduction

Processes involving the use of ion exchange membranes are fre-

∗ Corresponding author. Tel.: +1 807 343 8318; fax: +1 807 346 7775. quently employed in water purification and wastewater treatment
E-mail address: [email protected] (A. Chen). [1]. These strategies are known as “integrated membrane systems”,
1
ISE member. which may be classified as pressure-driven and electrically-driven

http://dx.doi.org/10.1016/j.electacta.2014.03.165
0013-4686/© 2014 Elsevier Ltd. All rights reserved.
584 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597

[2]. Pressure-driven processes include microfiltration (MF), ultrafil- studies were conducted with solutions that contained calcium,
tration (UF), nanofiltration (NF) and reverse osmosis (RO), whereas iron, phosphates and detergents in order to demonstrate the reli-
electrically-driven approaches encompass electrodialysis (ED) and ability of the process. However, various factors in the cell design
electrodeionization (EDI). Pressure-driven processes are typically were not taken into account. It was not until the late 1980’s that
applied when the removal of suspended solids and bacteria are EDI was commercially available for the production of ultrapure
the primary goals, whereas electrically-driven approaches are water. Table 1 depicts the historical evolution of electrodeioniza-
employed when the aim is ion removal, which is achieved through tion technology, where it is evident that initial progress was slow.
the selective control and transport of ionic species. The fundamen- EDI technology evolved to encompass various applications, and in
tal principle behind electrically-driven processes is the passage 1971 high purity water was first obtained through the application
of ions through a selective barrier (ion exchange membrane) due of this system. Subsequently, researchers began to investigate new
to a gradient or driving force (electric field). Ion exchange mem- types of membranes and combinations with other systems such as
branes play a critical role in these processes as they are responsible UV. Over the last ten years there have been additional strides made
for accepting or rejecting ions in the establishment of dilute and in the advancement of this technology, which have contributed to
concentrate compartments. In this way, processes that utilize ion enabling further benefits through its use. This has included a clearer
exchange membranes have important applications in water purifi- understanding, and as a result, an extension of its utility beyond
cation [3–6], ion removal or ion concentration [7–14]. In order ultrapure water production, into the realms of analysis.
to obtain enhanced selectivity for specific ions, researchers are The success of EDI for the separation of ions stems from its early
increasingly focused on the synthesis of unique materials in the applications in the isolation of radioactive metallic species and its
development of composite membranes [15–18]. evolution to the production of ultrapure water. Presently, it is con-
ED is the most popular technology for electrically-driven pro- sidered to be a next-generation technology for water purification
cesses in industry, as it separates undesired ions from aqueous and wastewater treatment, as well as for practical utility in the
solutions at low operational cost and with the advantage that it does pharmaceutical, semiconductor and energy sectors. Its ability to
not generate residues [19–21]. This technology, which combines almost completely segregate ionic species from dilute solutions
the principles of dialysis and electrolysis, was first applied for the endows EDI with the capacity for being utilized in myriad other
demineralization of syrup in 1890. An initial work that described areas. Beyond enabling the generation of ultrapure water, this tech-
this technology in a scientific journal was published in 1930 [22]. nology may facilitate the separation of toxic metallic ionic species
Since its inception, the capabilities of this hybrid technology have that are present in industrial waste effluents, and has been the basis
been demonstrated in several areas, encompassing desalination, of additional applications [31]. Hence, EDI is a green process that
acid and caustics production, organic compound separation [23], requires only electricity and proper ion exchange materials, negat-
radioactive wastewater treatment [24], ultrapure water production ing the necessity for regenerative agents or other chemicals [32].
and general ionic separation. Although ED qualifies as an excellent It is plausible that the slow advance of this technology may be
technology for applications that span a broad range of processes, a attributed to a general lack of understanding as to its functional
specific concentration limit must be adhered to in order to optimize kinetics. In order to elucidate the EDI process, in 1959 Glueckauf
energy efficiency. When ions are separated from the feed solution, proposed a theoretical discussion of the technology and suggested
there is an inherent drawback in which a phenomenon known as an ion removal model that involved two stages [33]: (i) diffusion
concentration polarization develops, whereby a high cumulative of ions into the resin; and (ii) ionic transfer through the resin bed.
resistance within the cell is built up, which decreases cell efficiency Moreover, in 1971, Matejka described a mechanism that encom-
[25]. In order to eliminate this disadvantage, a solid conductive ion passed three simultaneous stages [34]: (1) ion exchange between
medium has been introduced into the dilute compartment in the solution and resin bed; (2) transport of ions through a resin bed via
form of ion exchange resins. Thus, ED and ion exchange technolo- the application of an electric field; and (3) the electrolytic regener-
gies were combined, permitting the achievement of high quality ation of ion exchange resin.
ion separation with elevated energetic efficiency. This new hybrid Cumulatively, these works contributed to an improved under-
system was subsequently named as electrodeionization (EDI). standing of the role of ionic transport in the EDI process. In 1998,
EDI or continuous electrodeionization (CEDI) is a technology Verbeek and Neumeister proposed a model to predict ion exchange
that originated in the late 1950’s with the aim of minimizing the bed behavior via digital simulations that were based on Nernst-
phenomenon of concentration polarization, present in electrodial- Plank equations and interfacial solid-liquid equilibrium [35]. Other
ysis systems [26]. When dilute compartments are packed with ion authors have been engaged with gaining a greater understanding
exchange material, they behave as a conductor due to the pres- of regeneration mechanisms [36,37]. Meng et al. studied the phe-
ence of functional groups, which serve as a bridge between the ion nomenon of resin regeneration in EDI systems, and further clarified
exchange membranes. This strategy was successful in counterac- their kinetics by proposing the existence of four forms of interac-
ting ED concentration polarization, as was evidenced by an increase tion between ion exchange materials, where in situ ion exchange
in the maximum ion separation efficiency from 50% to 90%. There- may play a role in the regeneration of resins. EDI has progressed
fore, the synergistic integration of ED and ion exchange, which and improved to the point at which patents have been filed for the
combines the benefits of both technologies, effectively addresses marketing of systems that are designed to produce ultrapure water
some performance issues that are associated with each technology [38–48]. Steadily increasing activities have been focused on the
on its own [27–29]. creation of applications, opportunities and improvements for this
One of the earliest descriptions of electrodeionization was arti- technology, such as the use of electrodeionization reversal (EDIR)
culated in 1955 by Walters et al. at the Argonne National Laboratory to minimize membrane fouling [49].
[30], where it was utilized as a method for the removal of traces of
radioactive elements in water. In the late 1950’s an initial device
was developed by the Permutit Company, which incorporated a 2. Principles
mixture of anionic and cationic resins. In other work, Sammons
and Watts (Harwell Atomic Energy Authority) investigated the 2.1. Electrodialysis
deionization of a saline (NaCl) solution using an EDI module and
undertook to measure and correlate the relationships between Electrodialysis is a separation process that is based on the selec-
concentration values, flow rates and applied current. Subsequent tive migration of ions in solution through ion exchange membranes
 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597 585

Table 1
Electrodeionization evolution.

