Broad-Ranging Review: Con Figurations, Membrane Types, Governing Equations, and in Uencing Factors On Microbial Desalination Cell Technology

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Review

Received: 6 March 2022 Revised: 22 June 2022 Accepted article published: 30 June 2022 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jctb.7176

Broad-ranging review: configurations,


membrane types, governing equations, and
influencing factors on microbial desalination
cell technology
Hussein H Abd-almohi,a Ziad T Alismaeela and Mohanad J. M-Ridhab*

Abstract
Seawater might serve as a fresh-water supply for future generations to help meet the growing need for clean drinking water.
Desalination and waste management using newer and more energy intensive processes are not viable options in the long term.
Thus, an integrated and sustainable strategy is required to accomplish cost-effective desalination via wastewater treatment. A
microbial desalination cell (MDC) is a new technology that can treat wastewater, desalinate saltwater, and produce green
energy simultaneously. Bio-electrochemical oxidation of wastewater organics creates power using this method. Desalination
and the creation of value-added by-products are expected because of this ionic movement. According to assessments, recent
investigations on MDC configurations have led to significant changes in their operating characteristics, as well as their design
and operational factors. Additionally, the study notes the expanding uses of MDC in bioremediation, nutrient recovery, water
softening, and value-added chemical manufacturing. Significant results show that the MDC system produced outstanding desa-
lination without the need for external power, in addition to achieving wastewater treatment and energy recovery without the
need for intermediary processes. When it comes to its practical application, some of the technical obstacles include keeping pH
stable in cathodic and anodic fluids, increasing internal resistance using catalysts as electrode fillers, along with issues of
biofouling and durability. Although MDC technology is currently being developed and scaled up, additional research on mem-
brane fouling avoidance, material feasibility, electron transport kinetics, growth of microorganisms, and catalyst durability is
needed.
© 2022 Society of Chemical Industry (SCI).

Keywords: microbial desalination cells; microbial fuel cells; power generation; wastewater treatment

MEDCC Microbial electrolysis desalination and chemical-


ABBREVIATIONS production cell
AC Anode chamber MFC Microbial fuel cell.
AEM Anion-exchange membrane. OsMDC Osmotic microbial desalination cell.
AP Acid production. PBS Phosphate buffer solution.
A’P Alkali production. PMDC Photosynthetic MDC.
BAC BPM–AEM–CEM stack structure. rMDC Re-circulation microbial desalination cell.
BES Bio-electrochemical systems. RO Reverse osmosis.
BPM Bipolar membrane. SEM Scanning electron microscope.
CE Coulombic efficiency. SMDC Stacked microbial desalination cell.
CEM Cation-exchange membrane. TDS Total dissolved solid.
DR Desalination rate. UMDC Upflow MDC
ED Electro dialysis.
FO Forward osmosis.
IEM Ion-exchange membrane.
IEMs Ion-exchange membranes.
IER Ion-exchange resin. * Correspondence to: MJM Ridha, Department of Environmental Engineering,
IER- Ion-exchange resin packed MDC. College of Engineering, University of Baghdad, Al-Jadryah, P.O. Box 47012,
MDC Baghdad, Iraq. E-mail: muhannadenviro@coeng.uobaghdad.edu.iq
MCDC Microbial capacitive desalination cell.
a Department of Biochemical Engineering, Al-Khwarizmi College of Engineering,
MDC Microbial desalination cell. University of Baghdad, Baghdad, Iraq
MEDC Microbial electrolysis
desalination cell. b Department of Environmental Engineering, College of Engineering, University
of Baghdad, Baghdad, Iraq
1

J Chem Technol Biotechnol 2022 www.soci.org © 2022 Society of Chemical Industry (SCI).
www.soci.org HH Abd-almohi, ZT Alismaeel, MJM Ridha

INTRODUCTION the external voltage of the system significantly reduced energy


Energy has become critical for society to maintain economic consumption. Reducing the intensity of cathodic recycling, for
development and a good quality of life. IEA (International Energy example, from 18.2 to 8.9 L per minute, reduced energy consump-
Agency) predicted that the global energy demand in 2030 will be tion and COD removal, plus salt removal was reduced by 40%.16
50% higher than it is at present.1 However, in addition to the mas- To continue the oxygen reduction process, ‘wet’ catholyte recircu-
sive growth of the population and their increased demand for lation was used. This process also allowed for an increase in COD
fresh water, climate change has negatively affected large areas removal via aerobic treatment. Consequently, improving opera-
of the planet, resulting in, for example, an increase in desert areas. tional conditions may decrease energy use. Importantly, an MDC
Studies have proven that human consumption of clean water has uses the same amount of power for wastewater treatment as it
increased sevenfold since the year 1900, as the percentage dou- does for saltwater desalination when assessing its energy use.17
bles every 20 years.1 Currently, many countries around the world
suffer from scarcity of fresh water, and countries in the Middle Thermal (phase-change) process
East are those most affected. The amount of fresh water accessi- Thermal distillation techniques are commonly used in the Middle
ble for human use is only 1% of the water that covers the East because the oil reserves in this region maintain a consistent
globe.2–4 Meanwhile, traditional thermal-desalination and high- cost for the energy used in the process.18 The primary thermal
pressure membrane-desalination methods are extremely desalination process involves multi-effect distillation (MED), mul-
energy-intensive, using 3.7 to 650 kWh of energy per m3 of water tistage flash distillation (MSF), and vapour compression (VC).
desalinated.5,6 The effort of building water treatment plants pow- The VC process includes two types: mechanical (MVC) and
ered by renewable energy aims not only to meet the global need thermal (TVC).
for potable water but also to reduce the harmful gas emissions
that affect humans and living organisms; the use of fossil fuels
and combustion processes results in toxic gases, global warming, MED
and climate change.7 On this basis, several technologies have One of the most common methods of seawater distillation and
been introduced to avoid these technical problems; one of these purification is carried out in several stages, the first of which is
latest technologies is the microbial desalination cell (MDC) heating the seawater that enters the system using the water
system,8,9 which is a modified form of the microbial fuel system vapours inside the tubes in all steps, where some of the water
(MFC) and the bio-electrochemical system (BES) system.10,11 evaporates. Then, the water vapor flows to the later stages, the
MDC has exhibited a high efficiency in reducing pollution in process is repeated, and the water is heated and evaporated.15
wastewater, even with water containing less than 2000 mg L−1
of COD, by converting it into electrical energy. This system will
help the processing and production of wastewater and electrical MSF
energy, respectively. It has given promising results in wastewater In the desalination method, seawater is distilled by flashing a
treatment and energy production over the years.12 MFC is a type part of it into steam in distinct stages of what are basically
of BEC, wherein the production of bio-electrochemical energy counter current heat exchangers. Although desalination facili-
comes from the bacterial oxidation of the organic matter present ties provide approximately 26% of all desalinated water on
in the wastewater by bacteria that grow in anaerobic conditions; the globe, nearly all new desalination plants now utilise reverse
this method exhibited very high efficiency in the production of osmosis (RO) because of the significantly reduced energy
electrical energy and in the treatment of wastewater.13 usage.19,20
The concept of solar energy was recently introduced to treating
water through a solar collector-assisted multi-effect desalination
CONVENTIONAL DESALINATION (MED) and multi-stage flash (MSF) plant. The station consists of
several stages. Solar energy is used to heat the water fed by steam
TREATMENT PROCESS AND ENERGY in the tubes. Part of the water is evaporated and the steam moves
CONSUMPTION to the pipes in the next stage. The steam heats up and more water
Clean water consumption has increased and the expected aver- evaporates. The concentration of salts at the top of the plant is
age of clean water per capita would decrease by 1/3 in the next non-existent, whereas the concentration of salts at the bottom
20 years.14 The systems that work on desalinating salt water can of the unit is very high. In the centre of the unit, a gradient is
be divided into two types: the most widely used (e.g., phase- observed in the extraction of salts.21 In each stage, when heating
change thermal processes) and the commercially approved (e.g., the water from the previous stages, additional energy must be
membrane processes).15 Desalination technologies significantly derived from the collected solar energy, thus reducing the energy
reduce the water shortage problem and improve water quality, required for the seawater desalination unit. Using a solar collector,
quality of life, and economic status. One of the most crucial factors saltwater is pumped in and heated before being pumped into a
that should be included in most literature is the study of energy heat accumulator made up of many neighbouring tanks. With
consumption. To determine the appropriate fields of application the help of a heat accumulator, the evaporator's temperature
for the MDC system, the energy performance of the system must remains stable no matter how much solar energy is pumped into
be understood.16 Studies have shown that the energy consump- it. However, the evaporator runs at extremely low pressures and
tion of the system is still higher than those of traditional electrol- extremely high temperatures (up to 99 °C) (e.g., 0.07 atm). Once
ysis or wastewater treatments. Thus, reducing the energy the warmed water has been collected, it will go into the first tank,
consumption of the system is necessary for its practical applica- whilst the water that enters the evaporator will be drawn from the
tion; several ways have been proposed to modify the system to very top of the first tank and recirculated to the very bottom. This
avoid a large consumption of energy through a modified system instance raises the temperature of the water before it enters the
that recycles the catholyte and the applied voltage. Reducing evaporator.21
2

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Broad-ranging review: configurations, membrane types, governing equations www.soci.org

Table 1. Types of membrane process, methods of separation, and their applications

Membrane process Membrane type Driving force Method separation Range of application

Microfiltration20 Symmetric microporous Hydrostatic pressure Sieving mechanism due to Sterile filtration clarification
membrane; 0.1 to 10 μm pore difference 0.1 to 1 bar pore radius and
reduce absorption
Ultrafiltration20 Asymmetric microporous Hydrostatic pressure Sieving mechanism Separation of
membrane; 1 to 10 μm pore difference 0.5 to 5 bar micromolecular solution
radius
Reverse osmosis20 Asymmetric skin type Hydrostatic pressure Solution diffusion Separation of salt and micro-
membrane difference 20 to 100 bar mechanism solutes from solution
Dialysis20 Symmetric microporous Concentration gradient Diffusion in convention-free Separation of salt and micro-
membrane; 0.1 to 10 μm pore layer solutes from
radius macromolecular solution
Electrodialysis20 Cation and anion exchange Electrical potential gradient Electrical charge of particle Desalination of ionic solution
membrane and size
Gas separation20 Homogeneous or porous Hydrostatic pressure Solubility diffusion Separation of gas mixture
polymer concentration gradient

Membrane processes and the energy consumption of every conventional desalination


Membrane technologies are driven by one of these two forces: process are explained in detail in Tables 1 and 2.
electrical potential or pressure. It is vital to note the usual pressure
driving force ranges and separation mechanisms when under- MDCs
standing the removal abilities of the membrane system because MDC is an integrated form of MFC and ED cell that is developed
they can influence their power consumption.22,23 The type of for simultaneous desalination, wastewater treatment, and elec-
membrane process and method of separation, their application, tricity production. Cao et al. first introduced MDC in 2009, and
the developed system achieved a 90% salt removal rate within a
single cycle.24 The system consists of three chambers: anode,
desalination, and cathode. In these chambers, electrical energy
is produced from the movement of electrons outside the cell
Table 2. Energy consumption of every conventional desalination through the oxidation of the available organic materials in the
process anode chamber; this is due to the growth of anaerobic bacteria
Desalination units Energy consumption on the anode electrode that helps oxidise organic materials to
produce carbon dioxide. A proton and an electron are transmitted
MVC Only electricity needed and the energy through an external circuit. The cation and anion of the salt water
cost is accountable for about 50% of are separated in the middle chamber by the electrode in the
the product water cost.19 anode chamber and the electrode in the cathode chamber
[MSV, MED, and TVC] Two energy forms required for the through ion exchange membranes (IEMs); these membranes help
operation of thermal distillation in separating anions and their movement across the ion separa-
process (MSF, MED, and TVC): heat tion membrane (CEM) towards the electrode in the anode
with low temperature and electricity
power. The energy cost is
accountable for about 50% of the
product water cost.18
RO unit process Depends on two factors: (i) salinity of
the rate feed water, (ii) the recovery
rate. The capacity size of RO units
ranges between 0.1–
395 000 m3 day−1 and the plant
consumption is ranges from 3.7–8
kWh m−3,18.19
Seawater RO unit process Consumption range from 4–6 kWh m−3
for standard RO unit capacity
(24 000 m3 day−1).18,19
ED unit process Electricity consumption of an ED unit
from 0.7–2.5 kWh m−3 for low salinity
(< 2500 ppm) and from 2.64–
5.5 kWh m−3 for a salinity between
(2500–5000 ppm).19
Figure 1. Typical scheme of microbial desalination cell.
3

