Desalination 472 (2019) 114187

Contents lists available at ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Brine management in desalination industry: From waste to resources T

generation
Musthafa O. Mavukkandya, Chahd M. Chabiba, Ibrahim Mustafaa, Amal Al Ghaferib,
⁎
Faisal AlMarzooqia,
a
Center for Membranes & Advanced Water Technology, Department of Chemical Engineering, Khalifa University of Science and Technology, P.O. Box 54224, Masdar City,
Abu Dhabi, United Arab Emirates
b
Department of Mechanical Engineering and Materials Science, Khalifa University of Science and Technology, P.O. Box 54224, Masdar City, Abu Dhabi, United Arab
Emirates

A R T I C LE I N FO A B S T R A C T

Keywords: Desalination brine has high salinity and contains various chemical contaminants and its disposal causes a major
Resource recovery concern for desalination around the world. Environmentally friendly and economically feasible methods are
Desalination essential for sustainable management of desalination brines. On the other hand, adequate supply of various
Brine minerals is essential in meeting the increasing demands of growing populations across the world. Land-based
Seawater mining
mining industries suffer from limited supply of water and energy, depletion of high-grade minerals, environ-
mental issues and various geopolitical conflicts. Although suffers from high cost, low recovery efficiencies and
absence of mature technologies, seawater mining offers a potential solution for this. Seawater contains large
quantities of various minerals, of which some are rare and expensive in their land-based forms. This can mitigate
the mineral scarcity to some extent and reduce the desalinated water price significantly as we get an additional
product from desalination. In addition, the environmental impacts associated with the brine discharge can be
avoided as well. This paper reviews recent research and technologies on recovering resources from desalination
brine. Major thermal and membrane technologies for recovering water, minerals and energy are included.
Recent developments in solar ponds, membrane distillation, membrane distillation crystallization, electro-
dialysis and reverse electrodialysis, chemical precipitation, adsorption/desorption, eutectic freeze crystal-
lization, pressure retarded osmosis and microbial desalination cell etc. are discussed. Although extraction of
several materials from desalination brine is technically possible, it is currently expensive and largely restricts the
commercialization. Last decade has witnessed an increased academic interest on this topic, however, the number
of pilot-scale research has been very limited.

1. Introduction water desalination has been reported to have reached 95 mil-

Scarcity of freshwater and its increasing demands are stressing on
the needs to develop low-cost and efficient technologies for water
production and supply. Water desalination technologies such as reverse
osmosis are capable of removing salts from saline water to produce
potable water [1]. This has resulted in increased world-wide attention
for their development and implementation. Currently, the amount of
lion m3 d−1, of which the Middle East and Africa (MENA) region con-
tributes to a 48% water production share [2]. Fig. 1 illustrates the
global desalination forecasts for the increasing desalination capacity.
1.1. Issues with brine management
Desalination is a multi-stage process and typically yields two

Abbreviations: AEM, Anion exchange membranes; CaSO4, Calcium sulfate; CEM, Cation exchange membranes; Cl2, Chlorine; COD, Chemical oxygen demand; CTA,
Cellulose triacetate; DS, Draw solution; ED, Electrodialysis; EDBM, Electrodialysis with bipolar membranes; EFC, Eutectic freeze crystallization; FO, Forward osmosis;
H2, Hydrogen; HCl, Hydrochloric acid; HRT, Hydraulic retention time; KCl, Potassium chloride; KCuFC(PAN), Potassium copper hexacyanoferrate polyacrylonitride;
MCr, Membrane crystallization; MD, Membrane distillation; MDC, Microbial desalination cell; MED, Multi-effect distillation; NaCl, Sodium chloride; NaOH, Sodium
hydroxide; NF, Nanofiltration; PA, Polyamide; PES, Polyethersulfone; PRO, Pressure retarded osmosis; PVDF, Polyvinylidene fluoride; RED, Reverse electrodialysis;
RO, Reverse osmosis; S-ED, Selective electrodialysis; SRT, Sludge retention time; SWRO, Seawater reverse osmosis; UF, Ultrafiltration; ZLD, Zero liquid discharge
⁎
Corresponding author.
E-mail address: faisal.almarzooqi@ku.ac.ae (F. AlMarzooqi).

https://doi.org/10.1016/j.desal.2019.114187
Received 16 September 2019; Received in revised form 17 October 2019; Accepted 17 October 2019
Available online 07 November 2019
0011-9164/ © 2019 Elsevier B.V. All rights reserved.
M.O. Mavukkandy, et al. Desalination 472 (2019) 114187

Fig. 1. Desalination capacity forecast plot over 30 years, showing a doubling of the installed capacity in 12 years, and a capacity of > 200 million m3/day in 2030
[3].

Fig. 2. Various brine disposal methods currently practiced around the world.

products: (i) fresh water (water that meets quality for human use) and
(ii) brine (water with high salinity and reject concentrate). In addition
to its high salinity, reject brine is also chemically contaminated. A ty-
pical reverse osmosis brine consists of a total dissolved solids (TDS)
concentration of ~70,000 mg L−1, which contains several chemical
residues from pretreatment and cleaning processes, in addition to so-
dium chloride [4,5]. Chemicals such as NaOCl, FeCl3, AlCl3, H2SO4,
HCl, and NaHSO3 are typically applied at the pretreatment stage to aid
in water treatment for minimizing algal growth, reducing corrosion,
inhibiting scaling, adjusting the pH, and chlorinating the water. Brine
also has a higher density than that of typical saltwater. Thus, brine
disposal will contaminate the marine environment, causing a major
concern for desalination around the world and therefore appropriate
environmental-friendly brine management is essential [6,7]. As seen in
Fig. 2, there has been several methods implemented for brine disposal,
including sea disposal, land disposal, evaporation, membrane distilla-
tion, forward osmosis, deep electrodialysis, capacitive deionization,
well injection, and sewage disposal [8–10]. In a recent review, Pana-
gopoulos et al. evaluated various practices in brine management com-
prising treatment technologies and disposal methods and argued for
developing zero liquid discharge systems for recovering freshwater and
solid salts [11].