Year Researcher Development Company

1953 Kollsman CEDI: device for acetone purification Dutch company

1955 Walters et al. Electrodeionization: concentration of radioactive waste Argonne National Lab.
1959 Glueckauf CEDI: theory, operation and conditions NA
1960 Sammons and Watts Sodium salts deionization through EDI device Harwell Atomic Energy Authority
1971 Matejka Continuous Production of High-Purity Water by Electro-deionisation NA
1986 Giuffrida, Jha, Ganzi. Electrodeionization apparatus Millipore Co.
1989 Parsi Apparatus for the removal of dissolved solids from liquids using bipolar Ionics Inc.
membranes
1991 Katz, Elyanow, Sims Electrodeioization polarity reversal apparatus and process Ionics Inc.
1992 White Electredeionization ad ultraviolet light treatment method for purifying water Millipore Co.
1999 DiMascio, Gary, Ganzy Electrodeionization apparatus and method United States Filter Co.
2004 Srinivasan, Nebojsa, Avdalovic Water purifier and method Dionex Co.
2005 Chidambaran, Devesh, Sharma, Raina Fractional deionization process Aquatech International Co.
2005 Avijit, Gareth Apparatus and method for continuous electrodeionization Chemitreat Pte. Ltd.
2008 Barber Method and apparatus for shifting current General Electric Company
2011 Riviello Method of ion chromatography wherein a specialized electrodeionization Trovion Singapore Pte. Ltd.
apparatus is used
2012 Riviello Method of simultaneous anion and cation suppression in a continuous Trovion Singapore Pte. Ltd., Co.
electrodeionization apparatus

under activation of an electric field. As shown in Fig. 1, an ED sys- [50]. The reactions that take place within these compartments
tem consists of a series of anion and cation exchange membranes are:
that are alternately spaced between two electrodes, which results
in the formation of concentrate and dilute solution compartments. 2H2 O + 2e−  H2 + 2OH- Cathodic reaction
The solution is circulated through each compartment and an elec-
trical potential difference is applied between the two electrodes in 2H2 O  O2 + 4H+ + 4e- Anodic reaction
the process. In response to the presence of the electric field, cations
migrate toward the cathode, whereas anions gravitate to the anode The flow of solution through the membrane during an ED
target; however, the interposed permselective membranes act as process is determined by the applied electric potential gradient.
barriers to their migration, which allows or prevents ions from Ion exchange membranes are permeable to ions because they
passing in accordance with their electrical charge. Over time, one have a matrix that is comprised of synthetic ion exchange resin.
of the compartments is stripped of ions (diluted), while the other The polymer matrix of the membrane contains fixed functional
becomes more ionically populated (concentrated). An electrolyte groups that are electrically charged (ions), whereas interchange-
solution is circulated through the electrode compartments, which able mobile ions (called counterions) reside within the pore spaces.
are called electrode rinse compartments, as the processes that take This arrangement serves to maintain electrical balance within the
place within them are different than those occurring within the matrix. In this way, there exists an electric field that is sufficient
central compartments (those that are delimited by membranes) to overcome the forces that constrain mobile ions, and the ions

Fig. 1. Representation of electrodialysis process.

586 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597

Fig. 2. Ion exchange membrane structure.

that enter the pores from solution replace the loads, enabling the Ilim in order to harness the full extent of energy via the transport of
selective passage of ions [51]. If the matrix is positively charged, ions.
the counterions are negative and therefore permeable to anions.
With the application of an electric field, they replace the counter- 2.2. Ion exchange
ions and the fixed charges of the matrix prevent the passage of
co-ions (ions with the same charge of the fixed groups), in this Ion exchange (IX) is the diffusive ionic redistribution that occurs
case cations. Otherwise, if the polymer matrix has fixed negative between an insoluble material that is capable of exchanging cations
charges, the counterion is positive and therefore, the membrane or anions, and a solution, which contains ionic species. This pro-
is permeable to cations and impermeable to anions [52,53]. The cess begins when a chemical potential gradient arises between
flow thus partially selectively deionizes through the membranes. the solution and the ion exchanger. As shown in Fig. 3, the ions
Fig. 2 depicts the structure of the ion exchange membranes, in the solution diffuse into the exchanger surface and displace
with a description of each of the ions that are present in each the mobile species within the resin, which are then retained as a
case. result of intermolecular attractions between fixed sites and the ion
When current is applied, an electric potential difference is exchanger. However, in a solution that contains several ions of the
obtained as a current response, which is the result of the speed same charge (positive or negative), introduced exchangers exhibit
at which the ions are transported within the system. By increasing an ionic preference. The causes of such selectivity are associated
this potential difference, the current is also amplified as a result with ion exchanger dimensions (steric hindrance), its valence, the
of the enhanced transport velocity of the ions that contact the pore size within the matrix, as well as electrostatic interactions
membrane and traverse it. However, since the rate of ion transport between the matrix and the counterions [55].
is much higher within the membrane in contrast to the solution, The kinetics of the process depends on the mobilities of the ions
this increase in current attains a threshold where the concentra- to be exchanged within the resin, counterions and the prevailing
tion of ions at the membrane/solution interface is degraded to the core temperature. Thus, the process efficiency is a function of the
point that any subsequent increase in the electric field results in affinity of the ion exchange resin for a particular ion, the pH of
the dissociation of water [54]. This is because the population of the solution, the concentration of ions in solution and tempera-
ions that is present at the membrane/solution interface is insuffi- ture. Once the ion exchange resin has been saturated, the recovery
cient to carry an appropriate current flow. Hence, the H+ ions and of eluted ions that have been exchanged by the resin via an ionic
OH− products that are generated from the dissociation of water solution is necessary, which exchanges mobile ions with those that
begin to conduct electrical current. The current at this juncture is are present in the resin. As membranes, ion exchange resins are
called the limiting current, Ilim . Beyond this point there is an increas- synthetic polymers that contain a cross-linked matrix through the
ing resistance in the cell and the pH of the solution is altered. action of a crosslinking agent and fixed functional groups. Most
This causes a decrease in system efficiency via the requirement commercial resins are based on styrene-divinylbenzene and are
for higher energy consumption, and the changes in pH may lead acrylic-based. Crosslinking imparts mechanical stability, strength
to the precipitation of insoluble hydroxides on the surface of the and insolubility to the polymer, which in turn determines the
membrane [55]. The appearance of the concentration polarization swelling capacity, with swelling defined as the property that allows
phenomenon prevents the treatment of very dilute solutions in ED the permeability of ions into the matrix and improves the accessi-
systems. Hence, it is convenient to operate the system at 80% of bility of ions to the functional groups [57].
 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597 587