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www.soci.org HH Abd-almohi, ZT Alismaeel, MJM Ridha

chamber and the movement of cation across the ionic separation


membrane (AEM) towards the electrode in the cathode chamber,
where the electron accepted. O2 is an acceptor that is usually used
to reduce water. The proton is moved from the anode chamber to
the cathode chamber and combined with the oxygen and elec-
tron to form water. The potential difference between the anode
and cathode helps the electrons to flow in the system through
the external electrical circuit, and this can be operated in
self-powered mode, as shown in Fig. 1.25
The anode chemical equation is expressed as:

Active microorganisms +biodegradables organics


+ anaerobic condition ð1Þ
→nCO2 +4ne− +4nH +

The cathode chemical equation is expressed as:

O2 +4ne− +4nH + →2H2 O ð2Þ


Figure 2. SMDC configuration.
− −2
The removal of the anions (Cl and SO4 ) from the middle cham-
downside is that traditional sensors are manufactured with batte-
ber to the anode chamber through the AEM and the removal of
ries of a limited life, such as lithium batteries and others like them.
the (Na+1 and Ca+2) to the cathode chamber through the CEM
Therefore, the microbial desalination cell (MDC) has proven the
lead to the removal of 99% of the salt from the middle cham-
possibility of generating long-term energy for biosensors and
ber.21,26,27 To the best of the authors' knowledge, MDC was first
remote monitoring. It was found that the cost of manufacturing
studied in 2009 by a group of researchers from Tsinghua Univer-
sensors has decreased significantly and become environmentally
sity, China, in collaboration with Penn State University,
friendly.30 The desalination cell is also used to determine COD
United States. The researchers investigated the creation of a
levels in water pollutants.31 Controlling COD levels in water is
cubic-shaped MFC with three chambers instead of two and
important to maintain the level of pollution in rivers, groundwa-
divided by AEM and CEM clampers. The anode, desalination,
ter, and other parts of the environment. It is possible to use the
and cathode chamber volumes were 27, 3, and 27 mL, respec-
microbial desalination cell to sense, purify, and treat many com-
tively. By introducing carbon felt as an electrode material into
pounds (for example CaSO4, CaCO3, MgCO3, Ca(NO3)2,
the anode and cathode chambers, the volumes of the corre-
Mg(NO3)2, and MgSO4), but the microbial desalination cell still
sponding chambers decreased from 27 to 11 mL. A 5 mm graph-
needs periodic maintenance of the cell (in terms of washing the
ite rod was inserted into the carbon felt and a 1.6 g L−1 sodium
ion separation membranes, monitoring the acidity of the solu-
acetate solution was introduced to the anode chamber. The cath-
tions, etc.) for cell sustainability.31
ode chamber was fed with ferricyanide catholyte, whilst the desa-
lination chamber was filled with NaCl in varying quantities,
namely 5, 20, and 35 g L−1. The cell's exterior resistance was kept MDC CONFIGURATIONS
constant at 200. The results indicated a power output of
Stack structure MDC (SMDC)
31 W m−3 and a salt removal rate of 90% in a single desalination
The efficiency of removing salts from the desalination chamber
cycle. As the salt was withdrawn, it was discovered that the cell's
and the efficiency of electronic transfer can be improved by using
ohmic resistance grew from 25 to 970 at the conclusion of the
multiple pairs of electronic exchange membranes (IMS) between
cycle.24
the anode and the cathode chambers. This system is called SMDC.
Figure 2 contains several pairs. A series of separation films further
increases the separation of ion pairs from the brine for each elec-
APPLICATIONS OF MDC IN DIFFERENT tron that passes through the circuit.32 Table 3(a)–(d) summarises
INDUSTRIES the results of research conducted on SMDC.
The seawater content is not limited to the presence of Na+ and Cl− Choi and Ahn investigated five kinds of stacking connections for
ions in its composition. However, seawater presenting ions, such the treatment of household wastewater: series in parallel flow,
as HPO4−, PO4−2, Cl−, K+, and NH4+, is possible. When using real parallel in parallel flow, series in series flow, parallel in series flow,
wastewater, its content may consist of several complex com- and individual in series flow. According to the findings of their
pounds, such as CaSO4, CaCO3, MgCO3, Ca(NO3)2, Mg(NO3)2, and research, parallel electrode connections in sequence flow mode
MgSO4. The desalination process of seawater transfer of some of produced 15% to 20% greater power production and 80% to
these ions may lead to water contamination, as well as the pollu- 85% higher coulombic efficiency when compared with series con-
tion of IEMs. These results can be observed by the SEM test of IEMs nections.33 One of the issues with this design is the increase in the
and cation exchange membranes when treating domestic waste- IEM pairs in the stack that causes the MDC internal resistance to
water.28 Several MDC configurations, including (cMDC) configura- grow. The resistance inside the MDC stacks rises with the rate of
tion, have been proposed to overcome this IEM contamination simultaneous desalination. As a result, the use of stacks improves
(AEM, CEM).29 On the industrial side, the microbial desalination the charge transport efficiency and accelerates desalination.34
cell (MDC) has proven its efficiency in the production of biosen- Thus, the stacked MDC system should be designed to produce
sors, wastewater treatment, and water desalination plants. The the most energy from exoelectrogens while providing a
4

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Table 3. The SMDC and results found from the research

(a)

J Chem Technol Biotechnol 2022


NaCl concentration
in the middle External TDS
Configuration Anode/cathode material with volumes AEM & CEM Anolyte/catholyte chamber Resistance, (Ω) Power density removal Ref.
−1 −1 6 −2
Stacked MDC Graphite fibre brush, (Mill-Rose Lab Inc., USA) AMV/Asahi glass, Sodium Acetate (1 g L )/ 35 g L 10 1140 mW m 98% 34
with 30 mL/Carbon cloth as air-cathode Japan & Selemion Synthetic Seawater
(30% wetproofed, Eltek, Type B with 18 mL CMV

(b)

NaCl
Anode/cathode concentration in
material with the middle External Coulombic
Configuration volumes AEM & CEM Anolyte/catholyte chamber resistance, (Ω) COD removal efficiency (CE), % Power density TDS removal Ref.

Stacked MDC Carbon graphite DF120/Tianwei Xylose (1 g L−1) in 20 g L−1 101 000 60 ± 2–59 ± 2 49 ± 4–35 ± 1 860 ± 11 76% ± 1–97% 32
fibre brushes with Membrane & 50 mmol L−1 mW m−2 ±1
28 mL/Carbon Ultrex PBS/50 mmol L−1
cloth as air- CMI7000/ PBS buffer
Broad-ranging review: configurations, membrane types, governing equations

cathode (30% wet Membra ne


proofed, BASF, International
USA) with14 mL

© 2022 Society of Chemical Industry (SCI).


(c)

Anode/cathode material NaCl concentration


Configuration with volumes AEM & CEM Anolyte/catholyte in the middle chamber COD removal Power density TDS removal Ref.
−1 −1 −2
Stacked MDC Graphite fibre brush AMV/Asahi glass, Japan Sodium Acetate (1 g L ) in 50 35 g L 55.2 ± 1.7–62.8 ± 0.4 685 mW m 26% ± 0.5% 35
(Mill-Rose Lab Inc., & Selemion CMV mmol L−1 PBS/Synthetic Seawater
USA) with 160 (35 g L−1 NaCl)
www.soci.org

mL/Carbon cloth as
air-cathode30% wet
proofed) with 53 mL

wileyonlinelibrary.com/jctb
5
www.soci.org HH Abd-almohi, ZT Alismaeel, MJM Ridha

significant decrease in the system's internal resistance. If more


than one chamber is used between both poles, the pH imbalance

Ref.

31

36
between the anode and the cathode chambers may also affect
MDC efficiency.35
Shehab et al. discovered that its anode chamber pH inside the
SMDC structure dropped from about 7.03 to 6.30, and the cathode
desalination rate)

chamber pH increased from around 7.40 to 11.60.36


−1

90.8 ± 8.3
TDR (total

In another article by Qu et al.,35 they found that extending the


25.2 mg L

mg h−1
salt solution's hydraulic retention period from 1 to 2 days when
using four hydraulically linked MDCs improved salt removal rates
from about 76% to 97%; meanwhile. the coulombic efficiency
declined from about 49% to 35%. This finding shows that increas-
ing the number of MDC units may improve desalination
efficiency.
TDS removal

According to the requirements of SMDC's alternate AEM and


99.4%

CEM stacks, when compared with a standard MDC reactor, the


desalination rate increases by 40%. Furthermore, the charge
transfer that is efficient for energy recovery and ionic pair separa-
tion have been improved.35

Recirculation MDC
resistance,
External

1–1000

The pH imbalance in the anode chamber is caused by the ion sep-


10

aration membranes. As a result, these membranes were blocked,


leading to the non-transfer of protons to the cathode chamber,
which in turn caused the production of hydroxyl because of the
reduction reaction and pH imbalance.24,37,38 The buffer that is
NaCl concentration in

added in the anode and cathode chambers of the MDC system


the middle chamber

may be financially costly. Thus, a technique known as re-


−1

5 g L−1

circulation MDC (rMDC) has helped reduce the anolyte and cath-
20 g L

olyte without using buffer (Fig. 3) by successively recirculating


the cathode and anode chamber solutions in the cell for pH neu-
tralisation. New studies have shown the difference in the produc-
tivity of rMDC and other cells that produced rMDC cells after
adding 50 mmol L−1 of phosphate buffer solution (PBS) and gave
Potassium phosphate

30% greater power density. Another study added 25 mmol L−1 of


(2 g L−1)/Phosphate
Anolyte/catholyte

Phosphate buffered
Sodium Acetate

PBS and produced a 53% increase in power density. Therefore,


(100 mmol L−1)
Buffer solution
salts solutions
Sodium acetate
(1.64 g L−1)/

increasing the buffer solution concentration does not always


improve power density, and an optimal buffer concentration
should be provided. Recirculation also improved the desalination
performance by 48% and 13% for the 25 and 33 mmol L−1 PBS
solutions, respectively.38
Kim and Logan studied the possibility of exchanging oxygen
Membrane & Ultrex

with valuation hydrogen to improve the coulomb efficiency of


CMI7000/Me brane

the cell. One of the most important things that must be empha-
AEM & CEM

International
DF120/Tianwei

sised is that the recycling process must happen in very thin tubes
to avoid the appearance of equal potentials in the anode and
cathode chambers.32 Table 4 summarises the results on rMDC.