2
M.O. Mavukkandy, et al.
1.2. Challenges in mining industry
Adequate supply of various minerals is essential in meeting the
demands of growing populations across the world. Land-based mining
industries suffer from limited supply of water and energy, depletion of
high-grade minerals, environmental issues and various geopolitical
conflicts [12]. In addition, the production cost and the associated en-
ergy and water demands will be more when there is a degradation in
the quality of ores. Water consumption in mining industry has become a
debatable topic, which has forced some countries to put some restric-
tion for mining [13]. Although suffers from high cost, low recovery
efficiencies and absence of mature technologies, seawater mining offers
a potential solution for this. Seawater contains large quantities of var-
ious minerals, of which some are rare and expensive in their land-based
forms [12]. This can mitigate the mineral scarcity to some extent and
reduce the desalinated water price significantly as we get an additional
product from desalination. In addition, the environmental impacts as-
sociated with the brine discharge can be avoided as well.
Interests in the area of the conversion of brine (which was regarded
as a waste) to a resource was first proposed in the 1970s, but very little
was done until 2001, which marks the year at which a sharp increase in
the number of publications on the resource recovery and desalination
occurred, as shown in Fig. 3. Although important, very little has been
performed to review and assess current state of resource recovery from
desalination brine.
2. Types of resource recovery
A historical timeline on the recovery of resources from seawater and
brine is illustrated in Fig. 4. Sodium chloride was extracted from sea-
water for thousands of years. Over time, people started research on
mining valuable metals such as gold, magnesium, bromine, uranium,
lithium, cesium, rubidium etc. from seawater and brine [14]. Currently,
there are two main approaches for brine management – volume re-
duction and ZLD/crystallization. Volume reduction technologies aim at
recovering the additional water up to or beyond the saturation con-
centration, whereas ZLD/crystallization technologies aim at extracting
water and various salts from saturated brines [15,16]. Technologies
such as pressure retarded osmosis (PRO) aim at recovering energy as
well. Recently, Choi et al. published a review paper on the use of
membrane distillation crystallization (MDC) – a combination of
Fig. 3. Number of journal articles with topic keywords ‘resource recovery’ and ‘desalination’.
(Accessed from https://scopus.com, using the keywords “Resource recovery” AND “Desalination” in article title, abstract or keywords.)
3
Desalination 472 (2019) 114187
membrane distillation and crystallization, for mining from brine and
ZLD [17]. Authors report that MDC would help achieve water and other
resources recovery, with near zero liquid discharge, provided we solve
the challenges such as crystallization on the membrane surfaces,
membrane wetting and high energy consumption. Vane assessed the
thermodynamic efficiencies and operational difficulties of various de-
salination technologies employed for highly concentrated brines and
found that mechanical vapor compression had the highest thermo-
dynamic efficiency [18]. Despite having the technical capability,
thermal processes suffer from the low thermodynamic efficiencies and
this could be overcome by utilizing waste or renewable heat sources. A
summary of various processes used for recovering resources from sea-
water brine are listed in Table 1.
3. Resources recovery processes
There are a variety of technologies, which either operate as a stand-
alone or as a hybrid of multiple processes, can be employed for re-
covering resources from brine. These can be broadly classified as
membrane-based and thermal based, and their basic principle of op-
eration along with their recent application in resource recovery is dis-
cussed in the following sections.
3.1. Solar pond
Solar ponds are shallow, lined basins in which brine evaporates
using the solar energy leaving behind a concentrated salt solution/
crystals at the bottom of the basin. It can be a conventional evaporation
pond used for disposing brine or modern solar salinity gradient pond for
generating electricity from solar energy [28–30]. The precipitated
salts/minerals could be collected periodically and disposed-off or
gainfully utilized in other processes. A typical salinity gradient solar
pond has three zones – upper convection zone that has low salinity and
has temperature close to ambient temperature, middle non-convection
zone with increasing salinity and temperature with depth, and lower
convection zone with highest salinity and temperature [31]. Although it
is easy to construct, requires low maintenance and minimal mechanical
equipment, it has high footprint and is restricted to small capacities. It
is an effective method if land is available at low cost at an arid or semi-
arid region. These ponds have to be prepared with an impervious lining
in order to avoid the contamination of underlying aquifers. If the brine
M.O. Mavukkandy, et al.
Fig. 4. Timeline representing the development of resource recovery from seawater and brine.
(Adapted from [19].)
contains significant amounts of toxic materials, a double-lining may be
recommended. As evaporation rate is dependent of the local climate
and the solar flux, it is usually recommended for warm areas with low
rainfall and humidity and high evaporation rate.
By conducting a market assessment of minerals found in the brine
from Al-Khobar Desalination and Power Plant in Saudi Arabia,
Abdusalam et al.. argued that recovery of resources from seawater brine
could reduce the desalinated water cost [32]. Authors then integrated a
solar and evaporation ponds via a heat exchanger and pump, to facil-
itate the transfer of hot brine from the solar pond to the evaporation
pond and vice versa (Fig. 5). This enhanced the evaporation rate as heat
exchangers supplied more heat and they observed a significant im-
provement in the evaporation rate.
In another study, Yusuf et al. explored a new cheap method to
achieve zero liquid discharge desalination with high-energy efficiency
using solar distillation [33]. They fabricated a 3D cup shaped solar
evaporator that only uses sunlight as energy source, and produces salt
as byproduct. The cup was made of three layers of silica/carbon/silica
(SCS) and has nearly 100% solar evaporation efficiency and light ab-
sorption of 99.35%. Hyper saline streams (25 wt%) can be applied with
a slight decrease in evaporation rate. In addition, the salt precipitation
surface is separated from the light-absorbing surface so that the 3D cup
structure is able to treat near saturated NaCl brine (25 wt%) for up to
120 h with stable and high water evaporation rate of 1.26 kg m−2.
Overall, the clean water production using this technology was 0.55 and
0.50 kg m−2 h−1 for 15 wt% brine and 25 wt%, respectively. The 3D
cup structure can be used as brine crystallizer in open air and as a solar
evaporator for ZLD system in closed chamber. Other solar evaporating
devices can be similarly produced by separating the light absorbing
surface from the precipitation surface. Combing this technology with
other conventional desalination processes has the potential of achieving
zero liquid discharge goal.
Mohamed et al. assessed the feasibility of integrating PRO with a
salinity gradient solar pond for desalination multi-effect distillation
(MED) and photo-assisted chloralkali process [31]. Brine from the MED
was used the draw solution for PRO and feed in the chloralkali process.
The solar pond was able to supply the energy for the desalinating
seawater at a rate of 14,000 m3 year−1. In addition, useful products
such as hydrogen, chlorine and sodium hydroxide were recovered from
the seawater brine via photo-assisted chloralkali process. Production
rates of hydrogen and chlorine were mainly dependent on the power
generation from the PRO system. As seen in the Fig. 6, chlorine yield
was from 19.8–122 mg s−1 whereas hydrogen yield varied between
0.56 and 3.16 mg s−1, which corresponded to an annual production of
67.6 and 2377.8 kg of hydrogen and chlorine, respectively.
Solar ponds are attractive for countries which are relatively close to
4
Desalination 472 (2019) 114187
the equator with large areas available. In addition, the hot salty water
can be used to generate power during the process. A salinity gradient
naturally occurs in solar pond, where salinity increases with depth. The
sunrays reach the bottom of the solar pond, causing the lower layer
with high salinity to heat up. The high-salinity water at the bottom of
the pond does not mix with the low-salinity water at the top of the
pond, which reduces the heat loss of the lower layer. The hot brine at
the bottom can be pumped away to be used a source of thermal energy
or for electricity generation [34]. Another advantage of this technology
is the generation of accumulating salt crystals, which can be removed to
extract valuable minerals. However, the solar energy conversion
is < 2%, which makes this process slow and inefficient. As water eva-
porates from brine, the heat capacity of the remaining water increases,
making the process slower.
3.2. Membrane distillation (MD)
Membrane distillation (MD) is a thermally driven separation tech-
nique where a micro-porous hydrophobic membrane allows water
vapor to pass through while blocking the liquid, separating the vapor
phase from the liquid phase. Vapor pressure created by the temperature
difference across the membrane drives this process. Historically al-
though desalinating seawater was the key application explored for this
process, there is increasing focus of using MD in brine concentration
[35–39]. That is due to its ability to tolerate highly concentrated brine
with lower energy requirement than evaporation and crystallization
and the possibility of obtaining high solute rejection without hydraulic
pressure requirement. Membrane distillation could also be utilized for
resource recovery from concentrated brines. Polyvinylidene fluoride
(PVDF), polytetrafluoroethylene (PTFE) and polypropylene (PP) are the
widely used membrane materials in MD and have pore diameter be-
tween 0.1 and 0.5 μm [35]. Although the pores are much larger than
water molecules, liquid water does not pass through the membrane due
to the high water surface tension. There are several MD distillation
techniques, the most common are: direct contact MD, air gap MD, va-
cuum MD, sweeping gas MD, and permeate gap MD. The major ad-
vantage of MD in water desalination is its resistance to fouling and its
ability to offer higher water recovery. Bush et al. compared the per-
formance and fouling behavior of nanofiltration (NF) and MD using
silica concentrated solutions [40]. As silica concentration in the solu-
tion exceeded saturation, the flux of NF immediately declined due to
scaling. MD, on the other hand, was much resistant to scaling initially.
Performance of MD started declining when silica was concentrated
more than twice its solubility limit. Salt rejection in NF was between
79% and 90%, while salt rejecting in MD was ≫99.8% for all solutions
tested, indicating that MD is less affected by scaling. MD is better suited