Fig. 3. Top: example of an anion ion exchanger, with positive charges in the matrix and its counterions. Bottom: example of an anion exchange process.

2.3. Electrodeionization order to provide a substrate for electrical activity, which prevents
the occurrence of the concentration polarization phenomenon. The
Electrodeionization is a hybrid technology that is based on the applied electric field thus promotes ionic transport in two differ-
application of dual technologies, namely electrodialysis and ion ent compartments through the active medium (resin bed), which
exchange. Dynamic synergies between these two functions serve to collects and discharges the ionic species, thereby initiating mass
reduce the inherent disadvantages of each one (e.g., concentration transport through the ion exchange materials (membranes and
polarization phenomena and chemical regeneration). The combi- resins) [48]. The dissociation of water occurs simultaneously inside
nation of these capabilities has resulted in a technology that has the cell at sites where anionic and cationic exchange materials are
the capacity for treating low ionic strength solutions much more in contact, thereby creating protons and hydroxyl ions, which act
efficiently than the constituent processes on their own. The config- to regenerate the resin in situ. The function of the ion exchange
uration of an EDI cell involves cationic and anionic membranes that resin is to lower the resistance of the cell, which tends to increase
are alternately arranged between the anode and cathode to provide as the concentration of the diluted solution diminishes. The iono-
dilute and concentrated compartments as shown in Fig. 4. Beds of genic sites may acquire resin ion concentrations that are from 1,000
ion exchange resins are introduced into the dilute compartments in to 100,000 times higher with respect to the concentration of ions in
solution, and as a result resin bed conductivity is obtained. When an
electric field is applied, it influences the dissolution ions as well as
those that are derived from solid content (mobile ions). However,
when a higher concentration of ions exists in the solid in compar-
ison with the dissolution ions, the contribution of ion transport
through the solid is greater, relative to that obtained from the solu-
tion toward the membrane. This is because although ion mobility
within the solid is ∼20 times lower than what exists in solution,
the transport rate is determined by product mobility and concen-
tration, giving rise to a rate that is 50 to 5,000 times higher within
the solid [38].

3. Mechanisms

In 1969, Glueckauf proposed that the mechanism of removal of

ions in an EDI cell has two stages [33]: (i) diffusion of cations to
the strong cation exchanger and dissemination of the anions to the
strong anion exchanger; and (ii) ionic conduction of the solid phase
to the border of the membranes. Because the ion concentration
within the solid is very high, the process that controls ion removal is
the ion diffusion rate of the aqueous phase to the surface of the solid
ion exchange, which depends of three factors: (1) surface between
solid and solution; (2) thickness of the liquid layer through which
ions diffuse; and (3) concentration gradient between the solid and
liquid phase.
Fig. 4. Representation of an electrodeionization cell. The spheres represent the
ion exchange resin, AEM: Anionic Exchange Membrane, CEM: Cationic Exchange
When ions are transported by diffusion into the active sites of
Membrane. the resin via the application of an excess current that is higher than
588 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597

Fig. 5. Porous plug model: a) Conduction routes through resin bed, b) Model representation of three conductance elements. Reproduction from ref. 59 with permission of
ACS publications.

necessary for the movement of ions, a portion of the solvent (H2 O) 3 = c (5)
is separated into its constituents (H+ and OH− ). These elements are
responsible for the regeneration of the resin-displacing ions that b = resin bed, specific conductance
have been collected [58]. As a consequence of the applied potential 1 = solid and interstitial solution, specific conductance
difference the ions migrate to the membranes through the packed 2 = solid, specific conductance
bed, which is responsible for the ionic transport and transfer of 3 = liquid, specific conductance
current into the system, occurring as the porous-plug model pro-  = interstitial solution, specific conductance
poses. This model was developed by Wyllie et al. in 1955 [59] and  = resin specific conductance
was applied to elucidate the nature of current propagation through a = cross-section fraction in the conductance element: solid and
resin beds. Another model was proposed by Baron in 1954, which interstitial solution
was based on the conductivity of the resin bed, to describe the elec- b = cross-section fraction in the conductance element: solid
trical behavior of an ion exchange bed using the following statistical c = cross-section fraction in the conductance element: solution
model [56]: (liquid)
d = fraction in the conductance element 1 due at solid
b − 
ˇ= (1) e = fraction in the conductance element 1 due at solution
1/3
(b /) ( − )
The geometric parameters a, b, c, d, e are calculated from
b = resin bed, specific conductance electrolyte conductivity data derived from resin bed-specific con-
¯ = solid, specific conductance (discontinued phase) ductance vs interstitial solution-specific conductance, as illustrated
␬ = liquid, specific conductance (continued phase) in Fig. 6 [56]:
ˇ = bed empty volume fraction  b 
=b (6)
However, this model takes into account a discontinuous solid ¯ =0

and becomes inapplicable when conductivities approach zero.  d  a

b
When the conductivity of the liquid phase tends to zero, the model = +c (7)
d =0 e
predicts a zero electrical conductivity of the bed. However, this  d 
does not hold true as there exist continuous phase particles when b
= ae + c (8)
particles are in contact with one another. Therefore, the bed con- d =¯