Microbial electrolysis desalination cell (MEDC)


The multi-chamber MDC in Fig. 4, for which several configurations
Carbon brushes (Gordon
Anode/cathode material

Commerce, CA, USA)/


Carbon felt as bioanode
with 21.1 mL/Carbon
cloth as air-cathode

Eltek, Type B, BASF)

have been proposed, provides energy production, wastewater


Brush Mfg. Co. Inc.,
(30% wetproofed,
with volumes

desalination, and useful by-gas production. A system named


Carbon cloth

microbial electrolysis desalination cell (MEDC), which consisted


with 7.1 mL

of MDC coupling with microbial electrolysis cells (MEC), was pro-


posed and helped provide useful chemical products. In 2010,
Table 3. Continued

Luo et al. and Mehanna et al. carried out the first research that clar-
ified the principle of MDC, where the system consists of three
chambers (anode, desalination, and cathode). The anode cham-
Configuration

Stacked MDC

Stacked MDC

ber is separated from the cathode chamber by AEM, and the cath-
ode and desalination chambers are separated by CEM. The results
obtained are presented as follows: the desalination percentage
(d)

was 68% (20 g L−1 NaCl) and 98.8% (10 g L−1 NaCl), and the
6

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Broad-ranging review: configurations, membrane types, governing equations www.soci.org

resistance due to the aggregation of dissolved solids, they must be replaced


e- frequently.46,47 In 2012, Forrestal et al. proposed the cMCD sys-
e-
tem, where the MDC system was combined with CDI (capacitive
deionised), which was inserted in the form of adsorptive activated
carbon ACC as electrodes and CEM between the middle chamber
NaOH H++O2 and the cathode chamber to obtain 69.4% of the products of salt
Co2
H2O + NaCl Cl - separation of the adsorbed ions and without increasing the salts
in the cathode and anode chambers.27 Here, the ions are trans-
ferred from the middle chamber to the cathode chamber and

Sea water
AEM

CEM
H+ are kept in electrical double layers. The transfer of ions from the
desalination chamber prevents them from entering the anode
HCl H2O and cathode chambers, thus helping reduce the pH imbalance.
organic This work obtained results that were 18 times higher than those
Na+
maers obtained using conventional capacitive deionisation processes.46
Some research has been conducted on the establishment of the
anode
MDC-MCDI system, and this has assisted in treating the liquid
waste generated through MDC. The reduction in energy con-
Air Cathode sumed by MCDI was advantageous for the system, which was pro-
pump
vided with an energy source through a different group of MDCs
Figure 3. Recirculation microbial desalination cell (rMDC). whose connection is in series or in parallel. The results were
obtained with the desalination rate as high as 3.7 mg h−1 in paral-
lel connection.48
Stoll et al. used an MCDC plant to process shale gas generated
amount of hydrogen produced spontaneously was 0.16 and
water while also removing salt from salt water. This batch micro-
1.5 m3 m−3 day−1, respectively.38,39 The system was developed
bial reactor removed 6.4 mg of organic matter per hour and desa-
by introducing a device called microbial electrolysis and chemical
linated at 0.036 g salt per gram carbon electrode.49
production cell (MEDCC), thus inserting a bipolar membrane
Capacitive MDCs make use of the capacitive and deionisation
between the AEM and anode chamber. The device must be
principles. These essential concepts must be understood.
inserted to treat the pH imbalance in the system that resulted
Double-layered capacitors are formed on the surface of the elec-
from the introduction of ion separation membranes. The ion
trodes and salts are removed from electrodes on a continuous
migration from the desalination chamber to the anode chamber
or periodic basis. Ion migration is made less difficult when the pol-
and cathode chamber resulted in a reduction of the pH in the
lution of the electrodes decreases. A total of 69.4% of the salinity is
anode chamber and an increase of pH in the cathode cham-
removed.48,50 Table 6 summarises the results on capacitive MDCs.
ber.40–42
The MEDCC consist of four chambers: anode, acid production, Upflow MDC (UMDC)
desalination, and cathode chambers. H+ ions are separated from
The system (Fig. 6) consists of a tubular unit separated by an IEM.
the anolyte to the acid-producing chamber and form the acid.
The inner cavity is filled with graphite particles, which help
OH− moves from the acid-producing chamber to the anolyte,
increase the surface area for oxidation processes and microbes
and this process neutralises the pH of the anolyte solution.43
by keeping them in suspension to help oxidise organic materials
The membrane ion separation (AEM-CEM) BPM was used
with higher efficiency. It is replacing the anode chamber sur-
between the anode chamber and the desalination chamber (first
rounded by a tube with anion and cation exchange membranes,
type) or between the cathode chamber and the desalination
which represent the desalting chamber and the cathode, respec-
chamber (second type), and is called BPM - AEM - CEM or BAC
tively. This design helps increase the surface area for saline water
mode. Chen et al. obtained a 43% increase in desalination rate
treatment.51,52 In this system form, the cathode chamber was
with an estimated value (0.58 mmol h−1) with the use of AC mode
replaced with a carbon cloth around the reactor that surrounded
and 1.5 mm membrane space.44
the desalination chamber, which consisted of a mixture of plati-
In addition, MDC can be combined with a metal reduction reac-
num and carbon. The flow of saline water enters from the bottom
tion to aid in the separation of heavy metals present in wastewa-
of the system and comes out desalinated at the top. The water can
ter. For example, An et al. used a four-chamber MDC, which was
be desalinated with an efficiency of 100% using hydro osmosis
achieved by using a membrane (AEM) between the cathode
technology with UMDC. The UMDC system is one of the most suc-
chamber and the (CEM) membrane to avoid the rest of the cham-
cessful systems in controlling the pH imbalance.52–54
bers; the copper (II) was treated in industrial water in the cathode
Jacobson et al. studied the possibility of power generation and
chamber at a removal rate 0.941, the maximum removal of salts
continuous water desalination using another configuration of
from the desalination chamber reached 43.9%; while the highest
the microbial desalination cell system (UMDC), using synthetic
current density was 2 A m-2-.45 Table 5 summarises results in half
wastewater (Phosphate buffered Sodium Acetate) with 500 mL
cell coupled MDCs.
and acidified water with 350 mL as anolyte and catholyte solu-
tions, respectively; the initial TDS concentration in the middle
Capacitive MDC chamber was 30 g L−1, the maximum power obtained was
Na+ and Cl− are transported from the desalination chamber to the 30 800 mW m−3, and 99% of water desalination was achieved.55
cathode and anode chambers through the ionic membranes to Jacobson et al. used synthetic wastewater containing acetate
precipitate in the anolyte and the catholyte (Fig. 5). Considering (35 g L−1) with 1.9 L and acidified water as anolyte solution and
that the use of solutions in other experiments may be impossible catholyte solution in the system, respectively; the middle
7

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8

Table 4. Summarizes rMDC and the result of the researches

wileyonlinelibrary.com/jctb
Coulombic
Anode/Cathode Desalination External efficiency Total desalination COD Power Desalination
Configuration material with volume AEM & CEM Anolyte & catholyte chamber resistance,ꭥ (CE), % rate (TDR) removal, (%) density efficiency Ref.

rMDC Carbon cloth DF120/Tianwei Xylose (1 20 g L−1 1000 22 ± 2, 25 — 79 ± 4, 931 ± 34 ± 1, 37 ± 40


as air-cathode Membrane & Ultrex g L−1) in 25 or ±1 78 ± 3 29 2
(30% wet CMI7000/Membra 50 mmol L−1 PBS & mW
proofed, ne International 25 or 50 mmol L−1 m−2
BASF, US) with 14 PBS
mL/Carbon cloth
www.soci.org

as air-cathode
(30% wet
proofed,
BASF, US) with 14
ml
rMDC Activated Carbon 1.8 mol kg−1, Phosphate buffered 10 g L−1 150, 100, 124.4 95.4 mg h−1 — 11 800 93.4 41
granules Shanghua, China & Sodium 50 and 10 mW m−3
Weishimei 2.0 mol kg−1, Acetate
Environmenta Shanghua, China (1.64 g L−1) &
l Technology Co., Ltd., Phosphate

© 2022 Society of Chemical Industry (SCI).


China) with 675 buffered
mL/Activated sodium
carbon granules as bicarbonate
biocathode + ammonium
(Weishimei chloride +
Environmental
Technology Co.,
Ltd., China) with
338 mL

J Chem Technol Biotechnol 2022


HH Abd-almohi, ZT Alismaeel, MJM Ridha
Broad-ranging review: configurations, membrane types, governing equations www.soci.org

resistance anolyte solution. A bipolar membrane can be usually added next


e- to the anode chamber, thereby forming a fourth chamber that
e-
NaOH helps reduce the pH in the system.32,59 The main advantages of
using a bipolar membrane are its long life duration, and the min-
imal voltage drop and resistance when separating the water;

Na+
H++O2 increasing the ion-exchange membrane capacity of a membrane
Na+
N N
would increase the desalination efficiency from 50% to 63%,
improve the anode pH balance, and yield columbic effectiveness
Sea water

Sea water
ranges from 62% to 97%. The disadvantage of using a bipolar
BPM

AEM

CEM

BPM

AEM

CEM
membrane for MDC is that, in order to divide water into hydroxyl
H2O ions inside the anolyte and H+ in the catholyte, an external power
supply is needed, thus bringing a high cost to this type of MDC.5,53
Cl-

Cl-

OH- H+ OH- H+ Decoupled MDC


This form of MDC was developed to solve the problem of chang-
ing the volume of liquid needed in the anode or cathode cham-
HCL bers or to avoid the need for maintenance. The anode and
cathode units are placed in a saline solution instead of being
Figure 4. Microbial electrolysis desalination and chemical- placed in the chambers. In addition to collecting current, a
production cell.
stainless-steel mesh is used and carbon is wrapped with cloth as
the electrode to serve as a support structure.60
chamber used real seawater, the maximum power obtained was Zhang et al. studied the possibility of improving the MDC: car-
38 900 mW m−3, and 73.8% of water desalination was achieved.51 bon fibre felt was used as anode and cathode electrodes, as well
as acetate-laden synthetic wastewater with phosphate buffer
(90 mL) with 100 mL and 50 mmol L−1 potassium ferricyanide
Osmotic MDC
with 100 mL as anolyte and catholyte solutions in the system,
The MDC (Fig. 7) was developed with the principle of forward respectively. The maximum power obtained was 360 Mw m−2
osmosis (FO) by replacing the ion separation membranes with with 95–98% of water desalination.61
FO membranes similar to those used in the ion separation process Shehab et al. tried to improve the COD removal in the anode
from the desalination chamber to the anode and cathode cham- chamber and increase the desalination efficiency: phosphate
bers.32,56 This MDC configuration achieved wastewater treatment buffered with sodium acetate (1 g L−) with 30 mL and brackish
by transferring water from the anode chamber to the desalination water with 18 mL were used as anolyte solution and catholyte
chamber and from the cathode chamber to the desalination solution in the system, respectively. The maximum COD removal
chamber. This process decreases the concentration of salts in obtained was 78% in the anode chamber and93–100 % TDS
the desalination chamber. This method still contains many chal- removal in the middle chamber.36
lenges that should be solved, as its overlays are subject to fouling
and can increase the internal resistance of the system. Ion-exchange resin coupled MDC (IER-MDC)
According to Pardeshi et al., the efficiency of an FO membrane The MDC configuration in Fig. 9 helped reduce the ohmic resis-
consolidated inside an MFC that uses dextrose as a source was tance to improve the efficiency of MDC in terms of improving
investigated, and they discovered a power density of wastewater treatment and power production in the system. The
27.38 W m−3.57 addition of mixed anions and cation exchange resins in the
Zhang and He created a two-membrane bio-electrochemical MDC desalination chamber resulted in the conjugation of ion
reactor with a hydraulically linked OsMFC and MDC. While using exchange (r-MDC). These ion exchange resins have given high
the diluting and desalination possibilities in OsMFC and MDC, this conductivity even in low salinity water.24,62,63 The low NaCl con-
combination demonstrated a considerably higher desalination centration (2–10 g L−1) increased the desalination rate by 1.5–8
efficiency of 95.9% and a power output of 0.160 kWh m−3.58 times, and the resistance decreased to 3–4.7 Ω when compared
Zhang and He used sodium acetate with sodium bicarbonate with conventional MDC resistance (5.5–12.7 Ω), as studied by
and sodium chloride as anolyte solution, potassium ferricyanide Morel et al.64 Each MDC configuration helps overcome one of
as catholyte solution, and 10 g L−1 initial concentration of NaCl the obstacles that reduce the desalination rate and energy pro-
in the middle chamber. While using the diluting and desalination duction in MDC systems.
possibilities in OsMFC, this combination demonstrated a consider-
ably higher desalination efficiency of 57.8%.50 MDCs in hybrid systems
The efficiency of water desalination can be improved in different
Bipolar membrane MDC ways, such as by combining several desalination methods (e.g.,
The system (Fig. 8) consists of an MDC with an anion-selective RO, FO, or electrodialysis (ED)). The FO cell depends on the move-
dipolar membrane and cation-selective membrane together as a ment of water molecules from the permeable membrane due to
single membrane. The increase in the migration of Na and Cl ions the difference in concentrations between the feeding solution
from the middle chamber of the system helps increase the desa- and the intake solution.65 In an FO-MDC system, an MDC may
lination of water in the middle chamber. These membranes are function as an after-treatment cell because the intake solution
always exposed to organic and biological fouling that increase can flow from the FO cell to the MDC.66,67 This phenomenon
the internal resistance of the system. One of the reasons may be means that a better MDC/FO cell combination may be achieved
that the dirt on the membranes is exposed to wastewater in the by increasing the feed solution flow rate, lowering the HRT, and
9