Table 1
Various processes used for recovering resources from seawater brine.
Technology/process
Addition of an alkali (NaOH) to the brine
Integrated MD-SWRO, with an adsorbent KCuFC(PAN) in MD
feed tank
Adsorption of uranium and other competing ions by using
amidoxime adsorbents
5
Various concentration and purification pretreatment steps
including NF, ED, MVC, chemical softening, IX, membrane
electrolyzer, and dechlorination
Eutectic freeze crystallization technology
Reverse electrodialysis
Electrodialysis with bipolar membranes (EDBM)
Electrodialysis with monovalent selective ion exchange
membranes (S-ED)
Recovered Process efficiency
material
MgO Calcination at 500 °C for 2 h yields MgO with a specific surface area
of 51.4 m2 g−1 and has the highest reactivity
Rubidium With 2 L feed solution and 0.15 g KCuFC(PAN), the system removed
96.6% of Rb+, while recovering 65% of water. However, scaling is a
challenge in this system
Uranium The influence of competing ions needs to be minimized in order to
extract more uranium. The adsorbed mass of uranium was
6.22 mg g−1 in seawater and 3.95 mg g−1 in brine
NaOH, Cl2, and It is more feasible in comparison with other traditional processes.
H2 With 17.5 t/ h brine feed to the process, the membrane electrolyzer
produces 208.4 kg h−1 of 32 wt% NaOH
Salts in pure It has lower energy demand than traditional evaporation based
form separation processes
Energy Presence of organic matter in the RED stack reduced the power
density to 43%, while inorganic matter reduced power density only
up to 7%
Acids and bases The quality of the obtained products is strongly influenced by the
feed water composition. However, they are acceptable for self-supply
in desalination and other industrial activities
Lithium S-ED is a potential industrial method in the prefractionation of
lithium chloride from concentrated seawater/salt lake brines
M.O. Mavukkandy, et al.
Economic feasibility & environmental impact References
Production cost for a ton of MgO via this process is $1526, whereas its [20]
US market price is $617. However, synthesized MgO has higher
reactivity and purity than the commercial MgO. A cheaper base
would make the process more economically feasible
Rb+ has high market price ($14,720 kg−1) and successful extraction [21]
of rubidium can offset the desalination brine management cost. It
would also lower the environmental impacts by reducing the brine
volume
Uranium has high economic value. However, more analysis is needed [22]
to understand the economic feasibility of this process
- Assuming a price of $250 t−1 for chlorine, the potential revenue [23]
amounts to $0.22 kg−1 NaOH, covering the operational cost of the
system. Additional revenue can be obtained from H2 as well
– A total reduction of 29% of the RO facility effluent
– Reuse of ED dilute by feeding it back to SWRO system
Obtaining valuable sources in brine is a sustainable method to offset [24]
the treatment costs of brine
It offers an environmentally friendly solution for energy storage [25]
The membrane cost of EDBM is very high compared to other [26]
technologies that restrict its widespread use
Further work is needed to determine the efficiency of the process and [27]
its possible industrial application. The traditional methods of lithium
recovery have high energy consumption and high pollution. Using
brine to extract is more environmentally friendly
Desalination 472 (2019) 114187
M.O. Mavukkandy, et al.
Fig. 5. Heat circulation between the evaporation and solar ponds enabled enhanced evaporation rate. Adapted from [32].
for desalination of water with high silica concentration such as inland
brackish groundwater.
Reverse osmosis (RO) is a water purification technique that applies
pressure on a solvent, forcing it to pass through a porous membrane in
the reverse direction to that of natural osmosis. Although RO requires a
lot of energy, it is the most widely used process for seawater desali-
nation; it can generate up to 50% of freshwater from the input sea-
water. However, the key limitation of reverse osmosis is membrane
fouling caused by dissolved salts or other biological materials [41–44].
Strong chemicals or membrane replacements are the common ways to
deal with fouling, but it adds up to the total cost, making RO more
expensive. SWRO is the most important application of RO and a valued
desalination method, but it rejects a large amount of concentrated
brine. The disposal of the brine into the sea causes environmental is-
sues. MD can be integrated with SWRO to concentrate the brine and
extract good quality water from it. Furthermore, another advantage of
MD is its ability to trace valuable minerals. Naidu et al. investigated
MD-SWRO system (Fig. 7) and tested its ability to provide additional
good quality water, while simultaneously extracting Rb+ [21].
Fig. 6. Hydrogen and chlorine production (mg s−1) on a monthly basis [31].
6
Desalination 472 (2019) 114187
Rubidium is a valuable mineral with high market price (11,180 US
$/kg) [12,45]. Extracting Rb+ from SWRO would potentially reduce
brine treatment cost and generate economic benefit. Naidu et al. in-
tegrated MD and adsorption systems, which provided long contact time
for encapsulated adsorbent (granular potassium copper hex-
acyanoferrate (KCuFC)) to adsorb Rb+, when compared to traditional
fixed bed adsorbent columns [21]. In addition, mixing of the adsorbent
in the feed tank benefitted from the high temperature of the MD feed, as
adsorption performance of KCuFC was higher at high temperature.
They successfully extracted 2.26 mg Rb+ from 12 L brine, indicating
that approximately 0.7 t Rb+/yr can be mined from desalination fa-
cility, resulting in $10.3 million/yr (based on $14,720 Rb+/kg). [21]
Integrating MD with RO can maximize the production rate and re-
duce energy consumption. As shown in Fig. 8, Ali et al. studied different
configurations involving cascading and brine recycling using simula-
tions to find the best configuration, the increase in recovery rate, and
the reduction in energy consumption [46]. Authors found that recycling
MD brine to the RO as feed increased the recovery rate by 40% at an
energy cost of 0.9$ m−3, whereas recycling MD brine back to the MD as
M.O. Mavukkandy, et al.
Fig. 7. Process flow of Rb+ sorption, sorbent regeneration and Rb+ recovery.
Adapted from [21].
feed does not give a similar increase in recovery rate. Results also show
that using MD/RO interplay systems connected in series offer the
highest performance. 90% recovery rate was obtained with 8 stages
employed, but this increased production cost to 9$ m−3.
Yan et al. utilized hydrophobic PVDF membrane to treat RO brine
under different feed velocities and temperatures.Results showed that
MD is able to achieve excellent desalination performance with recovery
rate higher than 70%, and permeate conductivity lower than
11 μS cm−1. No membrane fouling was observed initially; however, a
decrease in thermal performance and pore wetting happens when
concentration factor exceeds 3.3. The desalination flux can be improved
to some extent by increasing the feed temperature, but fouling can be
aggravated at higher temperatures and cause a sharp decrease in flux.
Increasing the feed velocity can lower the severity of membrane
fouling, but when velocity exceeds 0.4 m s−1, the desalination perfor-
mance starts to decline. The scaling layer on the membrane can be
removed by flushing the membrane with pure water for 20 min.
However, increasing the feed temperatures lower flux reversibility,
since the scaling layer is less compact under low temperatures.
Chul Woo et al. investigated the modification of nanofiber by CF4
plasma treatment and evaluated their performance via air gap MD
(AGMD) using real RO brine [48]. Plasma treatment is a surface mod-
ification method that provides resistant coating on membrane surfaces.
Fig. 8. An integrated MD-RO setup for enhanced system performance [46].
7
Desalination 472 (2019) 114187
CF4 plasma treatment partially enhances anti-wetting properties by
enabling polymer modification or etching of the membrane. Treating
nanofiber membranes with CF4 causes the membrane surface to have
much lower surface energy, resulting in an omniphobic membrane with
anti-wetting properties. Authors demonstrated that plasma treated na-
nofiber membranes have increased fluorination, which led to higher
desalination flux (15.28 L m−2 h−1) even with the addition of 0.7 mM
sodium dodecyl sulfate to the RO brine. Commercial PVDF membranes
are unable to tolerate a 0.3 mM of surfactant addition, making this
technology suitable for producing clean water from highly saline water
that contains organic contaminates.
Bamufeh et al. designed an integrated system of multi-stage dis-
tillation (MED) and MD for water desalination and brine treatment
[49]. MED is an evaporation technique that is widely used to desalinate
water by spraying the brine over heated pipes. The hot water vapor is
then used to heat the next stage of the evaporation process where water
condenses and is collected as pure water. MED concentrated brine is
then directed to MD, which produces secondary distilled water. MD and
MED are integrated with adjacent industrial plant, where excess heat is
transferred from the industrial facility to the desalination system. The
cost of desalinated water is $1.65 m−3, and 4800 kW of excess process
heat is available from the hot source starting at 358 K. MD processes
2600 ton day−1 of concentrated brine, and reduces it to
M.O. Mavukkandy, et al. Desalination 472 (2019) 114187

backwashing the membrane was effective to reduce crystallization, al-

lowing to concentrate SWRO RO brine toVCF of 2.08.
Membrane distillation systems can be integrated with other tech-
nologies to recover various minerals from brine or reduce the volume of
brine. In most circumstances, a salt rejection of 100% is achievable.
Although it requires more energy than RO, it requires less energy than
the traditional evaporation and crystallization process and can tolerate
hypersaline brines. Moreover, it does not require extensive pretreat-
ment that is normally required for pressure-based technologies.
However, the main limitation of this technology is the fouling and
scaling on the membrane, lowering the flux of the membrane sig-
nificantly. Incorporating MD with other technologies to recover re-
sources from brine is possible but the performance limitations such as
scaling, fouling and low flux etc. need to be considered.