veys conductivity and there is conduction present despite the lack a+b+c =1 (9)
thereof within the liquid [40]. Wyllie et al. proposed a model that
more adequately described the electrochemical properties of the d+e=1 (10)
resin bed (porous plug model), which explained geometric param- Investigations of electrodeionization typically separate diffu-
eters derived from empirical evidence. This model is based on the sion and migration stages in the study of their effects on the
principle that electrical current flows via three different routes: recovery of metal elements. For example, Dzyazko et al. [60] stud-
through the interstitial solution, through particles and the mixture ied the electrical conductivity of a strongly acidic resin loaded with
thereof, between particles and the interstitial component of the chromium and showed a correlation between conductivity and the
solution. The model is represented by three parallel conductance pressure dropSpoor et al. studied the migration of nickel ions in
elements, corresponding to the three possibilities of flow as shown an electrodeionization system, where macroporous resins were
in Fig. 5. Hence, the specific conductance in the resin bed is defined loaded with Ni2+ ions, and observed the recovery of the ions in
by three conductance elements: the system through the application of an electric field [61]. Under
this system, the flux for the ion, J, is determined by the Nernst-
b = 1 + 2 + 3 (2)
Planck equation (11), taking into account only mass transport via
a migration (12):
1 = (3)
d + e
Di Ci di z FD C d
Ji = − − i i i + Ci u (11)
2 = b (4) RT dx RT dx
 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597 589
cm-1

d b a
c
d e
-1

0
Bed, specific conductance,

d b ae c
d
Fig. 7. Current-voltage curve of the CEDI system. Reproduced from ref. 67 with
permission of Springer.

Interstitial solution, specific conductance, -1 cm-1 was investigated initially, and subsequently a current was applied
in order to study the ionic electromigrative electric field, which
Fig. 6. Plot of bed specific conductance vs interstitial solution specific conductance, revealed a current efficiency of 100%. A more complete work on EDI
to calculate geometric parameters for the Wyllie model. Reproduced from ref. 56 was carried out in 2004 by Song et al., wherein the transport of Co2+
with permission of Dover.
in continuous EDI was studied. These results indicated that the flux
was constant over the first three hours, which is ideally when the
zi FDi C i d Nernst-Planck equation may be used. Following this time period
Ji = − (12)
RT dx the linear behavior observed was due mainly to the presence of
the H+ product derived from the dissociation of water, which was
where D is the diffusion coefficient, C the concentration,  the
also transported through the resin, and therefore modified the con-
chemical potential, z valence, F Faraday constant, R the ideal gases
centration of cobalt within the resin (C i ) [66]. On this basis it was
constant, T temperature in Kelvin,  electric potential, x the distance
proposed that the current efficiency and ␩i could be calculated for
and u the linear velocity. The mobility (ui ) of nickel ions within
Co2+ to reflect changes in the resin over extended time periods (16):
the resin according to the initial conditions of the system (13) was
calculated from the following relationship: t t
2F(ni 2 − ni 1 )
o o d i = (16)
Ji = −zi Fui (13) Q ot2 − Q ot1
dx
Meanwhile, a second part of this work was completed when the where ni is the number of moles of Co2+ in the concentrate eval-
researchers undertook to explore membrane and resin resistance uated twice and Qo is the charge accumulated over days 1 and 2.
[62], which encompassed the study of mass transport within a flexi- Also determinable, are the moles of Co2+ that are transported to
ble resin and the effect of an applied electric field, E, knowing that the concentrate compartment in relation to the applied load. The
(14): results indicated that Co2+ transport is a function of the applied
load; mobility data was obtained as relates to the residence of
Ebed = Ecell –(Eanode +Ecatode + Emembranes + Eec ) (14)
cobalt ions within the resin using the porous-plug model of beds
where “ec” refers to the electrode compartments. This study and the Nernst-Planck equation. In the same year, studies were
revealed a linear trend between the nickel ion flux and the applied reported that concerned optimal current density selection in con-
electric field. It also determined the apparent diffusion coefficient tinuous electrodeionization, Fig. 7, in which two regions appear.
considering that: The first region contains a higher resistance, which means that
water splitting takes place in the second region [67]. In 2005, Malh-
Di F moud et al. [68] studied ohmic drops in the ion exchange bed by
ui = (15)
RT applying the Wyllie model to various degrees of crosslinking for
Later studies focused on concentration and potential gradi- the treatment of CuSO4 solutions. Satisfactory results were found
ents [63] in the system utilizing the Nernst-Planck equation (11), only for short-term operations. Thus, in order to determine opti-
neglecting convective mass transport. Thereby applying a model in mal operational conditions, the effects of applied voltage have been
which diffusion coefficients, surface area, a number of ionogenic investigated by a number of researchers [69,70]. In 2008, Niko-
group constants, and a uniform distribution of counter ions within nenko et al. established a semi-empirical approach to predict mass
the pores was considered. This study was conducted under the transfer parameters in ED and EDI [71].
same consideration that was made for transport across membranes. An additional critical phenomenon in the study and understand-
In the same year, the current distribution in the resin bed of an EDI ing of EDI pertains to its regeneration in situ. It is known that the
stack was determined [64]. water dissociation reaction occurs at the interface of anionic and
In 2003, Mahmoud et al. worked under the same scheme of cationic materials, with the effect of regenerating the resin that is
transport phenomena in the EDI system, where diffusion and in close proximity to the sites where this reaction occurs, as illus-
migration stages were studied separately [65]. The diffusion of Cu2+ trated in Fig. 8. In this way, Meng et al. [37] proposed to explain this
590 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597

Fig. 8. Water splitting sites, where “in situ” regeneration has taken place. Reproduction from ref. 78 with permission of Elsevier.

phenomenon by estimating the potential gradient that is developed

between the interphase of ion exchange materials as:

F(X − Ci ) 2
= x (17)
2εo εr

d F(X − Ci )
= x (18)
dx εo εr

where εо and εr are the dielectric permittivity in vacuum and rel-

ative permittivity of water at the interface of material exchange,
respectively, and X represents the concentration of fixed groups. It
was considered that Ci = 0 (by the action of ion exchange), which
was obtained by d/dx = 5.45 × 108 V/m, constitutes a value that
leads to the dissociation of water within the interstices of the
bed material from cation and anion exchange. Later, Lee et al.
[72] studied and characterized the regeneration stage via electrical
impedance spectroscopy, and purposed an electric circuit to rep-
resent the bed system in EDI and a model application as presented
in Fig. 9. Song et al. continued to study the effects of current and
ionic transport in the dissociation of water [73]. Ion mass trans-
fer phenomena was approached through equilibrium principles
[70] and revealed the sequence of the separation of ions as: Ca2+ ,
Mg2+ , K+ > NO- 3 > Cl− > Na+ , as consistent with ion exchange prior-
ity. System simulations have been conducted since 2009 in order
to generate new knowledge in regard to the mechanisms involved,
toward the emergence of predictive operational parameters for EDI
in dealing with specific ion species. Kurup et al. studied a multi-
component electrolyte, and worked with subroutine DNEQNF in
Fortran90 to describe a steady state model of Wafer Enhanced-
EDI [74]. The simulations were validated with experimental results,
which were in good agreement. In 2010, Lu et al. studied water dis-
sociation during the EDI process through a numerical simulation
using COMSOL multiphysics [75], and later in the same year they
Fig. 9. a) Unit of contacting ion exchange beads in a CEDI system; b) Schematic
reported a numerical simulation of the EDI process that was focused
representation of the paths that the current may take; c) Equivalent circuit for deter-
on the production of ultrapure water (% removal vs current density) mining the special dispersion of current. (RB is resistance of the bead, Rc is resistance
where the ionic concentrations at membrane interfaces were dis- of the contacting point, Rs is resistance of the solution, Rb is resistance of the bound-
played via a computer program [76]. Another numerical model was ary layer, and C bis capacitance of the boundary layer). Reproduction from ref. 72
applied to weak acid conversion by DASSL (differential/algebraic with permission of Elsevier.
 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597 591

Fig. 10. Electrodeionization cell configuration. Reproduction from ref. 79 with permission of Elsevier.

system solver), adding complete information in regard to break- geometry with transport numbers of the ions in the solution and
through curves and conductivity parameters [77]. membrane phases, as well as the hydrodynamic conditions in the
system, respectively. A specific limiting current plot might be made
4. Experimental set-up with self-selecting parameters such as configuration, flow rate, and
operation temperature, and may be generated by performing a
A typical electrodeionization system consists of an EDI cell, potential (V) sweep and registering current measurements (I). A
reservoirs for each solution (concentrate, dilute and electrodic typical graphic to Ilim determination is shown in Fig. 11 at the inter-
rinse), pumps and a power supply. The cell consists of cationic section of two traced lines on the data tendency, indicating the
and anionic membranes, which are positioned alternately between current limiting value, as well as a plot of the resistance of the solu-
the anode and cathode as is shown in Fig. 10. This system was tion vs I−1 ; both plots were presented by Alvarado et al. [78] to
utilized by Alvarado et al. [78,79] for the removal of chromium, illustrate the process for the removal of hexavalent chromium.
which shows single concentrate and dilute compartment and two The physical and electrochemical properties of ion exchange
electrodic rinse compartments. The number of compartments and materials may be evaluated in an attempt to predict and under-
their configuration are contingent on the objectives to be pur- stand their behavior and the responses of the system within which
sued. An initial step involves the design of the cell, and in order
to achieve high-quality results, appropriate ion exchange materials
14
(resins and membranes) should be selected. Since there are myr-
iad materials to choose from which possess diverse functionalities,
typical resins and membranes have been summarized and listed in 12
Tables 2 and 3. The best results are found through the use of strong
exchange materials. Recently, some exchangers as zeolite and Poz- 10
zolana have been tested focusing in chloride absorption, since the
chloride gas generated in the positive electrode causes corrosion in 8
I [mA]

the EDI cell and damage to membranes [80].

On other hand, the system configuration should also take into
Ilim
6
account the mass transfer characterization of the cell, which may
be defined initially as an ED system. Cell characterization aids in
the prediction of limiting current values and imparts knowledge 4
of the factors that may influence mass transport within the cell.
Lee et al. [81] describe how cell characterization may be accom- 2
plished when the diffusion coefficients and transport numbers in
the membranes are plotted vs the molar concentration of the elec- 0
trolyte. When non-linear relationships between the Ilim /C vs molar 0 1 2 3 4 5
linear velocity of the electrolyte is obtained from different elec-
E [V]
trolyte concentrations, then plots assist with the prediction of new
limiting current values for the cell. Additionally, the plot may indi- Fig. 11. Limiting current determination in a Cr (VI) removal process. Reproduction
cate the values of coefficients “a” and “b”, which relate to the cell from ref. 78 with permission of Elsevier.
592 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597

Table 2
Resins used in electrodeionization systems.

Supplier Name Ion References

Bayer Leverkusen-Wolfen Lewatit MPC 64 CrO4 - [114]