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10

Table 5. Summaries of the half cell coupled MDCs and of different research results

Acid production/
Desalination Produced chemical External alkali
chamber & production resistance/ production COD Power density/
Anolyte/catholyte with Anode/cathode material fed NaCl volume/ coulombic chamber removal, desalination
Configuration volumes and AEM/CEM material concentration recovery, (%) efficiency (CE), % electrolyte (%) efficiency, (%) Ref.

wileyonlinelibrary.com/jctb
MEDC 50 mmol L−1 Carbon cloth (type A; 5 or 20 g L−1 H2 10/ — 38 ± 3, 54 ± 4 — 42
Phosphate buffer ETEK)/Carbon cloth & 48 ± 4,
solution/50 mmol L−1 (type B-1B; ETEK) (6.5 ± 1.4) mL/44 38 ± 3
PBS buffer And ± 10, (2.7 ± 1.0)
AMI-7001/CMI-7000 mL/15
±4
MEDC Phosphate buffered Graphite Brushes 10 g L−1 H2 10/— — — — 38
Sodium Acetate (Golden brush, &
(1 g L−1) with CA)/Stainless 48.7 mL/72
25 mL/50 mmol L−1 steel mesh (Type 304,
www.soci.org

phosphate buffer with 36 mL McMaster, IL)


&
AMI-7001/CMI – 7000
MEDCC Phosphate buffered Graphite brush/Carbon 10 g L−1 (10 Acid and 10/— 10 mL of 10 62–97 • /− 47
Sodium Acetate cloth with Pt (30% Wet mL) Alkali g L−1 NaCl
(1 g L−1) with 30 mL/30 mL proofed) &
of 10 g L−1 NaCl with & 2.1 ± 0.7
30 mL Ultrex AMI-7001/Ultrex mmol
CMI-7000 (AP)/75,
206 ± 0.9

© 2022 Society of Chemical Industry (SCI).


MEDCC Phosphate buffered Graphite 35 g L−1 Acid and 10/>95% 14 g L−1 of NaCl — —/63% 47
Sodium Acetate Brush/Carbon Alkali solution
(1 g L−1) with 30 mL/ cloth (30% wet proofed) &
Deionized water with & 0.079 ±
15 mL UltrexAMI-7001/ 0.006
UltrexCMI-7000 mmol h−1 (AP),
0.13
± 0.02 mmol h−1
(A’P)
MEDCC Sodium Acetate Carbon brush/Fabricated 35 g L−1 Acid 10/113 ± 9 1 g L−1 of NaCl — — 49
(1 g L−1) in 50 using Dong et al. & Solution
Mm PBS with 336 mL/1 g L−1 method (Dong et al., —
of NaCl solution with 2012 & Ultrex AMI-
1 g L−1 7001, MI, USA/Ultrex
CMI-7000, MI, USA

J Chem Technol Biotechnol 2022


HH Abd-almohi, ZT Alismaeel, MJM Ridha
Broad-ranging review: configurations, membrane types, governing equations www.soci.org

resistance was coated with electrodes, a process that is inexpensive and


straightforward. As a result, the efficiency of S. oneidensis was sig-
nificantly improved, and the current density in MDC was nearly six
times greater than that of an unprocessed electrode.72 Using
rGO/SnO2-CC hybrid nanocomposite electrode as an anode, the
power density of 1624 mWm−2, which was 4.8 times more than

Na+
Acetate N Ferri cya nide
that of a unprocessed electrode, was attained.73 An increase in
specific surface area was largely responsible for the improved per-
Cl-
formance. The hybrid composite also improved bacterial adhe-
AEM

CEM
Co2 sion and electron transfer efficiency due to greater
biocompatibility. Amongst the many functions of the hybrid elec-
Ferrocya nide trode system, the Ni nanoparticles can be catalysts for the oxygen

Na+
Cl-

N reduction process at the cathode and aid in the transmission of


microbes electrons from Escherichia coli.74 Exoelectrogenic bacteria adhe-
OH- H+ OH- H+
Sea water sion has been improved using a composite electrode that consists
of reduced graphene oxide–manganese oxide coated on carbon
Figure 5. Capacitive microbial desalination cell. felt (rGO-MnO2-CF). This electrode attained a power density of
2065 mW m−2. The greatest power density of 2143 mW m−2 is
generated by using stainless-steel fibre felt (SSFF) coated on a thin
increasing NaCl concentration initially. Yuan et al. studied the effi- graphene film as an anode material in MDC,75,76 Table 7 summa-
ciency of COD removal and desalination when placing the MDC rises the electrode materials used in MDC and MFC for bioelectric-
before and after the FO cell. MDC-OF achieved 93% of COD ity generation.
removal and 99.4% TDS removal; OF-MDC achieved 65.4% of
TDS removal and 90% of COD removal.66 MEDCC is an MDC con- Types of membrane
figuration used with RO cells to desalinate seawater with acid pro- Generally, IEMs consist of arrays on which groups of ions (which
duction. RO cells purify water by forcing water molecules to move are either positively charged or negatively charged) are attached
in the opposite direction of natural osmosis.68 Luo et al.65 studied (Fig. 11). These membranes are either anion exchange mem-
the performance efficiency of the RO-MEDCC system by examin- branes (AEMs) or cation exchange membranes (CEMs).77 The most
ing two different sizes of membranes (15, 1.5 mm) inside MEDCCs: important thing that distinguishes MDC from MFC is the use of
RO-MEDCC provided 79% and 86% desalination rates, 4.1 and ionic separation membranes, which help transfer ions (anions
7 A m−2 current densities, and 77% and 127% of CE, respectively. and cations) from the desalination chamber to the anode and
MDC treatment can be used as a pre-treatment of water before cathode chambers. Zuo et al. used a cellulose acetate membrane
the ED cell. An ED cell works to desalinate seawater by applying in an experiment and achieved 62% of TDS removal.78 The main
an external electrical voltage to force the charges (anion, cation) compounds that can be removed by IEM in the MDCs are sum-
to move towards the anode and cathode electrodes.69 The four marised in Table 8. The IEM prevents large bacteria cells from
phases of procedure can possibly take place in four MDCs with transferring (for example, Nitrosoarchaeum limnia and Photo-
five chambers each in the MDC-ED system. Once the stages have trophic eukaryotes).79 One of the biggest problems caused by bac-
been linked, an ED cell is added to the experiment. MDC-ED teria is biofouling, which prevents the maximum performance of
achieved 92.2% of COD removal, 76.5% removal of saline in MDC for an extended period. The hydrogen sulphide produced
MDC, and 30.4% saline removal in ED cell.70 by bacteria (Pseudomonas and Desulfovibrio) causes corrosion in
the ultrafiltration membrane. All these problems call for mainte-
nance during the operation process. One of the main H2O dissoci-
MDC PARTS ations in MDC during operation in the current density being low.
Types and shapes of electrodes
Electrodes in the anode and cathode chambers are some of the Catholyte and anolyte solution
most important parts of the MDC system. Basic materials, such Given that the toxicity of the solutions used in the cathode cham-
as carbon felt electrodes, carbon cloth electrodes, carbon brush ber prevents the development of the system, the catholyte solu-
electrodes, graphite granule electrodes, graphite fibre granules tion is the most important obstacle in the development of the
electrodes, graphite rod electrodes, and carbon fibre felt, are gen- MDC system. Therefore, some research has been conducted to
erally used as electrodes in MDC (Fig. 10).71 address this problem by reducing the use of a concentration of
The electrodes used in the MDC system should be very conduc- PBS, which is a non-buffer saline solution and biocathode.80 A
tive, non-corrosive, have a large specific surface area (area per vol- total of 0.1 M phosphate buffer was used as catholyte, which
ume), and be a highly porous, non-fouling material that is exhibited 9.87% efficiency in removing COD of the salts from
inexpensive and can be easily made and scaled to larger sizes.71 the wastewater.81 Sodium percarbonate solution was used with
Nanostructured materials, including 3D carbon black, carbon a concentration of 0.05 M as the catholyte, and it provided a
nanotubes (CNT), porous carbon, graphene, and polyanilines, COD removal efficiency of 14.74% of TDS.82 The wastewater in
are beneficial for modifying or implementing standard carbon- the MDC anode chamber contains many components that may
structured electrode materials, such as graphene and polyani- be harmful in high concentrations (e.g., boron,83 phenol,84,85
lines. The alteration of anodes with metals or their oxide-based nickel, lead,86 arsenic)87. Many types of wastewater, including
nanocomposites reduced ohmic loss and improved bacterial cell those produced from petroleum refining processes and wastewa-
adherence. For example, a new anode made of Fe3O4, with a ter from paper factories and wetlands, can be treated.88,89 Don-
power density of 830 mW m−3, was produced recently. Hematite
11

nan dialysis (DD) was used to remove boron by adding

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12

Table 6. Summaries of capacitive microbial desalination cell and research results

Coulombic Total COD Power density/


Anode/cathode material and Desalination chamber efficiency External desalination removal, desalination
Configuration Anolyte/catholyte with volumes AEM/CEM Material fed NaCl Concentration (CE), % resistance rate (TDR) (%) efficiency, (%) Ref

wileyonlinelibrary.com/jctb
−1 −1
MDC-MCDI Phosphate buffered Sodium Acetate Carbon felt/Carbon felt and 10 g L — 200 3.7 mg h — —/74.4 45
(1.6 g L−1)/Phosphate buffered AMI 7001S; Membranes
Sodium Acetate (1.6 g L−1) International, USA/CMI-7000S;
Membranes International, USA
cMDC Phosphate buffered Sodium Acetate Graphite Brush (Golden Brush, CA)/ Salt solution comprising — — — — —/74.4 54
(1.6 g L−1) with 23 mL/Phosphate Carbon cloth as air-cathode (30% of Sodium Chloride,
buffered Potassium Chloride (10 wet Proofed) and Assembly: Sodium Phosphate
g L−1) with 27 mL CEM/ACC/Ni or Cu (CMXSB, Astom and Sodium
Corporation, Japan; activated Biphosphate
carbon cloth (McMaster Carr, IL);
www.soci.org