3.3. Membrane distillation crystallization (MCr)

Fig. 9. A schematic of membrane distillation crystallization set up [55]. Membrane distillation crystallization (MCr) is a hybrid of mem-
brane distillation and crystallization in which brine becomes saturated
and then supersaturated to facilitate the formation of crystals, which
1339 tone day−1 with production of 1250 ton day−1 of distilled water.
are finally collected in an external crystallizer [52–54]. The membrane
Sanmartino et al. tested various chemical treatment strategies prior
employed in this process separates the vapor phase from the liquid
to direct contact membrane distillation (DCMD) for processing the re-
phase, producing a concentrated solution and pure water as shown in
verse osmosis brine [50]. The membranes employed are polytetra-
Fig. 9. Membrane distillation crystallization can form specific crystal
fluoroethylene (PTFE) membranes with different mean pore sizes
size distribution and these crystals can be modified to form specific
(TF200 and TF400). Authors' objective was to minimize the volume of
crystal superstructures. Quist-Jensen et al. utilized the membrane
RO brine and increase water production rate. The treated brine had an
crystallization for treating nanofiltration retentate and RO brine [13].
initial concentration of 55 g L−1 total dissolved solids (TDS), with NaCl
They also conducted thermodynamic modeling to predict the water
as the most abundant solid. Calcium present in brine is responsible for
recovery factor and the amount of minerals that can be extracted. It was
early membrane fouling and the continuous decrease in membrane flux,
found that multivalent ions such as barium, strontium, and magnesium
which causes the DCMD process to end early and limit its ability to
are easier to recover from NF retentate whereas lithium can only be
concentrate brine sufficiently. Chemical pretreatment of RO brine
extracted from RO brine. KCl and NiCl2 may be extracted from both NF
works on removing calcium hardness and/or sulfates by adding salts,
retentate and RO brine. In addition, it was suggested that copper and
which helps in extending the membrane lifetime and prevent pore
manganese compounds could also be recovered from desalination
wettings. The precipitates that resulted from the chemical treatment are
brine.
then removed by filtration techniques. Authors reported that the ad-
As a follow-up of above-mentioned integrated MD-adsorption study
dition of both NaOH and Na2CO3 to brine at high temperature (348 K)
[21], Choi et al. investigated an integrated submerged MD-adsorption
gave the best results. All Ca+ ions precipitated during the pretreatment.
system to extract Rb+ from brine and improve fresh water recovery
The flux of TF200 and TF400 membranes increased initially by 18–24%
[56]. They hypothesized that when compared to flat sheet cross flow
respectively and the final concentration of brine increased to 196 g L−1
MD, submerged hollow fiber MD has benefits in terms of low heat
of TDS using TF450, and 388 g L−1 of TDS using TF200. Without che-
consumption and process intensification since feed recirculation is not
mical treatment, the final concentration of brine using TF200 and
essential in this set-up. The adsorbent used was granular KCuFC and
TF400 is 153 g L−1 and 136 g L−1 of TDS respectively. Membrane
desorption was carried out using a solution of 0.2 M NH4Cl. Results
TF200 maintained full rejection, but membrane TF450 wetted slightly
show that the extraction of Rb at optimum temperature (55 °C) depends
after 5 h. This is due to the detergents present in RO brine that easily
on the dose rate of KCuFC. Rubidium extraction was 59.9% at a dose
penetrate into TF450 membrane pores, favoring wetting.
rate of 0.05 g L−1 and it increased to 97.5% at 0.24 g L−1, indicating
Submerged membrane distillation (S-MD) is an alternative to con-
high affinity of KCuFC for Rb+. The adsorption capacity depends on the
ventional membrane distillation, which reduces energy consumption
size and the form of KCuFC and the particle form had a higher ad-
and offer higher thermal efficiency. The membrane module is sub-
sorption capacity than the powder form. A continuous supply of feed
merged in the feed solution tank, resulting in a lower heat loss. Choi
solution, adsorbent separation and generation enhances the perfor-
et al. investigated three different S-MD configurations for RO brine
mance of the process. The system was able to generate fresh water and
treatment: submerged direct contact membrane distillation (S-DCMD),
extract Rb+ for two repeated cycles. It is to be noted that scaling poses a
submerged vacuum direct contact membrane distillation (S-VDCMD)
major challenge to this system. CaSO4 was crystallized and deposited on
and submerged vacuum membrane distillation (S-VMD) using hollow
the membrane surface, which deteriorated the performance of the
PVDF membrane [51]. Results show that 14–77% increase in flux was
membrane. More research is needed to prevent or delay the scaling on
obtained for submerged membrane distillation with vacuum in-
membrane surfaces.
corporation (S-VMD and S-VDCMD), in comparison with S-DCMD, due
to its higher driving force. More specifically, S-VMD at 50 mbar ob-
3.4. Electrodialysis (ED) and reverse electrodialysis (RED)
tained 40–77% higher permeate flux in comparison to S-DCMD and S-
VDCMD (500 mbar and 700 mbar). Although, S-VMD has the lowest
Electrodialysis system consists of a series of anion and cation se-
energy requirement and highest permeate flux, it is strongly influenced
lective semi-permeable membranes stacked together [57–59]. Under
by brine concentration. S-DCMD and S-VDCMD showed more promising
the influence of electric potential, anions and cations will move towards
results for highly concentrated solution; they were able to concentrate
the anode and cathode respectively. Cation exchange membranes
brine solution to over volume concentration factor of 2.08. However, S-
(CEM) would block the anions and anion exchange membranes (AEM)
DCMD was strongly affected by feed temperature losses because of the
would block the cations, creating the flow of separate diluent and
PVDF membrane tendency to form pore crystallization. Repeated air-
concentrate. In general, the ionic transport rate in ED depends on the