Bayer Leverkusen-Wolfen Wolfatit SZ 30 CrO4 - [114]
Central Drug House Ceralite IR 120 Ca2+ , Fe2+ [9]
Central Drug House Ceralite IRA 400 Cl- , SO4 2- , PO4 3- [9]
Chemical Plant of Nankai University, China D072 Ni2+ [109]
Chemical Plant of Nankai University, China D296 SO4 2- [109]
Dow Chemical Co.TM Dowex 50 WX 2% Cu2+ , Ni2+ [63,119,122]
Dow Chemical Co.TM Dowex 50 WX 4% Cu2+ , Ni2+ [63,119,122]
Dow Chemical Co.TM Dowex A550 UPW Cl- [152]
Dow Chemical Co.TM Dowex C650 UPW Na+ [152]
Dow Chemical Co.TM Dowex HCR-S 8% Cu2+ , Ni2+ [63,119,122]
Dow Chemical Co.TM Dowex Mac-3 K+ [79]
Dow Chemical Co.TM Dowex MSC-1 Ni2+ [94]
Hangzhou Resin Co. D001 Cu2+ [118]
Hangzhou Resin Co. D201 SO4 2- [118]
Institut Francais du Textile et de l‘Habillement AET cellulose PO4 3- [87]
Institut Francais du Textile et de l‘Habillement Bipolar IET Cl- , Na+ [85]
Institut Francais du Textile et de l‘Habillement CET cellulose Cd2+ , Fe2+ , HCrO4 - , Mg2+, Zn2+ [87]
Merck, Germany 4765 Na+ [69]
Merck, Germany 4766 Cl- [69]
Mitsubishi Diaion SA10A Amino acids [137]
Mitsubishi Diaion SK1A Amino acids [137]
Mitsubishi Diaion SKN 1 Co2+ [158]
Purolite Int. Ltd. Purolite 201 Cl- , F- , NO3 - [70]
Purolite Int. Ltd. Purolite C100E Ca2+ , Co2+ , Mg2+ , Na+ , Ni2+ , [7,131,143,148]
Purolite Int. Ltd. Purolite C 150 PHL Cu2+ [117]
Purolite Int. Ltd. Purolite A 520E NO3 - [142]
Purolite Int. Ltd. PFC100E Organic acids [100]
Purolite Int. Ltd. PFA444 Organic acids [100]
Purolite Int. Ltd. Purolite A400 Citric acid, Cl- , HCO3 - , NO3 - , SO4 2- [143,148]
Rohm and Haas Co.TM Amberlite IR-120 Ca+ , Co+ , HCO3 - , K+ , Na+ , Mg2+ [4,31,49,72,99,102,158]
Rohm and Haas Co.TM Amberlite IRA-67 HCrO4 - [79]
Rohm and Haas Co.TM Amberlite IRA-400 Cl- , SO4 - [99,106,109]
Rohm and Haas Co.TM Amberlite IRA 402Cl Cl- , CO3 2- , SO4 2- [4,49]
Rohm and Haas Co.TM Amberlite IRN 77 Co2+ , Na+, Ni2+ [67,89,158,161]
Rohm and Haas Co.TM Amberlite IRN 78 Cl-, SO4 - [67,89,161]
Rohm and Haas Co.TM Duolite C20 Pb2+ , Cu2+ , Zn2+ [124]
Synthesized in Lab Zirconium hidrophosphate Ni2+ [94]
The chemical plant of Nankai University, China D072 Cu2+ [120]
The chemical plant of Nankai University, China D296 SO4 2- [120]
Tianjin Hecheng S&T Develop. Co. Ltd. 001*7 Ca2+ [164]
Tianjin Hecheng S&T Develop. Co. Ltd. 201*7 CO3 2- [164]
Zhenguang Co. D354 HCrO4 - [113]

they reside. The membranes can be characterized electrically, via ion-exchanger textile has been tested and a conventional electro-
impedance measurements [55,82]; their capacities at operational dialysis comparison between EDI and ED technologies has been
temperature can be evaluated along with resins through adsorption undertaken, where EDI current efficiencies were found to be nearly
isotherms and within the EDI cell. The resin bed may be charac- 150% higher than ED, thereby demonstrating the success of the
terized using the Wyllie model [59] to quantify the current flow textile material for this system [84,85]. The production of high
into the cell. Subsequent to these characterizations the EDI stack resistivity water, the desalination of Na+ and Cl− [86], and the
is loaded and the dilute compartment is filled with wet cationic, extraction of impurities from phosphoric acid [87] have been stud-
anionic or mixed ion-exchange resin. The resin is wet to ensure that ied with this class of resin with good results.
the final volume is correct, taking into account that the mixed bed In seeking alternatives for ion exchange materials, immobilized
makes available additional regeneration sites. Finally, the EDI pro- ion-exchange polyurethanes (IEPU) containing polyurethane foams
cess is initiated in order to promote water splitting and the contin- have been synthesized by either bulk condensation [88] or a blend-
uous regeneration of the system, by introducing an applied energy ing method in order to obtain immobilized ion resin beads [89].
that exceeds the limiting current value. Electrodes that have been Effects about the permselectivity have been studied in order to
utilized by different authors are summarized and listed in Table 4, increase it, and new kind of ion exchange material developed [90].
in which one is used to function to the electrodic rinse media. Similarly, Dzyazko et al. have investigated a (hydrated zirconium
dioxide) xerogel ion exchange component of composite ceramic
5. Development of new materials membranes [91], and zirconium hidrophospathe has been vali-
dated in the electromigration of Ni2+ and Cd2+ [92–94]. In the case
New ion exchange materials have been continuously devel- of membranes, Larchet et al. proposed the use of profiled mem-
oped in order to obtain improved results in EDI applications. Ion branes in order to obtain a higher rate of mass transfer [95] or
exchange textiles (IETs) have been synthesized and characterized. techniques membrane-free, avoiding the problems associate to its
In 2004, a comparative study between a commercial resin (IRN use, as fouling or maintenance costs, including capacitive deioniza-
77) and a textile resin was conducted, which demonstrated that tion [96–98].
an equivalent removal of cobalt was possible, however, a higher A number of weaknesses may be found in EDI electrochemical
current efficiency was achieved when IET was employed [83]. The reactors, such as the leakage of ions and uneven flow distributions
 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597 593

Table 3
Types of membranes used in electrodeionization systems.

Supplier Name References

NA Composite ceramic membrane [115]

NA Graphite powder: Ionic current sinks (ICS) [133]
NA Porous conducting bipolar ceramic plates (EICM-IEs2 ) [103]
NA Polimeric composite carbon plates (EICM-Ies2 ) [103]
Asahi Glass Selemion AMV [69,85]
Asahi Glass Selemion CMV [69,85]
Astom Co., Japan CMX [49,73]
Astom Co., Japan AMX [49,73]
Astom Co., Japan CMX [49,73]
MA-41 [137]
DuPontTM Nafion 117® [23,91,113,115,116,119,122,123]
DuPontTM Nafion 450 [87]
Ionics CR67 [7,131]
Membranes International AMI-7001 [91,94]
Membranes International CMI-7000 [94]
Merck Packed beds of graphite powder (ESCC1 ) [102,103,125]
Morgane-Solvay ADS XL 10 [143]
Morgane-Solvay CDS XL 5 [143]
Shanghai Shanghua water treatment material Co. Heterogeneous ion Exchange [120,164]
SWTM Double Flower® Heterogeneous [113,116]
Sybron Chemicals Inc. Ionac MA-3475 [23,87,141,148]
Sybron Chemicals Inc. Sybron MC-3470 [31,49,148]
Tokuyana Soda Co. TM Neosepta ACS [99]
Tokuyama Soda Co. TM Neosepta AFN [79]
Tokuyama Soda Co.TM Neosepta AMH [100,152]
Tokuyama Soda Co. TM Neosepta AMX [3,4,49,55,73,81,89,125,163]
Tokuyama Soda Co. TM Neosepta APM [9,106]
Tokuyama Soda Co. TM C6610F. [100]
Tokuyama Soda Co. TM CM-1 [79]
Tokuyama Soda Co.TM Neosepta CMB [152]
Tokuyana Soda Co. TM Neosepta CMX [3,4,49,55,73,79,81,89,125,163]
UCC Ltd. MA-41 [137]
UCC Ltd. MC-40 [137]
1
Electrostatically shielded concentrate compartment.
2
Electronically and ionically conducting media-intermediate electrodes.