Ni or Cu mesh current)/Assembly:
(Ni or Cu/ACC/CEM/Ni or Cu)
mesh current; activated carbon
cloth/CMXSB, Astom Corporation,
Japan)
cMDC Phosphate buffered Sodium Acetate Activated Carbon Cloth (ACC) 10 g L−1 — 1 — — —/69.4 25
(1.6 g L−1) with (Chemviron Carbon, UK/Same as
23 mL/50 mmol L−1 Ferricyanide anode Electrode and Assembly:
Solution with 27 mL AEM/Ni or Cu/ACC (AMX, Astom
Corporation, Japan)/Ni or Cu

© 2022 Society of Chemical Industry (SCI).


mesh current collector/activated
carbon cloth/Assembly: CEM/Ni or
Cu/ACC (CMX, Astom Corporation,
Japan)/Ni or Cu mesh current
collector/activated carbon cloth
MCDC with CDI Phosphate buffered Sodium Acetate Carbon fibre brush as bioanode Produced water — — — — —/70 55
module inside DC (1.6 g L−1) with 23 mL/Sodium (Gordon Brush, CA)/Carbon cloth
phosphate buffer as air cathode (30% Teflon
coated) and No AEM used.
Another CEM was inserted at
place of AEM./CMX-SB, Astom
Corporation, Japan

J Chem Technol Biotechnol 2022


HH Abd-almohi, ZT Alismaeel, MJM Ridha
Broad-ranging review: configurations, membrane types, governing equations www.soci.org

wastewater effluent

sea water effluent


anode

Reci rculaon
Ca thode

s eawater influent
wastewater influent

Figure 6. Upflow microbial desalination cell.

Organics Cl -
Ferri cya nide
seawater

CEM
FO

Figure 9. Ion-exchange resin coupled microbial desalination cell.

Na+ Ferrocya nide


CO2 H2O Axenic Pseudomonas aeruginosa has been used alone in an
a node ca thode anode chamber of MDC that can remove 94% of phenol, 77% of
COD, and 64% of TDS.85
Figure 7. Osmotic microbial desalination cell.
Pseudomonas putida with sludge for phenol removal eliminated
82% of phenol, 70% of COD, and 68% of the TDS.84
Nickel and lead residues from industrial processes may affect
the environment. Mirzaienia et al.86 studied the conditions of
V nickel and lead removal and found that 74.5% of nickel and
75.1% of lead were removed for a maximum of 100 mg L−1
removal.
Malakootian et al.87 studied the removal of arsenic (a highly
toxic compound) from wastewater by using an MDC that
Organics Cl - achieved 75% of arsenic removal in ideal conditions. However,
Ferri cyanide in real wastewater, the ammonia affected the anaerobic digestion
and the performance of the desalination process.90
Acid chamber

seawater
AEM
BPM

CEM

Nannochloropsis salina algae can be used in the cathode cham-


ber and improve the TDS removal. This type of algae results in
Ferrocya nide 45% removal of NaCl with 35 g L−1 initial concertation, 79%
CO2 Na+
OH- H+ removal of NaCl with 17.5 g L−1 initial concertation, and 46%
a node cathode removal of NaCl with 8.25 g L−1 initial concertation and 90% of
nitrite.91,92
Figure 8. Bipolar membrane microbial desalination cell.
As shown in an experiment, Debaryomyces hansenii yeast has a
desalination rate of 29.17% for salty water with NaCl when the
substrate utilised was 1.5 times as much as the bacterial culture
sodium hydroxide as catholyte (boron is considered toxic at a in the anode. It may also help degrade organic materials in the
concentration of 2.5/L in water), and this resulted in the anodic chamber to increase the desalination rate.93
removal of 20–25% of boron. Before and after the MDC used In the anolyte solution, many microorganism cells can oxidise
Donnan dialysis, 42–40% and 30–40% of boron were organic materials in wastewater in the anode chamber of MDC.
removed,83 respectively.
13

Studies are still focused on identifying the organism that provides

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www.soci.org HH Abd-almohi, ZT Alismaeel, MJM Ridha

Figure 10. The basic materials of the electrode.

the best oxidation or reduction processes for organic materials to The process of transferring electrons from living organisms takes
produce electrons in MDC. The following challenges must be con- place in three ways (Fig. 12): Firstly, electrons are transferred to
sidered. The growth of living organisms under anaerobic condi- the growth medium, to the anode, and then through the external
tions, since the presence of any oxygen during the growth of circuit to the cathode. Secondly, electrons are transmitted
living organisms is toxic and discourages the growth of microor- through a terminal protein attached to the outer surface of the
ganisms.82 When treating real wastewater, difficulties are encoun- microorganism cells (Geobacteraceae species contains cyto-
tered in obtaining the required bacterial growth during the chromes attached to the cell surface responsible for transfer elec-
treatment process because microorganisms other than the added trons, while Shewanella oneidensis has the same cytochrome;
organisms can also grow and because the growth of organisms nevertheless, an anaerobic condition is essential).94 Thirdly, the
depends on the imprinting of microorganisms on the wastewater. anode attaches directly to the cells, transferring electrons without

Table 7. Summary of electrode materials used in MDC and MFC for bioelectricity generation

Anode Cathode Power density mW m−2 Reference

Graphite fibre brush Iron phthalocyanine/Pirlindole/Carbon 799 ± 41 84


nanotubes (FePc/PID/CNT)
Carbon mesh treated with ammonia Carbon cloth 1015 85
Ni-ACFs/CNFs Ni-ACFs/CNFs 1145 ± 20 81
Carbon fibre brush Iron-rich nanoparticle encapsulated, 1227 86
nitrogen doped porous carbon materials
Alumina and nickel nanoparticles-dispersed Polymer-Alumina and nickel nanoparticles 1270 ± 30 87
multi-scale web of activated carbon fibre dispersed multi-scale web of activated
and carbon nanofibers carbon fibre and carbon nanofiber
Porous carbon with a defined pore size Air cathode 1606 88
GO-SnO2 Pt rod 1624 80
Graphite plates Graphite plate 1771 89
Reduced graphene oxide (rGO) and Carbon brush 2065 90
manganese oxide (MnO2) coated on
carbon felt
Carbon brush Carbon cloth 2110 91
Graphene coated stainless steel fibre felt Carbon felt 2142 92
Carbon felt Fe-N-C 2437 93
Nitrogen-depend porous carbon cloth Carbon brush 2777.7 94
3D-carbon black/stainless steel fibre felt Graphite plate 3215 ± 80 12
14

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Broad-ranging review: configurations, membrane types, governing equations www.soci.org

Figure 11. Mechanism of anion-exchange membranes.

the need for an intermediary when using a cell immobilisation ability to transfer electrons to the anode electrodes without
method. The microorganisms that produce an electrical current the need for an electron acceptor. The age and thickness of
by oxidising the substrate and transferring it through the outer the biofilms are amongst the most important factors that affect
circuit to the cathode chamber are called exoelectrogenic. The the production of electrical energy and the treatment of waste-
high-performance efficiency of MDC depends on the optimal water because it can prevent the penetration of the
growth of a microorganism.Exoelectrogenic bacteria were found
in the sludge of a wastewater facility and biogas plant. Exoelectro-
genic bacteria use glucose and wastewater as carbon sources
(substrate) in MDC.95–99. Bacteria use their metabolic process to
oxidise the substrate and produce power. The quantity of gener-
ated power is determined by the choice of exoelectrogen and
the integration technique in the MDC system.33

Biofilm in MDCs
In the anode chamber, electrons are produced from the avail-
able bacteria in wastewater that produce electrons directly
without the need for an intermediary because they convert
the organic materials in the wastewater into electrical
energy.100 Another characteristic of these bacteria is their

Table 8. Compounds and wastewaters that can be removed by


MDCs

Compound or
wastewater target of
removal Removal, % Ref.

Boron 20–30% 132


Phenol 62–94% depending on the 134, 133
culture used in the anode
chamber
Nickel 74.5% 135
Lead 75.1% 135
Arsenic 75% 99
Ammonia 88% 136
Nitric 90% 91, 139
Sodium 84.2% 140
Chlorine 58.25% 140
NaCl 8.92–79% depending on the 93
anolyte and catholyte
Salts 9.87–32% depending on the 130
type of buffer used in the
anolyte and catholyte
Petroleum refinement 19.9% 141, 11
wastewater Figure 12. The process of transferring electrons from living organisms
15

takes place in three ways.94

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www.soci.org HH Abd-almohi, ZT Alismaeel, MJM Ridha

Figure 13. Stages of biofilm formation on a surface.147

substrate.100 Figure 13 describes the growth of microorganisms acts as terminal acceptor, so that would be environmentally
on the electrode in the anode chamber. The first process of sustainable.4
accumulating microorganisms on the electrodes is the bonding
of microorganisms together through their adherence to a Biocathode
mucilage-like substance secreted by microorganisms.101 Here,
It has been discussed how the use of chemicals is harmful and
the sticky substance consists of polysaccharides and proteins
economically costly. In addition, they must be replaced periodi-
known as slime. Colonies form bound structures on the surface
cally, and they are not considered a sustainable source to be used
of the electrodes due to the suitability of the surface and to the
as catalysts or as catholytes in the MDC. The use of electrically
environmental conditions in the chamber, where the cells
active bacteria as a cathode can help collect electrons in the cath-
adhere to each other before they adhere to the electrodes. A
ode biofilm and improve the oxidation–reduction process
detached stage leaves behind a hollow mound that leads to
(Fig. 15). The density power production depends on the density
the termination of the biofilm. These stages can be detected
growth of biofilm, and biofilm growth is applied in the anode
in order using SEM analysis.102 Table 9 defines the microorgan-
chamber to produce more optimised cells that help reduce the
isms and the TDS removal in MDC is shown in Table 10.
start-up time. Table 11 presents the research that used the bio-
cathode as catholyte solution. Wen et al. investigated the bio-
cathode used in MDC with aerobic conditions, and the carbon
MDC CATHODIC TYPES felt that increased the voltage produced compared with that volt-
Air catholyte age produced by the air cathode. When biocathode was used, the
The chemical electron acceptor can be replaced with pure oxygen voltage produced in MDC 136 mV, 92% salinity removal, and
from a the broad range of sources. Since it is free and ecologically 96.2% coulombic efficiency.104–108
acceptable, oxygen from the air may be employed as an electron Depending on the type of terminal electron acceptor being uti-
acceptor in the cathode chamber (Fig. 14).103 Mehanna et al. used lized in the cathode chamber can be divided into aerobic and
(Pt/C) electrodes and the results obtained from the air cathode anaerobic cathodes. Under anaerobic conditions, oxygen is used
MDC showed a decrease in the water–salt conductivity to 43%. as an oxidant because of its availability and low cost.
On the other hand, it gave good results in producing the maxi- Bergel et al. used a seawater biofilm-covered biocathode in MFC
mum power density and columbic efficiency of 480 Mw m−2 and the results obtained showed a power density of 0.32 W m−2
and (68 ± 11) %, respectively.5 and a current density of 1.34 A m−2.109
Compared with the other catholytes used, the use of air cathode Meng et al built a biocathode for desalination, electricity pro-
in the MDC showed a slowdown in the kinetics of the oxidation– duction, and anodic sludge stabilisation. The anodic pH value
reduction reaction in ambient conditions and in the equipment was between 6.6 and 7.6,and it had ±1.14% and 40.74 ± 0.89%
required to maintain dissolved oxygen levels in the cathode desalination rates, initial NaCl concentrations of 5 and 10 g L−1,
chamber. This may be one of the most important reasons for and maximum power outputs of 3.178 W m−3 and 1.118 V in
using catalysts, such as platinum, to improve the oxidation and the open circuit.110
reduction processes. The main advantage of using air cathode Anaerobic conditions have been intensively studied to avoid
16

modification in the MDC is its high reduction potential. Oxygen the introduction of dissolved oxygen because the lack of

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Broad-ranging review: configurations, membrane types, governing equations www.soci.org

Table 9. Microorganisms used and their TDS removal in MDC

Microorganism type TDS removal, % Power intensity Ref.