8
M.O. Mavukkandy, et al.
concentration of ionic species and the material properties of the ion-
exchange membrane, such as ionic site density and overall resistance.
As this is not a pressure-driven process, chances of formation of a
compact fouling layer is low and hence the requirement for cleaning
and regeneration chemicals is minimum [60]. However, the suspended
solids with positive or negative charges may be deposited on the
membrane surfaces or on the spacers, increasing its resistance [61–64].
This is largely mitigated by electrodialysis reversal, where the electrical
polarity is reversed at certain intervals (every 30–60 min), causing the
removal of deposited particles. ED offers high recovery rate making this
technology irreplaceable for high-salinity water treatment as well.
However, the energy requirement is proportional to the salt con-
centration in the feed, making its operation expensive for hypersaline
brines. In addition, ion exchange membranes get poisoned by the pre-
cipitation of the metal cations, causing degradation of the membranes,
which in return reduces desalination efficiency. It has to be noted that
beyond a certain current density limit, splitting of water into H+ and
OH− ions occurs, lowering the overall efficiency and therefore this has
to be operated below the current density limit [65].
Currently, the major application of ED is in desalination of seawater
or brackish water, and brine treatment. Several researchers have
modified the ED process for target-specific applications. For instance,
Wang et al. developed a selective electrodialysis membrane bioreactor
(EDMBR) by integrating ED into an electrochemical membrane bior-
eactor (EDMBR) [66]. The system is used to recover nutrients from
urine, treat source-separated urine, generate electricity, and utilize the
generated electricity for brine desalination. Ammonia concentration in
the dilute urine was significantly reduced by stripping before urine was
injected into the EDMBR system. After injecting urine, the system ex-
tracts phosphorus and ammonia, and generates electricity-using elec-
trodialysis at the same time. A maximum power density of 23.5 W m−3
was generated at a resistance of 1000 Ω. In addition, 94.5% of SO42−,
97.4% of NH4+, and 76.7% of PO43− were removed from urine. About
65% of the phosphorus and 54.9% of sulfate removed were recovered in
a concentrated solution, and other minerals such as NaCl were retained
as brine. As the results indicate, the system was able to successfully
recover nutrients, desalinate urine, and treat wastewater simulta-
neously. More specifically, EDMBR treated hypersaline wastewater
with simultaneous removal of carbon, nitrogen, phosphorus, and sulfur
from urine. To make the system more effective, operation conditions
and reactor construction should be optimized in further studies. Thus,
the recovery rate of phosphate could be improved.
In a recent study, Du et al. investigated the energy efficiency and
process design of an integrated system involving nanofiltration, con-
centration, chemical softening, ion-exchange softening, dechlorination
and membrane electrolysis, for producing sodium hydroxide from
seawater brine via a membrane chloralkali process [23]. A schematic of
the process is shown in Fig. 10. Authors established the technical fea-
sibility of this process with additional benefits of reduced environ-
mental impacts associated with the brine disposal and increased water
recovery of the RO facility. The proposed process (NF retentate at a rate
of 12.20 t/h and the brine purge at 0.26 t/h) can reduce up to 29% of
the effluent from the RO facility. These effluents have a higher con-
centration than RO brine and hence achieving zero liquid discharge via
further concentration using appropriate technology such as solar/eva-
poration ponds can be considered. Moreover, the ED diluate can be
mixed with the RO feed as it has a similar salinity with that of seawater,
increasing the RO recovery rate from 50% to 57% in a regular RO plant.
It has to be noted that this ED diluate does not require any extra pre-
treatment as it is coming from the RO brine. As NaOH is produced
within the desalination facility, the conventional method of con-
centration, transportation and dilution of NaCl and NaOH can be
avoided here. Authors found that for every kilogram of sodium hy-
droxide produced, 27.6 g of hydrogen and 870 g of chlorine can be co-
produced. It is also possible to produce sodium hypochlorite from
NaOH and Cl2. Further studies are needed to optimize the operations of
9
Desalination 472 (2019) 114187
each component and control issues, especially during start up and shut
down. However, this process is more feasible in comparison with tra-
ditional standard chlor-alkali process, Melian-Martel process, and
Garriga process. A thorough optimization of this integrated process can
significantly reduce the operational cost and the environmental da-
mages associated with various processes in the desalination facility, by
increasing the water and mineral recovery ratios.
Kumar et al. investigated another method for the production of
sodium hydroxide and hydrochloric acid from brine streams using di-
rect electrosynthesis (DE), and described the development of the pro-
cess and its limitations [67]. In the DE process given in Fig. 11, OH−
and H+ are produced using water-splitting reaction and are combined
with brine stream to produce HCl and NaOH. Figure below shows a
schematic diagram of DE. Hydrogen and oxygen are produced at the
anode and cathode, respectively, and upon the reaction with brine, HCl
and NaOH are generated. Only three compartments are required in this
process: one for the production of HCl, one for the production of NaOH,
and another for the circulation of the brine solution. It is important to
mention that DE is not a new technology; and it has been ruled out
previously due to the formation of chloride gas on the anode. This
problem was solved by Lin et al. using the novel elctrocoating ap-
proach, but the production of sodium hydroxide was low in their pro-
cess [68]. Kumar et al. proposed that adding catalysts that suppresses
chloride production and selectively produces oxygen can solve the
problem, while still generating NaOH and HCl efficiently without the
need of a pure NaCl stream. However, little studies are done on the
relative activity of electro-oxidation catalysts for the production of
oxygen over chlorine. With more research, DE has the potential to re-
cover HCl and NaOH from brine streams efficiently, reduce energy
consumption needs, and lower the negative environmental impact of
brine producing industries.
Allioux et al. introduced electrically responsive hybrid ion-selective
membranes for selective gated transport of ionic species for electro-
dialysis applications [69]. Normally, the ionic transport rate in elec-
trodialysis is limited by the concentration of ion species, the material
properties of the ionic-exchange membrane such as ionic sites density
and overall resistance, and other process conditions. To increase the
ionic transport rate, Allioux et al. developed an electrically responsive
hybrid ion-exchange membrane that is independent of the composition
of the feed and the electrodialysis stack configuration. This process is
called capacitive electrodialysis and it requires hybrid ion-exchange
membrane materials that are made of macro-porous and inorganic
electricity conductive reinforcement, filled with a polymeric ion-ex-
change material. The hybrid ion-exchange membrane is able to pro-
mote the migration of selected ionic species by up to 6 folds, and does
not get damaged by high voltages or water oxidation and reduction
reactions during ED process. This new technology is cost-effective and
has potential applications in resource recovery and desalination.
As the demand of lithium resource has been growing rapidly, Guo
et al. investigated the feasibility of extracting lithium from seawater or
salt lake brine using selective electrodialysis technology (S-ED).The
results show that S-ED is a potential industrial method in the pre-
fractionation of lithium chloride from concentrated seawater/salt lake
brines. Typically, an ED comprises of a series of anion selective and
cation selective semipermeable membranes stacked together. However,
S-ED has monovalent selective ion exchange membranes. It can sepa-
rate monovalent and multivalent ions due to the strong retention of
multivalent ions and high permeability of monovalent ions of the
membrane. The initial volume ratio of concentrating and desalting so-
lution (VC/VD) is an important factor in S-ED process. At the same
applied voltage, the smaller the VC/VD value, the faster the increasing
rate of ionic concentration. The optimal voltage for the lithium chloride
recovery process for the concentrated seawater is 7 V. The optimal VC/
VD value found is 0.6 for concentrated seawater. These conditions give
high recovery ratio of Li+.
Fernandez-Gonzalez C. et al. investigated the ability of
M.O. Mavukkandy, et al.
Fig. 10. Schematics for producing sodium hydroxide from seawater brine [23].
Fig. 11. A schematic of the direct electrosynthesis process [67].
electrodialysis with bipolar membranes (EDBM) in recovering brine as
acids and bases [26]. Authors focused on the technical performance of
EDMB and the possibility of valorization of brine with high NaCl con-
centration. Authors additionally discussed economic barriers to the
technology that prevents its use. The membrane cost of EDBM is very
high compared to other EDMB technologies that prevent its use. A
diagram of EDMB process is shown below. In another study, Hoshino
introduced membrane based process for recovering lithium (Li) from
seawater [71]. Because of it high Li conductivity of 10−3 Scm−1, Li+
ion conductive glass–ceramics was selected as the lithium ion selective
membrane (LISM), which allowed the selective transport of Li+ ions
from negative electrode to the positive electrode. LISM functions as a
salt bridge and facilitates the transport of Li+ from high- to low-con-
centration solution (from seawater to Li recovery solution). It can be
noted that this separation process generates electricity as well and it
was observed that lithium recovery ratio increased to ~7% after 72 h
without any external power supply.
10
Desalination 472 (2019) 114187
Reverse electrodialysis (RED) is an emerging membrane based
technology that harvests salinity gradient energy from the difference in
the salt concentration between seawater and river water. Similar to
electrodialysis, reverse electrodialysis is made of CEM and AEM stacked
together in an alternative order. Positively charged ions diffuse through
CEM, while negatively charged ions diffuse through AEM. This trans-
portation of positive and negative ions creates charged poles in the RED
system, similar to an electrochemical cell. The maximum amount of
electrical energy that can be possibly generated in the RED system
depends on the temperature of water, the chemical composition of the
dissolved salts, and the concentration of the two solutions. However,
the actual amount of electricity generated depends on the selectivity of
the membrane and the internal resistance of the cell.
Reverse electrodialysis (RED) has been used in past few years to
generate electricity by mixing seawater with river water. RED has other
applications that are currently being investigated, such as generating
power from concentrated brine. Despite its ability to generate high
M.O. Mavukkandy, et al.
power density from concentrated brine, RED has not received much
research attention. Most of the experiments only used concentrated
NaCl, while real RED applications may involve water that includes
other inorganic and organic matter. Kingsbury et al. determined the
impact of organic matter and ions (other than Na+ and Cl−) on RED
performance, using five types of real water salinity gradient (seawater,
river water, desalination brine, saline wastewater from a pickling plant,
and treated wastewater) [25]. The pairs used are seawater/brackish
water, seawater/rainwater, seawater/treated municipal wastewater,
reverse osmosis (RO) brine/RO influent (i.e., brackish groundwater),
and pickling brine/storm water. Results show that the presence of or-
ganic matter in the RED stack has a greater impact on power density
than inorganic matter, indicating that organic matter plays an im-
portant role in determining RED performance. Organic matter reduced
the power density to 43%, while inorganic matter reduced power
density only up to 7%. In addition, the presence of UV-absorbing or-
ganic matter in dilute water results in a lower energy efficiency and