within the dilute compartment [99]. In seeking to improve these little effect on the ability to transport. However, cation-anion resin
deficits toward the reliable and robust development of EDI, in 2007, ratios, polymer volumes (used to bind the resins) and resin selectiv-
Arora et al. reported the use of a “wafer in an electrodeionization” ity represented significant factors for improved development [99].
system [100]. The synthesis of this porous wafer involved the use of Other developments involved the use of an electrochemi-
ion exchange resins that were combined with a binding agent. This cal Faraday cage concept, which was introduced by Dermentzis
technology was dubbed Wafer Enhanced Electrodeionization (WE- [101–103], where electronically and ionically porous media were
EDI) and its development demonstrated the capacity for reducing used in place of membranes to function as ion traps. This media col-
the weaknesses of EDI. WE-EDI was carried out with the aim of lected ions by acting as a concentrate compartment; hence these
studying variables such as porosity, capacity, permeability and ion types of systems may operate without fouling issues, as illustrated
exchange beds. Wafer thickness and capacity were shown to have in Fig. 12.

Table 4
Electrodes used in electrodeionization cells.

Electrode material C-Cathode/A-Anode References

Graphite A, C [85]
Graphite powder A [102]
Platinized Ti A [102,103,115]
Platinized Ti C [115]
Platinized Ti grids A, C [125,133]
Pt A [60,72,94,114,148]
Pt C [60,72,94]
Stainless steel A [99]
Stainless steel C [7,9,23,26,70,78,79,99,106,112,131,140,142,148,164]
Stainless steel grids C [102,103]
Ti mesh C [113,114]
Ti plate C [114]
Ti/IrO2 -SnO2 -Sb2 O5 A [113,116]
Ti/IrO2 -Ta2 O5 A [79]
Ti/Pt A [4,7,49,122,123,131,142]
Ti/Pt C [4,49,119,122,123]
Ti/RuO2 A [9,23,70,118,164]
Ti mesh/TiO2 , RuO2 A [112]
594 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597

Fig. 12. Electrochemical cell applying the Faraday cage concept. Reproduction from ref. 103 with permission of Elsevier.

6. Applications the reuse of industrial aqueous effluent water, which contained Zn,
Cu, Cd and Pb by IX, and a comparison with EDI was conducted,
Since its inception, EDI has been utilized primarily in the gen- with the best results obtained with EDI [108]. Thus, the success
eration of ultrapure water to serve the energy, microelectronics, of EDI has been validated and researchers currently strive to attain
food, chemical and pharmaceutical industries. The product water optimal operational parameters and define major application fields.
obtained can be between 8 - 18 M cm from solutions that con- For example, parameters such as the influence of resin particle size
tain from 1 to 20 ppm TDS (total dissolved solids), with an energy distribution on the performance of the electrodeionization process
consumption of ∼0.26 kW-h/m3 . Hence, most EDI studies have have been reported by Lu et al. [109], where it was found that a
involved the evaluation of efficacy for the removal of various ions, mixed bed with a narrow size distribution improves performance.
such as Co2+ , Cu2+ , Ni2+ and NH4 + , with the aim of obtaining ultra-
pure water. EDI is capable of removing all of these ions and has 6.1.1. Chromium removal
since found utility in a number of associated applications, such as Hexavalent chromium is a harmful ion that is frequently found
the removal of wastewater resident pollutants and organic com- in industrial wastewaters as the result of mining and electroplat-
pound purification [104]. On other hand the research about this ing processes. Therefore, various technologies have been applied in
issue involves the search of better operation parameters, and stud- an attempt to remove these species of ions, and EDI has not been
ies about technical and economical aspects have been discussed by an exception. The capability of EDI holds major significance inso-
some authors [105]. far as the protection of the environment, as hexavalent chromium
is highly toxic [110,111]; and an increasing number of studies
6.1. Heavy metals removal have investigated its removal. For instance, the application of the
hybrid ion exchange and electrodialysis system achieved an over
Electrodeionization systems have been applied for the removal 98% removal of Cr (VI) [112,113]. In addition, Bergmann et al. car-
of ions from various types of wastewater, such as mining, electro- ried out experiments using three types of resins and conditioning
plating and nuclear processes, where the ions primarily present to remove CrO4 2- , where transport numbers and conductivities
are those related to chromium, copper, nickel, cobalt and oth- through the ion exchange bed were determined [114]. Further,
ers. Mining effluent is typically treated via precipitation, which Dzyazko et al. evaluated diffusion coefficients in ion exchange
forms sludge; thus researchers are focused on finding alternative materials used during the electrodeionization of this compound
methods. In this way, for example, electrochemical ion exchange [115]. A comparison between EDI, ED and IX was also done for
combined with ED has been applied for the removal of arsenic [106]. the removal of Cr(VI) in order to elucidate the robustness of EDI.
Yeon et al. studied the removal of Fe, Co, Cr and Ag ions from syn- Results indicated that 99.8% of Cr(VI) was efficiently removed by
thetic solutions, attaining 99% removal [107]. Souilah et al. studied this technology [79]. Xing et al. noted a significant Cr(VI) removal by
 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597 595