Debaryomyces hansenii 55% 7.4 mW m−3 93


Mix anaerobic consortia 72.3% 1470 mW m−3 142
Anaerobic sludge from wastewater 74% 4060 mW m−2 143
Proteobacteria 55% 3600 mW m−3 27
Pretreated consortia 80.7% 348 mW m−3 144
Bacillus subtilis 62.2% 150 mW m−3 145
Sludge from wastewater 90.4% 30.85 mW m−3 146
Debaryomyces hansenii yeast 29.17% — 96
Nannochloropsis saline algae Depending on the compound removal — 96
(90% of nitrite removal) and 79% of NaCl
Pseudomonas putida with sludge 82% of phenol removal — 96
Axenic Pseudomonas aeruginosa 64% of NaCl removal and 94% of phenol removal — 96
Only sludge 94% of phenol removal — 133
Pseudomonas putida pure culture 65% of phenol — 134
Pseudomonas aeruginosa 91% of phenol — 133
mixed with sludge in anode

sufficient oxygen in the system may reduce its performance. Nev- Hydrogen production was improved to 0.63 m3 when compared
ertheless, anaerobic conditions have shown difficulty and delay in to the 0.08 m3 production by controlled electrode.115
the processes of separation and power production.111,112 Wen in 2012, Sharma in 2010 and Sun in 2012 studied a new
Microbial electrosynthesis, which transforms carbon dioxide technology to reduce the start-up costs of the anaerobic condi-
and water into valuable multi-carbon organic molecules, is one tions. To speed up the establishment of an anaerobic facultative
of the most transformational uses of electrography. In the litera- autotrophic biocathode, heterotrophic pre-enrichment was cre-
ture, many methods for creating biocathodes under anaerobic ated. By substituting H2 with the cathode as a source of energy
conditions have been published. One of the few ways established and electrons, acetogenic bacteria converted CO2 into organic
for producing anaerobic biocathodes that showed tremendous molecules. Initially, the heterotrophic enrichment of bacteria with
promise was the inclusion of hydrogen/organic chemicals to dextrose was conducted via a pre-enrichment technique that was
cathodes.113,114 also based on the facultative autotrophy of anaerobic microor-
In 2008, Rozendal et al. first investigated a novel anaerobic micro- ganisms. As a result, microbes were able to transition from being
bial biocathode system by MDC with a three-phase chamber that heterotrophic to autotrophic metabolic by supplying CO2 as the
depended on the concept of reversibility of hydrogenases. only source of electron uptake and carbon.107,116,117

Table 10. Summary of the MDC with chemical cathode and the results

TDS removal from


Anode/cathode Anode/cathode Anolyte/desalination/ External Power desalination
Type of MDC volume electrode AEM/CEM catholyte resistance density chamber (%) (Ref.)

Three 11 mL/11 mL Carbon DFI120 or Tianwei Sodium 200 2000 mW m−2 90 21


Chamber Felt/Carbon Membrane/Ultrex Acetate (1.6
MDC Felt CMI7000, g L−1)/5, 20 and 35
Membrane g L−1/Ferricyanide
International
Three — Carbon Cloth, AMI-7001 or Sodium 50–1000 480 mW/m−2 43–67 42
Chamber (BASF, NJ)/30% Membrane Acetate (1
MDC Wetproofed International or 2 g L−1)/(5 g L−1)/
Carbon Cloth + Experimental 50 mmol L−1 PBS
(0.5 mg cm−2 AEM or Aminated Buffer
Pt, 4 layers of Radel R-5500/
PTFE), (type CMI-7000 or
B 1B, E-TEK) Membrane
International +
Experimental
CEM Sulfonated
Radel R-5500
17

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www.soci.org HH Abd-almohi, ZT Alismaeel, MJM Ridha

ADVANTAGES AND DISADVANTAGES the slight decrease in voltage in periods of darkness and for the
significant lack of voltage drop. Moreover, the non-
OF MDC photosynthetic respiration of algae cells produces carbon dioxide,
The microbial desalination cell (MDC) has introduced a new concept
which is also an electron acceptor.119 Some studies showed that
for desalination processes: producing electrical power with high effi-
algae cells did not grow and divide due to the prolonged illumina-
ciency and removing COD from wastewater simultaneously. In addi-
tion. That is, the high intensity of illumination damages the chlo-
tion, it has proven its ability to remove salts and other ions (such as
roplast plates and disrupts the enzymes responsible for
boron, lead, nickel, etc.) from water, as well as its efficiency in remov-
inhibiting the growth of carbon dioxide. The growth rate of Duna-
ing COD from real wastewater (such as oil wastewater, industrial
liella viridis decreased to 63% with an increase in the intensity of
wastewater, etc.).81,86,87 However, one of the disadvantages of the
lighting at around 700–1500 μmol m−2 s−1.120,121
microbial desalination cell is the extra chamber that was introduced
into the system, which causes an increase in the internal resistance of
Effect of intermembrane distance
about 10 when compared to the MFC; in addition, the separation of
Increasing the distance between the ion separation membranes
salt ions in the cell led to an imbalance of pH in the cathode and
in MDC can affect the performance of power production and
anode chambers.118 One of the advantages of the MDC is that it is
desalination rate. A small distance provides a low resistance in
environmentally friendly if non-chemical catholyte solutions are
MDC and a large distance between the ion separation mem-
used. Extensive research and studies in the field of MDC have shown
branes leads to higher internal resistance in MDC, but the
different configurations and cathodic types of energy production
increased spacing of the ionic films provides more desalination
and wastewater treatment. Table 12 provides a summary of the ben-
volume. The effect of membrane distance (from 0.3–2.5 cm) was
efits and disadvantages of each of the MDC system configuration
investigated in terms of desalination efficiency; the results pro-
Table 13.
vided a desalination rate that is 12 times higher at a distance of
0.3 cm by 7 at a distance 2.5 cm and a concentration of 10 and
30 g L−1, respectively.60
FACTORS AFFECTING MDC OPERATION In later studies, reducing the distance between the membranes
EFFICIENCY led to high power density and improved the desalination and
Effect of illumination high recovery of freshwater.122,32
The MDC system (including PMDC, one of the configurations of
the MDC system) is affected by lighting in terms of the growth Effects of electrical set up
of biological microorganisms under dark and light cycles. The Bio-electrochemical reactors can be connected in two ways: series
effect of algae growth in batch mode and the amount of dissolved and parallel. In the MDC system, it is preferable to have a parallel
oxygen and oxygen generated because of algae growth in the coupling over a series coupling. The shilling of a series coupling
cathode chamber were studied. The total voltage increased at generates short circuit effects for neighbouring reactors because
the beginning after a short period of delay due to the adaptation of the conductivity of fluids.123 Two connection methods have
of the organisms in the cathode and anode chambers.13 The influ- been proposed to connect the electrodes of the MDC system.
ence of light/dark on microorganisms or substrate depletion in The first method aims for the combined connection where all
the anode chamber showed a sinusoidal effect of PMDC. During the anode electrodes or cathode electrodes are collected and
the dark period, a slight voltage drop occurs because of the lack made into one pole (either one anode pole or cathode pole) as
of light for the photosynthetic activity in the cathode chamber. the circuit consists of only one external resistance. The second
The voltage is restored during the light period due to the photo- method refers to individual connection, where an individual elec-
synthetic activity. One of the studies indicated the reason for trical circuit is configured for each MDC system and the circuit will

e- e- Resistance
Load

CEM Anode
AEM Desalinaon chamber Cathode

biofilm Organics
O2+H
O2 +H2
Na +
e-
- +
Co 2+H ++e+ Seawater

released
into anolyte
Cl - H 2O

concentraon gradient H2 O H ++CO2

anode chamber desalinaon chamber AEM CEM Air


Cathode chamber
18

Figure 14. Air cathode microbial desalination cell. Figure 15. Biocathode microbial desalination cell.

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J Chem Technol Biotechnol 2022
Table 11. Summary of the MDC biocathode configuration

Desalination Power density/


Anolyte/Catholyte with Anode/cathode material chamber fed External Coulombic Total desalination desalination
Configuration volumes and AEM/CEM material NaCl concentrations resistance, (Ω) efficiency (CE), % rate (TDR) COD removal, (%) efficiency, (%) Ref.

Biocathode Sodium Carbon 35 g L−1 200 96.2 ± 3.8 2.83 mg h−1 56.2 ± 6 960 mW m−3 107
MDC Acetate (1.6 Felt/Carbon /92%
g L−1)/Sodium Felt
Acetate. and
49 mL/40 mL AMI 7001S/CMI-7000S
Biocathode Dewatered Graphite fibre 5,10,35 g L−1 1000 — — 25.71 ± 0.15 — 110
MDC Sludge/Soil solution brush/Graphite
in deionized brush
water. embedded in
1400 mL/500 mL graphite
Broad-ranging review: configurations, membrane types, governing equations

granules
and
Ultrex AMI-7001/CEM,

© 2022 Society of Chemical Industry (SCI).


Ultrex CMI-7000
PMDC Synthetic Wastewater with Graphite paper/Graphite 10 g L−1 10 000 — 6.7 mg L−1 65.6 84 mW m−3/40% 149
aerobic sludge with paper and AMI 7001/
180 mL/Mineral CMI 7000
solution with microalgae as
biocatalyst with 180 mL
www.soci.org

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19
www.soci.org HH Abd-almohi, ZT Alismaeel, MJM Ridha

consist of no less than 30 external resistances in the electrical cir- method was much higher than that of the multi-fed, reaching
cuit of each MDC system. Some studies have compared the per- 76% and 57.2%, respectively. It is possible that the electrochemi-
formance of the system between the two parallel connection cally active bacteria outcompete better COD oxidisers when
methods. No significant difference was observed between the exposed to high current generation. Nevertheless, further
two types of binding in the MDC system. The combination of research is needed to confirm this.124
the two methods resulted in 96% COD removal and 42% salt
removal. The only difference was given by two different connec-
tions. The single connection system produced 30 mA, while the Effects of the applied voltage
combined connection provided a current of 13.8 mA. One of the MDC consists of BES and MFC, and its system is derived from elec-
most important reasons for this difference in current yield may trolysis. However, to improve some of the productivity of remov-
be the exchange between the anode electrodes caused by the dif- ing salts, organic substances, COD and others, the system was
ferences in their potentials. However, this possibility has not been operated with an external effort and was used to assist the effort
confirmed yet.124 generated by the system during the operation process. Studies
show that the system runs at a primitive COD of 3000 mg L−1 with
Effect of anolyte feeding modes four different voltages (e.g., 0, 0.4, 0.8, and 1.1 V). The amount of
The form of the feed affects the performance of a multi-MDC sys- COD removed from the system was not affected because the
tem, as a single-stream feed (the feed flows through all units in a removal amount was fixed at 95%.124 However, the amount of
chain) or through multiple inputs. Expectations of multiple feed- current was greatly affected by the difference in voltage because
ings give a better distribution of units, unlike single-stream feed- it increased by 1000 mA from 0 to 1.1 V, causing the TDS removal
ing, because there are no mixing or recycling units currently to increase. The results confirmed that the extra effort could help
existing in the system. Zhang He experimented by feeding the in improving the performance of the system. However, the addi-
system with either a single feeding or a four-point feeding. The tional external voltage added must be evaluated with the eco-
system fed with four points gave an extremely high current pro- nomic feasibility of the system, which may vary in power
ductivity of about 663 mA, while the single fed one gave about consumption from 0.26 to 0.37 kWh kg−1 TDS with 0.4–1.1 V. 0 V
445 mA, but the amount of COD removed by the single fed is not needed for external voltage.124