lower membrane permselectivity. The organic matter in pickling brine/
stormwater behaved differently; it increased the RED performance
significantly in comparison with the controls. This shows that RED
might have a promise for industrial recovery application.
Wang et al. attempted to solve the ED energy problem by combining
RED with ED and tested it on phenol containing wastewater char-
acterized by high COD and high salinity [72]. RED operates by ex-
tracting the potential due to salinity gradient through the natural
transport of ions and simultaneously attains chemical separation, while
ED utilizes the energy produced by RED to complete desalination. The
authors tested RED/ED system on phenol containing wastewater, but it
can be used in other high salinity process based on a list of conditions
that include a low percentage of multivalent ions, and suitable condi-
tions for ion exchange membrane such as temperature and pH. Results
show that the system uses less electrical energy than stand-alone ED
(i.e. 17.65 kWh m−3 vs 25.32 kWh m−3), and recover more salinity
power gradient (0.35 kWh m−3) under a pre-desalination rate of
27.44% in the RED stage. Overall, the system has several advantages
including lower-energy desalination, high-valued resource reclamation,
and salinity energy usage in a high-salinity wastewater treatment pro-
cess.
Electrodialysis has been used in several studies to recover certain
resources from brine by integrating it with other technologies. It se-
parates ions from water without phase change, which results in a low
energy consumption. The product water generated by this system re-
quires minimum disinfection treatment, typically performed through
chlorination. One of the main limitations is the selection of membranes
and the stack, which are highly dependent on the feed water chemistry.
Thus integrating ED with other technologies can result in complications
if there is a change in the feed composition. In addition, it requires
water pretreatment to prevent fouling. Reverse electrodialysis is used to
generate power by mixing seawater and with river water. Other ap-
plications such as generating power from concentrated brine are being
investigated. A major drawback of this process is that beyond a parti-
cular current density, the diffusion of ions through the EDR membranes
is no longer linear to the applied voltage but leads to water splitting and
lowers the system's efficiency.
3.5. Chemical precipitation
Precipitation methods are usually simple, cheap and easy to com-
mercialize [73]. A typical precipitation process involves various steps
such as reagent addition, pH adjustment, flocculation, sedimentation
and separation of the solids from liquid. Employing membranes could
substitute the flocculation, sedimentation and separation steps. Dong
et al. studied the recovery of reactive MgO from reject brine by pre-
cipitating with NaOH [20]. Authors show that reject brine can be used
to produce MgO with high reactivity, which can be used in several
industries such as food and pharmaceutical industries. NaOH is chosen
11
Desalination 472 (2019) 114187
as an alkaline source to react with Mg2+present in the rejected brine
solution. The products of the reaction are reactive Mg(OH)2 and small
amount of CaCO3. The Mg(OH)2 is further calcined under a range of
temperature and duration to produce reactive MgO, which has various
applications in the construction industry as an additive and a binder, in
refractive industry, agriculture, and environmental and chemical ap-
plications [74–79]. Results show that a NaOH/Mg2+ ratio of 2 gives the
highest purity of Mg(OH)2. Increasing calcination temperature and
duration lowers reactivity of MgO. A calcination temperature of 500 °C
and a duration of 2 h was reported to produce the most reactive MgO
samples, with SSA of 51.4 m2 g−1. The production cost of MgO in the
market is $617 per ton. Producing MgO from reject brine using NaOH
costs $1526 per ton MgO, thus a cheaper base would make the process
more economically feasible. It is noted that synthesized MgO has higher
reactivity and purity than the commercial MgO. On the other hand,
Mohammad et al. evaluated the recovery of magnesium from brine via
precipitating Mg2+ with ammonia [80]. The recovered Mg(OH)2 can be
utilized in the post-treatment of desalinated water for remineralizing
the water, thus saving the transportation and production costs. A 5-
level, 3 factor central composite design was employed for maximizing
the recovery of magnesium with respect to brine salinity, reaction
temperature and ammonia to magnesium molar ratio. At 15 °C, authors
report a maximum 99% recovery from a brine of salinity 85 g L−1 and a
molar ratio of 4.4 NH3:1 Mg. As the solubility of Mg(OH)2 is directly
proportional to the temperature, low temperature is recommended for
the complete recovery for magnesium. In another study, Na & Kim re-
ported a 3-step process for recovering Mg from brine [81]. The process
involves precipitating magnesium using paper sludge ash, dissolving
Mg in sulfuric acid (H2SO4, 1.0 M), and precipitating magnesium sulfate
(MgSO4) using ethanol with solution to ethanol ratio of 1:1. Best con-
ditions yielded a reaction efficiency of 98%, 70.8%, and 88%, respec-
tively for each step with an overall efficiency of 61.1%.
3.6. Adsorption/desorption process
Past studies reported the adsorptive recovery of minerals at low
concentrations. In general, it is complicated to recover a specific mi-
neral at high concentration due to low adsorption capacities and se-
lectivities. However, recent lab-scale studies show that high con-
centrations of minerals can also be recovered [82–84]. The adsorbent
needs to have high adsorption capacity and selectivity towards the
mineral of interest. The complete selectivity of adsorption/desorption
of specific minerals has not been established yet, because of the pre-
sence of much higher concentrations of other minerals that compete for
adsorption. Wiechert et al., investigated the uranium recovery from
brine using amidoxime functionalized adsorbent [22]. Desalination
brine reject makes a good source of uranium as it has a significantly
higher concentration of uranyl than seawater. Nuclear fuel resources
are needed to be explored due to the expected rise of nuclear power.
The mass of the adsorbed uranium and other ions (zinc, copper, iron,
vanadium, calcium, and magnesium) were found using inductively
coupled plasma mass spectroscopy technology. The adsorbed mass of
uranium in brine was 3.95 mg g−1 adsorbent, and 6.22 mg g−1 ad-
sorbent in seawater. However, the adsorbed mass of iron and vanadium
increased in brine in comparison with seawater. The adsorption of ur-
anium in brine is over-predicted due to the presence of other competing
ions in the sample. The influence of those competing ions need to be
minimized in order to extract more uranium in brine.
In another study, Dindi et al. proposed a process to capture CO2 and
utilize it to treat reject brine for safe disposal, and produce chemicals
like NaHCO3 [85]. The first step of the process is to remove chloride
ions from brine using mixed metal oxide, and then separate the mixture
(Fig. 12). The resulting brine becomes more alkaline due to the higher
level of OH-ions, which are transformed to a chloride-form hydro-
talcite. The brine containing NaCl and NaOH is then used for CO2 ab-
sorption (25 °C, 1 bar) to precipitate the NaHCO3. This process removes
M.O. Mavukkandy, et al.
Fig. 12. Schematic diagram for the proposed process for recovering CO2 and resource recovery from brine [85].
Na+ from the brine, which its absence makes the brine safer to dis-
charge into the environment, in addition to Cl−. The chloride-form
hydrotalcite can be recycled thermally or using ion-exchange to re-
generate Mg-Al-O for another cycle of CO2 adsorption and chloride
removal. The process is shown in the schematic diagram below. Final
product NaHCO3 can be sold to partially compensate for the high cost of
carbon capture, utilization, and storage technology. Sodium and
chloride concentrations in brine were successfully reduced to 20% and
70% respectively using this method, making the brine safe for disposal
in seawater.
3.7. Eutectic freeze crystallization (EFC)
Phase-diagram of the salt-water mixture has a specific point, known
as eutectic point, at which an equilibrium exist between salt, ice and the
solution with a specific concentration. Eutectic freeze crystallization
(EFC) involves simultaneous crystallization of ice and salt [86,87]. As
ice, salt and solution have different densities at the eutectic point, they
can be separated by gravimetric methods. Randall and Nathoo con-
ducted a thermodynamic assessment on the resource recovery via
freezing from RO brine, seawater and stored urine [24]. They showed
that salt recovery from RO brine and seawater is possible using EFC
technology. EFC can retrieve water and salts in pure form with a low
energy requirement in comparison with the traditional evaporation
based separation processes. Each salt has a certain eutectic point;
therefore, several pure salts can be recovered from the solution. The
brine is cooled down below its freezing point and when it reaches a
certain temperature, crystals start to form resulting in a brine/ice
crystals mixture. Further cooling increases the salt concentration and
the formation of ice crystals. At the eutectic point, no further ice is
formed and the salt reaches the saturation and the products (ice and
salt) are then separated. The feasibility of the process for a specific type
of water depends on many variables. Authors also explained various
tools that can be used to check the feasibility of the process without
having to run complex simulations and calculations. Producing more
salts at higher temperatures can be achieved by adding acid to the EFC
streams, which in return increases the economical profitability.
One of the issues in EFC is the formation of ice scale layer on the
12
Desalination 472 (2019) 114187
surface of heat exchanger following long steady state operations
[88,89]. Leyland et al. investigated the impact of nature of brine and
crystallizer operating conditions such as hydrodynamics and subcooling
on the ice scale formation [90]. The time between formation of initial
nucleation in the bulk and the development of ice on the wall – scaling
induction time – was used to characterize the scaling tendency. As the
hydrodynamics improved (i.e., when the flow conditions changed from
less turbulent to highly turbulent), authors found that the scaling was
delayed, which was attributed to the rapid supersaturation distribution
into the bulk at higher Reynolds number. It was also found that at
turbulent conditions, scaling induction time was a function of heat
transfer driving force, with higher driving force reducing the scaling
induction time because of the rapid solid build-up in the bulk and
higher adhesion of ice with the cold walls. Authors also studied the
influence of impurities on the scaling induction time for the eutectic
Na2SO4-H2O system. It was reported that presence of impurities delayed
the scaling induction time, because of their electrostatic interactions
with the electropositive ice surface. Impurities reduced the force of
adhesion between the ice and the wall by lowering the partial positive
charge on the ice surface. In addition, it was also noted that scaling
tendency was inversely proportional to the solute concentrations as
high mass transfer resistance of solutes away from the ice-liquid in-
terface created a higher resistance for the growth of ice layer.
3.8. Pressure retarded osmosis (PRO)
Pressure retarded osmosis (PRO) is an emerging technology for
harvesting salinity-gradient energy by separating a solvent from a
concentrated pressurized solution [91–93]. It utilizes the Gibbs free
energy of mixing freshwater with brine to generate power. Brine
streams from desalination and municipal wastewater treatment plants
can be combined in the PRO system to produce energy and power fa-
cilities. Municipal wastewater flows through the membrane and dilutes
the brine, increasing its volume. Subsequent increase in the saltwater
chamber pressure can be utilized to generate energy, particularly up to
10 W/m2 depending on the salinity of the streams. However severe
fouling by the waste effluent is a major limitation in this process. In
addition, PRO is not considered economically feasible as there is no
M.O. Mavukkandy, et al.
cost-effective and high performing PRO available in the market. This is
the main reason why Statkraft, Norway's leading power company, dis-
continued investments in pressure retarded osmosis in 2012.