CEDI, resulting in concentrations of 0.09 and 0.49 ppm, from 40 and starting solution [136]. These ionic species removals have been
100 ppm Cr(VI) solutions, respectively, over 50 h of operation, with studied by other authors as well [137,138]. In addition, silicon and
an energy consumption of 4.1-7.3 kWh/mol Cr(VI) [116,117]. Most boron from ultrapure water have also been successfully attempted
recently, Alvarado et al. reported the integration of ion exchange [139]. Nitrates are frequently found in organic separations, and
and electrodeionization as a new approach for the continuous treat- these types of ions are also present in groundwater; hence their
ment of hexavalent chromium wastewater [78]. When the mixed separation from water has been successfully achieved [140–143].
resin bed was completely saturated, over 98.5% of the Cr(VI) was In comparison with ED, this technology (EDI) exhibits almost com-
still continuously removed with the continuous electrodeioniza- plete removal (99%) [144].
tion (CEDI) process being operated at a 10% over limiting current,
which facilitates the electro-regeneration of the resin in situ and 6.2. Organic compounds separation
the continuous removal of Cr(VI) from the dilute compartment,
while Cr(VI) is recovered in the concentrate compartment for re- EDI has the capacity to work with ions and their use as ED has
use. The energy consumption of the developed CEDI process is very been applied to organic compounds. For example, wafer-enhanced
low (<0.07 kWh/m3 ). electrodeionization in a continuous fermentation process has
been applied in the production of butyric acid with Clostridium
6.1.2. Removal of Copper, Cadmium and Nickel tyrobutryricum. The separation was shown to be efficient and oper-
Evaluations focused on the recovery of heavy metals from sim- ated without interruption for more than one month, demonstrating
ulated dilute industrial wastewaters have been carried out for the a 40-fold increase in concentration [145]. This technology (EDI) has
recovery of copper from CuSO4 , which employed simulated rins- also been shown as successful in the production of organic acids
ing waters from copper plating lines [118–122] and their models of [146]; biomolecules such as amino acids, peptides and proteins
operation have been studied and reported [123,124]. The treatment have been separated by this method as well, due to their ampho-
of solutions with variable ions is difficult due to the competition teric properties [147]. The extractive fermentation of L-(+)-lactic
that is established between each ion, hence a study involving the acid by Pediococcus pensosaceus allows for various operating condi-
priority of separation between heavy metals with the same valence tions [148]. Citric acid recovery has attained up to 6000 ppm in the
was conducted, and it was found that it follows the sequence: concentrate compartment from a solution containing only 70 ppm
Pb2+ > > Cd2+ > Cu 2+ ≥ Zn2+ [125]. [149].
Dermentzis, et al. [126] studied the ion and ionic current sinks
for the electrodeionization of simulated cadmium plating rinse 6.3. High purity water production
waters, applied for Cd2+ removal and obtained ultrapure water,
achieving 50 ppm to 0.1 ppm Cd2+ . The properties of IX mem- Because of corrosion, environmental concerns and unsafe treat-
branes were evaluated during the EDI process, which showed that ment media, developments in EDI systems have been evolved in
a 99% nickel ion removal was attained with EDI membranes, while order to obtain high purity water [150–158]. The electrochemi-
this separation efficiency was lower using heterogeneous IX mem- cal characterization of ion-exchange resin beds and the removal
branes. of cobalt from the coolant of an energy plant have been studied by
On other hand, nickel ion removal from dilute heavy metal Yeon et al. [159], which showed a point a capacity of over 4 meq/g
solutions via the electrodeionization process has been studied with 97% removal. In order to obtain improved results several tech-
extensively; examples of solutions containing 50 ppm Ni2+ have nologies have been combined in order to generate new alternatives,
attained 99.8% removal and a concentration stream as high as such as RO-EDI [160,161], EDR and EDIR [162] and Osmosis-CEDI,
1583 ppm during the process [127–130]. Electrostatic shielding which replaces RO-IX, and does not employ chemical regener-
electrodialysis/electrodeionization has been applied to the removal ation, as it implies the generation of a secondary wastewater.
of nickel. It was found that with this new system, which incorpo- Hence, RO-EDI is available to obtain water with a resistivity of 10-
rated fewer membranes that 80% removal was obtained in 35 min 16 M cm [163]. A Reverse Osmosis-Electrodeionization-Layered
under 30 A/m2 current. Bed (RO/EDI/LB) filtration system was utilized to obtain ultrapure
water, 17 M cm was attained with the treatment of 0.7 kWh/ton
6.1.3. Cobalt removal of water [164]. Pure water production from aqueous solutions con-
An electrostatic shielding-based system has been employed taining low hardness ion concentrations can be treated by EDI [165]
for removal of cobalt ions. A resulting concentration of 0.1 ppm and RO-EDI processes to obtain pure water with 99.8% hardness
was achieved from solutions containing 300 ppm cobalt [131]. In rejection [166].
addition, the selective separation of Ni(II)/Co(II) ions from dilute
aqueous solutions using continuous electrodeionization in the 7. Conclusions and future outlook
presence of EDTA showed success in the separation, since EDTA
worked as complexing agent [132]. Li et al. removed Co2+ and Sr2+ Electrodeionization has immense possibilities over an expand-
from a primary coolant by continuous electrodeionization packed ing range of applications, not only for the generation of ultrapure
with weak base anion exchange resins attaining 2 ng/L for cobalt water, but for selective separation and concentration. Its develop-
ions and 58-114 ng/L for strontium ions, which is much lower than ment was quite slow (∼60 year span since its inception) due to the
the concentration achieved through the use of commercial stacks lack of a detailed understanding of its mechanisms. A solid knowl-
[133]. A study on the removal of cobalt from a primary coolant by edge of the fine kinetics of these systems constitutes an important
CEDI with various conducting spacers was undertaken [134], where prerequisite for the further development and advancement of this
the cobalt ions were removed with a stack of EDI that contained technology. This green, environmentally compatible separation
three types of gaps: ion exchange resin, immobilized polyurethane strategy has a very promising future, with primary advantages that
ion exchange resin and textile ion exchange and as a result a max- include residue free operation, low process cost and exemplary effi-
imum of 99% removal was obtained [135]. cacy in ionic separation. The advent of improved novel materials,
electrostatic shielding, wafer ion exchange and nanomaterials, as
6.1.4. Removal of other ions new electrode coatings with enhanced activities and higher sur-
Ammonium ions have been removed by applying a two-step face areas emerge, will translate to the potential for significantly
EDI process, which attained 1 ppm from a 200 ppm ammonium increasing the efficiency of EDI systems. Further improvements will
596 L. Alvarado, A. Chen / Electrochimica Acta 132 (2014) 583–597

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