Table 12. Advantages and disadvantages of different configurations of microbial desalination cells (MDCs)26

Type of MDC Advantages Disadvantages

Air cathode MDC High reduction potential. The kinetics of redox reactions takes a long time.
Environmentally friendly. Expensive catalysts are required (e.g., platinum)
Biocathode MDC Self-renewing and long-lasting. The setup of a biocathode is difficult and time consuming.
Desalination of seawater is being improved. Pre-enrichment process is required.
Start-up time has been reduced.
Scalability is simple.
Stacked-structure MDC More energy is recovered. Internal resistance in MDC stacks has increased.
Charge transfer efficiency has improved. Unbalanced pH
Desalination efficiency has improved.
Power density has been increased.
Recirculation MDC pH in the cell is stabilized. Decreased coulombic efficiency.
Power density has been increased.
Desalination rate has increased.
Capacitive MDC Desalination rate has increased.
pH is stabilized.
Prevents salt ions from migrating between chambers.
Upflow MDC Microbes are still floating in the air. Longer period of retention.
Increased surface area. Large reactor capacity.
No need for mixing. Expenses of capital have risen.
Osmotic MDC Desalination is being improved. Membrane fouling decreases internal resistance.
FO membrane is less expensive than IEM. FO membranes increase generation of current.
Degradation of organic waste has improved.
Bipolar membrane MDC Chemicals, such as HCl and NaOH, are produced. Mineral precipitation causes cathode scaling.
pH equilibrium is improved. BPM has been tainted.
Necessitates the use of an external power source.
Decoupled MDC Easy to control. Due to the lack of separate chambers, desalination
Parts are simple to fix and replace. efficiency may suffer.
Easy to scale up.
Ion exchange The ohmic resistance has been reduced. Mineral encrustation on the resin surface causes scaling.
resin–coupled MDC Energy usage is reduced. Internal resistance is increasing.
Increased salty water conductivity and desalination rate. Coulombic efficiency may be reduced.
20

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Table 13. Important equations used to calculate the MDC parameters

Factors Variables defined Equation Ref.

The potential Ecell: potential of cell (V). E cell =Rexternal ×I 150


Rexternal: external resistance connected (Ω).
I: electric current (A)
The potential Ea: refer for the anode potential (V). E cell = ðE c −E a Þ−I×ðRmembrane +Rsaline Þ 151
Ec: refer for the cathode potential (V).
Rmemb: refer for the sum of the electric resistance (Ω).

J Chem Technol Biotechnol 2022


Rsaline: refer for the electric resistance due to the saline
compartment (Ω).
 
Resistance of saline EC: refer for the electric conductivity of the saline stream Rsaline = ð1=ECÞ× L=Am 152
(S m−1)
L: refer for thickness of the saline compartment (m).
Am: refer to the geometric area of electrode (cm2).
The power Ecell: potential of MDC (V). Pcell =E cell ×I 151
Pcell: the power of the MDC cell (W).
I: refer to electric current (A).
Current density I: refer to electric current (A). j = AIm 150
Am: refer to the geometric area of electrode (cm2).
j: refer to current density (mA cm−2).
Percentage of the salt removal from cell Csi; refer to the initial concentration of salt in the saline tank C is −C fs 152
SR%= C is
×100%
(mol m−3).
f
Cs : refer to the end concentration (after desalination process)
of salt in the saline tank (mol m−3).
Broad-ranging review: configurations, membrane types, governing equations

SR %: the percentage of the salt removal from desalination


chamber.
The nominal desalination rate (NDR) NDR: refer for the nominal desalination rate (L m−2 h−1). NDR= AmQ×tt d 152

© 2022 Society of Chemical Industry (SCI).


Am: refer to the geometric area of electrode (cm2).
td: refer for the desalination time (h).
Qt: the desalination water volume (L).
The amount of transferred salt from cell TNaCl: refer for the amount of transferred salt. Qt ×M:W:×ðC is −C fs Þ 151
T NaCl = V s ×t d
TNaCl Qt: the desalination water volume (L).
MW: refer for the molecular weight of NaCl.
Vs: refer to the volume of the desalination chamber (m3).
Csi; refer to the initial concentration of salt in the saline tank
www.soci.org

(mol m−3).
Csf: refer to the end concentration (after desalination process)
of salt in the saline tank (mol m−3).
td: refer for the desalination time (h).
 
Current efficiency ηc: the current efficiency. z×F× C is −C fs 152
z: is the salt ions valence. ηc =
ðCEC
F: faraday constant (96 485 C mol−1). 1
CEC = IðtÞdt
Qt

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21
22

Table 13. Continued

Factors Variables defined Equation Ref.


i
Cs ; refer to the initial concentration of salt in the saline tank
(mol m−3).
Csf: refer to the end concentration (after desalination process)
of salt in the saline tank (mol m−3).
I: refer to electric current (A).
CEC: the circulated electric charge (CEC, C m−3).

wileyonlinelibrary.com/jctb
Ð
The efficiency of columbic M: is the oxygen molecular weight (32 g mol−1) M× Iðt Þdt 153
ηcb = F×b×QAn ×ΔCOD
b: is the exchanged number of electrons (i.e., for oxygen the
exchange number of electrons = 4).
I: refer to electric current (A).
QAn: is the anolyte tank volume (L).
ΔCOD: is different of chemical oxygen demand during the
experiment (g O2 L−1).
F: faraday constant (96 485 C mol−1).
The removal of chemical oxygen demand VA: is the volume of liquid in the anode compartment (m3). CODrate = ΔCOD
V A ×t d
153
rate CODrate: is rate of the COD removal (g m−3 day−1).
www.soci.org

ΔCOD: is different of chemical oxygen demand during the


experiment (g O2 L−1).
td: refer for the desalination time (h).
Ð
The specific energy production (SEP) SEP: is the specific energy production (kWh m−3). SEP = Q1t × E cell :IðtÞdt 161
Ecell: potential of MDC (V).
I: refer to electric current (A).
Qt: the desalination water volume (L).
Power density I: refer to electric current (A). P = I×E
A
153
E: the voltage of cell
A: the surface area of electrode

© 2022 Society of Chemical Industry (SCI).


P: power density (W m−2)
Power density I: refer to electric current (A). P = I×E
V
157
E: the voltage of cell
A: the surface area of electrode
P: power density (W m−3)
Power density produced for the surface PAn = power density (W m−2) V2
cell 155
ext
P = AAn ×R
area of anode in MFC AAn = anode surface area (m2)
Vcell = cell voltage (V)
Rext = external resistance (Ω).
The desalination rate (DR) DR: desalination rate g h−1 e Þ×Q×60 160
DR= ðCi −C
2×1000
Ci: conductivities of influent (mS cm−1)
Ce: conductivities of effluent (mS cm−1)
Q: is the flux (mL min−1)
(60, 1000, 2): used to conversion the mS cm−1 to g L−1 and the
minute to hour.

J Chem Technol Biotechnol 2022


HH Abd-almohi, ZT Alismaeel, MJM Ridha
Table 13. Continued

Factors Variables defined Equation Ref.


 F

The consumption rate of carbon source at Cs: Substrate concentration in the anode chamber (mg L−1). r 1 =K 1 × exp ⊍× R×T ×V act1 × KCs Cs s ×X 156
the anode chamber Ks: The half velocity rate constant for substrate (mol m−3).
X: Concentration of biomass on the anodic electrode (mg L−1).
Vact1: Anodic over potential (v).
⊍: Charge transfer coefficient of the anodic reaction.
K1: Rate constant of the anode reaction at standard

J Chem Technol Biotechnol 2022


conditions(mol m−2 s−1).
r1: Reaction rate of the anode chamber (mol m−2 s−1).
R: Gas constant (8.314 J
mol−1 K−1)
T: Temperature (K)
F: Faraday number (96 485 C mol−1)
 F
 C O2
The reduction reaction of dissolved oxygen CO2: Concentration of oxygen in the cathode chamber r 2 =−K 2 × exp ð⊎−1Þ× R×T ×V act2 × 157
ðK O2 +C O2 Þ
in the cathode chamber KO2: Half velocity rate constant for O2
Vact2: Cathodic over potential
⊎: Coefficient of charge transport for the cathodic reaction
K2: Rate constant of the cathode reaction at standard
conditions
r2: The rate of reaction in the cathode chamber
R: Gas constant (8.314 J mol−1 K−1)
T: Temperature (K)
F: Faraday number (96 485 C mol−1)
Broad-ranging review: configurations, membrane types, governing equations

Rate of charge Q: is the charge I = dQ


dt
155
t: is the time

The cell voltage Vcell is decreasing from the Vcell: MDC voltage V cell =V ocv −ðV act anod + V act cath Þ−V Ω − V CONC anode +V CONC cathodeÞ 157

© 2022 Society of Chemical Industry (SCI).


equilibrium potential by a series of Vocv: MDC open circuit voltage
irreversible losses Vact_anode: anodic activation potential
Vact_cathode: cathodic activation potential
V(CONCanode):anodic concentration potential
V(CONCcathode):cathodic concentration potential
VΩ: the ohmic potential
Resistance due to the membrane resistance Rionic: Ionic resistance of membrane (Ω) I = dQ
dt
159
www.soci.org

tm: Thickness of membrane (m)


⊞1 : Conductivity of membrane (Ω−1 m−1)
Am: Area of membrane (m2)
The cell impedance due to the resistance of Relect : Electric resistance of solution (Ω) m 161
s
Relect = ⊞2d×A
substrate dm : Depth of solution (m)
⊞2 : Conductivity of solution (Ω−1 m−1)
As : Cross sectional area of solution (m2)
The membrane resistance Rionic : ionic resistance of membrane (Ω) m 162
m
Rionic = ⊞1t×A
tm : thickness of membrane (m)

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www.soci.org HH Abd-almohi, ZT Alismaeel, MJM Ridha

One important characteristic of these systems (MFCs and MDCs)

58

81
Ref. is that the cell is strongly affected by mass transfer limitations. It is
expected that a more turbulent regime in the vicinity of the anode
will lead to a slight polarisation of the electrode, giving the illusion
of producing more energy, especially at very low current densi-

dt =Dsalt ðC salt,in −C salt,m Þ−d ðC salt,m −C salt,a Þ−d ðC salt,m −C salt,c Þ− FV salt
IMDC
ties. However, the turbulence will also cause bacterial stress, neg-
atively impacting its performance and impeding the formation of
biofilms.125

Effect of hydraulic retention time (HRT)


The HRT component has a significant influence on the evident
reaction mechanisms in MDC systems. Qu et al. studied increasing
the effect of HRT from 1 to 2 days in the continuous mode of MDC.
V ohmic =Rionic ×i cell + Relect ×i cell + Rsalt ×i cell

The result of the study gave a flow rate of 0.02 mL min−1 of trea-
dt = d ðC salt,m −C salt,a Þ−Danode ×C salt,a

ted water with a decrease in the amount of energy produced in


the system, as well as a reduction in the imbalances of the pH.35
Jacobson et al. confirmed that the amount of generated current
increases with HRT because of the increment in the total dissolved
dt = d ðC salt,m −C salt,c Þ

TDS removal.55
Ping and He concluded that the increase in HRT for water puri-
fication in the desalination chamber of the MDC improved the
purification and treatment of saline water, but that the increase
Equation

in the distance between the membranes and the increase in the


dC salt,m
dC salt,a

dC salt,c

volume of the desalination chamber led to an increment in the


ohmic resistance and affected the improvement of water desali-
nation. There were no detrimental effects on performance due
to a greater intermembrane distance with an equal influent flow
Csalt,a, Csalt,m, Csalt,c: concentrations of salt in the anode, middle,

rate, whereas a short intermembrane distance increased desalina-


tion efficiency and specific desalination rate substantially.60
Rsaline: refer for the electric resistance due to the saline

Liu et al. created two MDCs under different hydraulic retention


dsalt: coefficient of membrane salt transfer (day−1).

times (4, 6, 8, 10 h), and the study observed that when the time
increased the conductivity was increased. The desalination rate
was increased twice as much as most similar systems.126
⊞1 : Conductivity of membrane (Ω−1 m−1)

R_elect : Electric resistance of solution ðΩÞ


Variables defined

Rionic : ionic resistance of membrane (Ω)

cathode chamber, respectively.