O'Toole G. et al. investigated the membrane module efficiency and
parasitic loads within the PRO system by determining net-specific en-
ergy production using simulations [94]. The overall net specific energy
that can be produced using PRO is approximately 0.12 kWh m−3 of
permeate, if freshwater and seawater are used as feeds. In addition, the
authors determined relationship between net specific energy and power
density as function of flow rates, membrane area, and operating pres-
sures. To maximize resource recovery, authors suggest a low power
density or low membrane productivity. Coupling PRO with RO has been
suggested to generate power and increase water recovery by using RO
brine as PRO feed. In another study, Altaee et al. modeled various
parameters of PRO-RO system and investigated their impacts on the
system [95]. Using an RO process with 52% recovery rate and feed
salinity of 35 g L−1, the power density of PRO obtained was 24 W m−2
using 4.5 M NaCl draw solution. Increase in the RO feed salinity to
45 g L−1 resulted in RO recovery rate of 46% and PRO power density
increased to 28 W m−2 using 5 M NaCl draw solutions. This shows that
increasing the feed salinity of PRO increases the power density and RO
recovery rate. It was concluded that PRO-RO system gives more ad-
vantages than a stand-alone RO.
Capacitive mixing (CapMix) is another method for generating en-
ergy by taking advantage of the voltage difference between two salt
concentration-dependent electrodes. CapMix systems generally have
low power density (~0.4 W m−2) when compared with typical PRO
(7.5 W m−2) or RED (2.9 W m−2) and intermittent power output
[96–98]. Kim et al. reported a new method of capturing the salinity
gradient energy by a concentration flow cell with copper hex-
acyanoferrate electrodes which developed electrode potentials based on
Na+ activities and an AEM which developed a Donnan potential based
on Cl− activities [99]. A peak power density of 12.6 ± 0.5 W m−2
(with an average of 3.8 ± 0.1 W m−2) was obtained when a synthetic
seawater (30 g L−1 NaCl) and freshwater (1 g L−1 NaCl) were used. On
the other hand, when a hypersaline brine (300 g L−1 NaCl) and fresh-
water (1 g L−1 NaCl) were used, peak power density was increased to
26.3 ± 1.3 W m−2 (with an average of 9.4 ± 0.9 W m−2). Authors
also found that the total power was doubled when two flow cells were
stacked in series. Tan et al. demonstrated a new method of extracting
salinity gradient energy that has higher power density than RED and
CapMix cells [100]. The method is based on the extraction of chloride-
ion (Cl−) and insertion with metal chloride electrodes, which works
similar to chloride-ion batteries, but by utilizing salinity gradient to
power it instead of electricity. The electrochemical characteristics of
the electrodes are important for power generation. Authors reported a
maximum power density of 3.17 W m−2 for the cells with BiCl3 elec-
trodes.
3.9. Microbial desalination cell (MDC)
Most desalination technologies that exist today are relatively effi-
cient, but highly energy intensive. This challenge may be solved by
microbial desalination cell (MDC) technology, as it has the potential to
convert energy stored in wastewater to useful energy and use it in de-
salination [101,102]. This technology is an extension of microbial fuel
cell technology. It consists of a cathode, anode, cation-selective mem-
brane, and anion-selective membrane as shown in Fig. 13. Organic
matter from wastewater passes through the membrane and accumulates
in the anode chamber, producing a biofilm that clings to the anode. The
geobacteria oxidizes the organic matter, releasing proton and electrons.
MDC can be used as stand-alone energy production and salt removal
system, or as a pretreatment for reverse osmosis. The most important
parameter is the desalination rate. As MDC uses energy from its system
while treating water, it can be considered as an alternative to RO [103].
However, MDC is still in its early stage of development. Previous studies
13
Desalination 472 (2019) 114187
Fig. 13. A microbial desalination cell [104].
showed that a single MDC is unsuitable for a real water desalination
application, but multiple MDC can be stacked together to increase
production. Sevda et al. determined the suitable conditions for high
current and high power generation in two UMDC connected in cascade
mode [103]. Using the first UMDC at high power generation mode, and
the second UMDC at high current generation mode gives the best re-
sults. The highest salt removal was 72% at SRT of 40 h, and the highest
COD removal achieved was 83% at a HRT of 60 h. The maximum
current density was 2375 mA m−2, while the maximum power obtained
was 5879 mW m−2. The results indicate that two UMDC in cascade
mode are suitable for scale up. They provide high power generation,
high current generation with high salt and COD removal.
MDC has the ability to convert energy stored in wastewater to useful
energy and then use to desalinate water. However, this process is still at
an early stage of development. A single MDC cell cannot be used for real
water treatment application, but several cells combined in a cascade
mode are suitable for scale up. The main limitation is that the perfor-
mance of the cell is severely affected by irreversible reactions and
processes that occur in the cathode and anode compartments (Table 2).
4. Conclusions and future outlook
Brine management is one of the major problems facing the desali-
nation industry. Disposing brine to the sea has serious negative impacts
on the environment and marine life. Although modern brine discharge
designs are being developed with lower negative impacts, they are
usually expensive. Recovering various valuable resources from brine
can lower the cost of treating brine and resolve the economic and en-
vironmental concerns. The most common technologies used to recover
resources from brine are: solar pond, membrane distillation, membrane
distillation crystallization, pressure retarded osmosis, electrodialysis,
reverse electrodialysis, microbial desalination cell, and adsorption.
Some of these technologies are effective to a certain degree, yet each
one of them has certain operational limitations. Although there are
several technologies available for resource recovery from brine, they
are expensive as of now and hence more research is needed in order to
develop advanced low-cost technologies.
All mentioned technologies have the ability to extract various re-
sources with high economic value from brine in a sustainable and en-
vironmentally friendly way. The major differences between these
technologies lay in the process efficiency, economic feasibility, and the
type of resource extracted. For concentrating brine, MD in combination
with other technologies has the highest potential due to its relatively
low energy requirement. However, limitations such as membrane
 Table 2
Benefits and limitations of different technologies used in ZLD systems.
Technology/process
Concentration flow cells
Concentration flow cells
ED modified: inserted hydrophobic
macro-porous carbon cloths
between CEM and AEM
Electrically responsive hybrid ion-
exchange membrane for ED
Electrodialysis (ED)
Fertilizer drawn forward osmosis
(FDFO)
14
Hybrid RED/ED system
Ion exchange membrane electro-
dialectic
Ion-exchange membranes that are
mono-/multi-valent anion-selective
and with high permselectivity for
ED
Membrane distillation (MD) and reverse
osmosis (RO)
Modified reverse osmosis (RO)
Pressure retarded osmosis (PRO)
Application Benefits Economic feasibility & environmental impact Limitations References
Harvesting salinity This method has higher power density than RED This process uses expensive ion exchange The electrochemical characteristics of the [100]
gradient energy and CapMix cells membranes that restricts its commercialization. electrodes are important for power generation
M.O. Mavukkandy, et al.
Energy harvested from brine can be utilized in brine
treatment before disposal or other processes
Harvesting salinity This method has higher power density than RED Method has been experimented only with sea water, Na+ intercalation and deintercalation processes [105]
gradient energy and CapMix cells but shows potential for brine energy harvesting is affected by electrode structure and
composition
Used for ED – Solves the poisoning problem of ED by Heavy metals have high economic value. Extracting The use of complexation agents need to be [106]
applications capturing heavy metal ions on the surface of heavy metals from brine can offset brine treatment investigated to treat streams made of heavy
the carbon cloth cost metal ions and increase selectivity of the
– This process can be scaled to an industrial size reduction process
– Increases desalination efficiency
Selective transport of – Promotes migration of selected ionic species It offers cost-effective solution to selective ionic Feedwater pre-treatment is essential to minimize [69]
ionic species by up to 6 folds transport the ED stack fouling
– Cost effective approach
Brine source recovery Can be combined with renewable energy to treat If the profit is used in brine treatment, it can help in Highly concentrated brine causes scaling [107]
brine reducing the cost of brine treatment
Water recovery from – A stand-alone process where regeneration step Lowers brine volume by recovering water from Flow rate change only affects energy [108]
brackish water is not required brine. consumption significantly. To obtain the lowest
– Consumes less energy in comparison with NF Process is economically feasible. However, it is not energy consumption possible, high DS
and RO commercialized yet because of the lack of high concentration and low flow rate should be
– Lower irreversible fouling rate and lower performance membranes considered
fouling in general
– Easy cleaning procedures
– Can attain high recovery rate and high
contaminate rejection
Energy recovery and Consumes less electric energy and recover more Hybrid RED/ED system lowers the overall operating Low percentage of multivalent ions, and suitable [72]
desalination of high salinity gradient power costs. conditions for ion exchange membrane such as
salinity wastewater This system outperformed ED system in respect to temperature and pH are required for the system
energy consumption to work with hypersaline brine
Brine source recovery Produces salt from brine with energy consumption Helps in lowering the cost of desalination water, Organic matter and colloidal material causes [107]
< 20% in comparison with sea water increase fresh water recovery, and decrease the fouling
environmental impact of discharging brine to the sea
Used for ED At a current density of 2.5 mA cm−2, the perm- Economic analysis has not been conducted. Intricate controls are necessary in order to keep [109]
applications selectivity is 47.12. This high permselectivity Beneficial for various applications such as resource the system running
makes the membrane good for several recovery and desalination. It has the ability to
applications such as water desalination and extract various minerals from water efficiently
resource recovery
Maximize the Recycling brine increased the recovery rate by Energy cost of 0.9$ m−3 for brine recycling in one 90% recovery rate was obtained with 8 stages [46]
production rate and 40% at an energy cost of 0.9$ m−3 stage. However, this increases with more stages. employed, but this increased production cost to
reduce energy Brine is recycled back to the system, which lowers 9$ m−3
consumption the volume of brine disposed
Desalination Reduces fouling, energy consumption, and Closed-circuit RO system has lower energy – Maintaining the crossflow and flux across [110]
increases recovery consumption. It lowers the average feed pressure multiple membranes and stages is difficult
compared to that required by traditional RO – Frequent feed flushing is needed to reduce
processes at the same operation conditions. scaling and fouling
Recovers brine partially, lowering output brine
volume and therefore reducing impact of brine
disposal
Harvesting energy The overall net specific is 0.12 kWh m−3 of It has low energy requirement and has niche To maximize resource recovery, authors suggest [94]
permeate, if freshwater and seawater are used as applications with high salinity brine utilized, since a low power density or low membrane
feeds specific energy is linearly proportional to osmotic productivity
pressure difference. Energy harvested can be used in
RO facility, lowering the total cost of brine discharge
(continued on next page)
Desalination 472 (2019) 114187
M.O. Mavukkandy, et al. Desalination 472 (2019) 114187

References scaling has to be mitigated. For harvesting energy from brine, con-
centration flow cells have the highest power density in comparison with

[107]

[103]

[107]
[95]
other technologies, but the efficiency lays in the electrochemical
characteristics of the electrode. Minerals with high market price such as

generation and salt removal efficiency decreases

concentration is high or evaporation rate is low uranium and rubidium can be recovered from brine by combining ad-
More work is required to show that the system

Membrane fouling is a major problem. Power

sorbents with other technologies. Using absorbents requires minimal
energy, but the presence of other competing ions lowers the process

Not feasible for large amount of brine

efficiency. The economic feasibility of resource recovery from brine
Needs large surface area when brine

depends on the resource recovered and the type of process used. The
as the operational time increases
has potential in practical terms

higher the market value of the resource recovered, the closer the pro-
cess is to economic feasibility. To ensure economic feasibility, the
process is required to have low maintenance needs, have low energy
consumptions, and the capability of extracting high market value pro-
ducts. Processes that are not pressure driven such as membrane dis-
Limitations

tillation, membrane distillation crystallization, electrodialysis, reverse

electrodialysis, etc. have low energy requirements, but suffer from a
number of limitations related to maintenance that makes them less
economically feasible. Although extraction of several materials from
– Uses natural methods to recover resources from
Sustainable method that removes salt and generate

desalination brine is technically possible, it is currently expensive and

Increase the recovery rate of RO and reduce brine

Poorly constructed polar bonds can contaminate

this largely restricts its commercialization. Use of chemicals in the

Economic feasibility & environmental impact

upstream can be fine-tuned based on the target resources which can be

recovered at the downstream. Last decade has witnessed an increased
academic interest in this topic, however, the number of pilot-scale re-
– Low cost and low productivity

search has been very limited. This calls for more demonstration-scale
Low cost and low productivity.

resource extraction studies by evaluating the technical and economic

underlying water aquifers.

feasibility, process efficiency, environmental benefits and product

purity.

Declaration of competing interest

discharge

brine

The authors declare that they have no known competing financial

energy

interests or personal relationships that could have appeared to influ-

ence the work reported in this paper.
Uses natural energy sources such as winds and sun
Low maintenance and operation, easy to construct

current generation with high salt and COD

PRO-RO system gives more advantages than a

Acknowledgments
– Provide high power generation and high

This work was funded by the Cooperative Agreement between the

Masdar Institute of Science and Technology (Masdar Institute), Abu
Dhabi, UAE and the Massachusetts Institute of Technology (MIT),
Cambridge, MA, USA.
– Suitable for scale up

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