Evaluation of desalination alternatives


Dsalt: the rate of dilution (day−1)

Temperature, water desalination, liquid waste composition, and


Am : area of membrane (m2)

waste disposal site are amongst the most crucial factors that
affect the efficiency of MDC performance. For example, gases
compartment (Ω).

and liquids that contain toxic compounds (or complex salts) and
organic substances are known to affect living organisms when
they are discharged into areas that contain rich marine organ-
isms.127 The World Health Organisation directs all factories and
treatment and desalination plants to follow a specific protocol
regarding concentration percentages suitable for the disposal of
desalination and treatment waste into rivers or seawater. Recent
studies have focused on the impact of the MDC system on the
environment and in reducing its damage. Some studies have
The salts concentration was quantified by

researched the future and sustainability of the system, especially


when it comes to the management of wastewater stations.128,12
the following developed ordinary

However, studies have a minimal impact on the MDC system envi-


ronment. Due to the comparison of the effects of MDC in relation
to the effects of other technologies of treatment on the environ-
ment, MDC has zero waste on the environment when using a bio-
Table 13. Continued

The internal resistance

cathode. Steven and Kotz proved this when they studied the
effect of Scenedesmus, an abundant microalga used as a catholyte,
with petroleum wastewater as an anolyte. The result of the pro-
differential

cess with 35 g L−1 NaCl resulted in 55.3% of NaCl removal and


that with 20 g L−1 NaCl resulted in 42.6% of NaCl removal.129,130
Factors

Table 14 defines the type of catalyst that can be used in MDC to


24

improve the performance of the MDC process.

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Table 14. The types of catalyst that can be used in MDC to improve process performance

Initial power Current Desalination Columbic


Catalyst type density Power density production, A efficiency, % Voltage, V efficiency, % Ref.

Platinized carbon — — — — — — 107


Platinum 49 μW cm−2 — — — — 38% 97
Iron nitrogen carbon (Fe-N-C) 34 μW cm−2 — — — — 39% 97
Activated carbon 23.5 μW cm−2 — — — — 24% 97
Biocatalysts — 0.35 W m−2 10 mA 51.5% — — 144
Methylene blue (MB), — 337.13 mW m−3 — 16.1–5.86% 77.9 mv — 124
known as methylthioninium decreasing with
chloride increasing MB
concentration

MEMBRANE FOULING AND SCALING IN MDC U


I=
The biofouling/scaling that occurs on the IEMs due to bacterial R
growth in the anode chamber decreases the performance of the
The power density (P) produced across each membrane stack
MDC in general. The ion transfer, low power density generation,
could be determined as follows:
and desalination rate in MDC, as well as the pH imbalance in the
anode chamber and cathode chambers, all decreased.116,127
U×I
Luo et al. explained the migration of ions, with studies that clar- P=
A
ified the basic concepts of ion migration and the reason for the
biofouling/scaling on the IEMs (AEM, CEM). Only 0.4–0.1% of the Where, U: external circuit voltage, I: current under certain external
ions (Ca+2, Mg+2) move through the membranes, while the rest resistance, and A: the desalination sectional area (DA) of the MDC.
of the ions are scaled on the IEMs. The internal resistance in the Internal resistance or ohmic losses are the final substantial losses
MDC increases because of the accumulation on the IEMs, where that should be avoided for the optimum MDC design. These losses
resistance increased to 3.7 times its normal value, and the amount appear from the resistance of proton conduction due the following:
of current density production decreased to 210 mA m−1. The bio-solution, membrane, salty solution. To reduce the internal resis-
water desalination efficiency reached 13 due to the presence of tance and ohmic losses, the distances between the electrodes are
Cl− (with Mg+2, Ca+2) in treated saline water as a common counter reduced; selecting to use low-resistance ion exchange membranes
ion, even compared with the 660 and 29 produced without scal- and coating the electrodes can help reduce internal resistance, and
ing on the membranes.126 increasing the conductivity of solutions may reduce the value of the
The accumulation of biofouling on the CEM membrane in the internal membrane.71 Table 13 defines the important equations used
mixed IER-MDC reduced the performance of the system from in calculating the MDC parameters.
the water desalination process. This result is due to the scaling Oxidation and reduction reactions are divided into two parts:
of Ca + and Mg + compounds on the membrane and to their reduced half and oxidized half, both of which occur together. When
exchange with sulphate or carbonate groups within.62 reducing processes gain electrons, theamountofoxidations decreases,
Studies on the treatment of real wastewater or synthetic waste- but when electrons are lost from oxidation processes, the number of
water have been conducted. Membrane fouling increased the oxidations increases. There is no change in the number of electrons in
resistance of the CEM membrane compared with that of the the oxidation–reduction reaction, as the number of electrons lost is
AEM membrane because of the scaling of inorganic materials on always equal to the number of electrons gained in the reaction.129
the CEM membrane. Thus, reactor maintenance is necessary.127 The following is an example of an oxidation–reduction reaction:130
Luo et al. discovered a significant variation in current density,
which they ascribed to membrane scaling and the changes in
Zn+2H +2 àZn +2 +H2 ð3Þ
transport behaviour between divalent anions and cations.

Although they provided methods to reduce membrane scaling, ðCH2 OÞ2 +2 H2 Oà2CO2 +8H +8e +
ð4Þ
such as changing the membrane surface, lowering the pH of a − −
O2 +4 e +2 H2 Oà4OH ð5Þ
cathode chamber, and cleaning the membranes on a regular
basis, further study is needed to improve long-term use.128 Scal-
ing the size of the membrane will always reduce the performance
in comparison to small-scale devices.128
MDC POWER GENERATION AND ITS FUTURE
APPLICATION
The production of electrical power is one of the advantages of the
GENERAL GOVERNING EQUATIONS AND microbial desalination cell, and studies are still in progress with
PARAMETERS IN MDC the goals of harnessing energy and dispensing with energy desa-
The generated current (I) can be calculated according to Ohm's lination systems that need additional external energy. The addi-
law, as follows: tional chamber in MDC did not only serve for water desalination
25

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but it also provided a higher productivity of electrical power and a concentration PBS (10 mmol L−1 PBS), (100 mmol L−1 NaCl),
higher stability than the MFC system with stable pH.78 saline buffer solution (50 mmol L−1 PBS with 100 mmol L−1 NaCl),
Ebrahimi et al.131 studied the amount of additional resistance as well as the possibility of using biocathodes, such as algae or
resulting from adding a chamber to the MDCs and noticed that, bacteria.136
at a concentration of 30 g L−1, the amount of current and energy N. R. Faze investigated the economic analysis and the possibility
density increased to 3.17 mA and 204.5 mW m−2, compared with of developing the existing MDC system into cost-effective future
MFCs 2.59 g L−1 and 141.6 mW m−2, respectively. technologies. The MDC reactor was designed to produce
Studies have been conducted to find the best catholytes with 100 cm3 of desalinated water each day. Desalinating a cubic
the least environmental defects. Ebrahimi et al.132 studied the metre of water from a single MDC system, including the time
comparison of different cathodic solutions and concluded that required to clean rooms, inoculate solutions, replace materials,
the best catholyte solution is a bio-catholyte that gives volatile and perform annual maintenance, takes approximately 28 years.
organic compounds 0.818 V and 32.6 W m−3 of power density. However, if multiple MDC systems were constructed in parallel,
Due to the improved quantity of organic compounds in the cath- the rate of electricity production and water desalination might
ode (which improves the electron capacity of the chamber), a be increased.135
6.15 mA current and 0.85 NaCl L−1 per hour desalination rate RO is the most common method used in water desalination.
were obtained. Various catholytes were used to vary the pH value, Desalinating 1 cubic metre of water by using RO technique
with the risk of damaging the MDC bacteria.107 Wet carbon was requires approximately 2.2 kW. However, desalinating the same
used as a catalyst membrane to cover the cathode electrode in volume of water in the MDC system resulted in an electricity pro-
MDC. The catalyst helped increase the electric power output ductivity of approximately 1.8 kW per hour of clean energy.137
and the production of volatile organic compounds in MDC.133 Finally, research and development in this subject is still ongoing.
Santoro et al.134 compared the types of catalyst (e.g., platinum, To introduce the MDC system on a large scale, a wide range of
activated carbon, and iron nitrogen carbon) and found that their economic analyses and comparisons with the rest of the existing
initial power density is 49, 34, and 23.5 μW cm−2 and CE was desalination technologies is required.
38%, 24%, and 39%, respectively. The bio-catalyst provided
10.1 mA, 0.35 W m−2 in close circle, and 51.5% desalination effi-
ciency.80 In another study, the continuous operation of the MDC CONCLUSIONS
system improved the power density, which reached 15.9 W m−3, The study dealt with the concept and applications of the microbial
and achieved an average of 68.1% desalination, 83.7% COD desalination cell in terms of the working principle, the mem-
removal, and 13.9 W m−3 power density.131 branes used, and their forms. The microbial desalination cell is still
under development and research. The microbial desalination cell
produces electrical energy during the desalination process that
SCALE UP OF MDC can be used in desalination plants and wastewater treatment; this
In recent years, studies have been directed towards the scaling can significantly reduce the process's energy requirements. The
up and configuration of MDC systems because of the character- electrically active microbes showed the possibility of electron
istics and solutions they provided to most of the problems transfer in the system as well as wastewater treatment under
encountered in wastewater treatment, and because of their anaerobic conditions. The factors affecting the microbial desalina-
ability to generate electric power and spontaneously desali- tion cell were studied; they showed the reasons for the deteriora-
nate water. Despite their characteristics and ability to treat tion of the cell over time and the causes of the pH imbalance, as
sewage water, the implementation of water desalination well as the effect of external and internal resistance on the micro-
directly from the MDC by using municipal wastewater has not bial desalination cell. The different criteria for operating the cell, as
been realised. The pH value imbalance in the system negatively well as the different configurations of the system, gave different
affected the possibility of scaling up the MDC because of the results to the system according to the standards and configura-
generation of protons in the anode chamber and to the con- tion, and this is one of the reasons why it was not possible to make
sumption of protons in the cathode chamber.135–139 In addi- a comparison of the performance of the system. However, the sys-
tion, the MDC system requires 200 mL of synthetic tem is still under research and studies are underway to determine
wastewater to treat approximately 3 mL of saline water, so the solutions to several problems of MDC (concerning scaling/
the scale-up of the MDC is still under analysis and study.21,102 fouling of the membrane, electrode compatibility, electron trans-
fer kinetics, and microbial growth).

ECONOMIC ANALYSIS
Many recent studies have assessed the economic impact of the
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