water

Article
A Thermodynamical Approach for Evaluating Energy
Consumption of the Forward Osmosis Process Using
Various Draw Solutes
Lan-mu Zeng, Ming-yuan Du and Xiao-lin Wang *
Beijing Key Laboratory of Membrane Materials and Engineering, Department of Chemical Engineering,
Tsinghua University, Beijing 100084, China; zenglanmu@126.com (L.Z.); dmy11@foxmail.com (M.D.)
* Correspondence: xl-wang@tsinghua.edu.cn; Tel.: +86-10-62794741

Academic Editor: Stephen Gray

Received: 26 December 2016; Accepted: 2 March 2017; Published: 6 March 2017

Abstract: The forward-osmosis (FO) processes have received much attention in past years as an
energy saving desalination process. A typical FO process should inclu de a draw solute recovery
step which contributes to the main operation costs of the process. Therefore, investigating the
energy consumption is very important for the development and employment of the forward osmosis
process. In this work, NH3 -CO2 , Na2 SO4 , propylene glycol mono-butyl ether, and dipropylamine
were selected as draw solutes. The FO processes of different draw solute recovery approaches
were simulated by Aspen PlusTM with a customized FO unit model. The electrolyte Non-Random
Two-Liquid (Electrolyte-NRTL) and Universal Quasi Chemical (UNIQUAC) models were employed
to calculate the thermodynamic properties of the feed and draw solutions. The simulation results
indicated that the FO performance decreased under high feed concentration, while the energy
consumption was improved at high draw solution concentration. The FO process using Na2 SO4
showed the lowest energy consumption, followed by NH3 -CO2 , and dipropylamine. The propylene
glycol mono-butyl ether process exhibited the highest energy consumption due to its low solubility
in water. Finally, in order to compare the equivalent work of the FO processes, the thermal energy
requirements were converted to electrical work.

Keywords: forward osmosis; process simulation; energy consumption; customized model

1. Introduction
The shortage of freshwater has become a main challenge in the 21st century as a consequence
of world population growth, increasing industrial consumption and pollution, development of
agriculture, climate change, etc. [1,2]. The commercialized desalination technologies such as reverse
osmosis (RO), multi-effect distillation (MED), and multi-stage flash (MSF) have been widely used,
which still have the common problem of high energy consumption [35]. In recent years, Forward
Osmosis (FO) has received much attention as a low energy cost desalination technology when
compared with the above traditional processes [68]. In FO, the water molecules from the feed
solution move to the draw side through a semipermeable membrane as a result of an osmotic pressure
difference across the membrane. As the osmotic pressure of the draw solution drops due to the
dilution, the draw solute recovery step is often necessary to regain the osmotic pressure after the FO
operation [9].
The recovery of draw solutes in an FO process contributes to the major the energy consumption
of the FO process. The selection of draw solutes significantly affects the performance of an FO process.
Over the past decades, various draw solutes have been proposed [10]. One of the most commonly
used draw solute is ammoniacarbon dioxide (NH3 -CO2 ), which was first commercialized by HTI

Water 2017, 9, 189; doi:10.3390/w9030189 www.mdpi.com/journal/water

Water 2017, 9, 189 2 of 17

Inc., Powell, OH, USA [1113]. In the NH3 -CO2 FO process, ammonium salts such as ammonium
bicarbonate, ammonium carbonate, and ammonium carbamate are used as draw solutes. After FO, the
ammonium salts in the diluted draw solution can be thermo-decomposed into NH3 and CO2 gases
at elevated temperature, and then the concentrated ammonium salt solution is regenerated from the
mixture of NH3 and CO2 gases. Switchable polarity solvent (SPS), which is capable of changing its
solubility in water by the addition and removal of CO2 , was proposed as a new FO draw solute [1416].
By heating up the SPS solution, CO2 is driven off and the hydrophobic form of SPS is separated from
the diluted draw solution. Other examples of utilizing low-grade heat in draw solute recovery are
the solutes with a lower critical solution temperature (LCST) point that exhibit liquid-liquid phase
separation with water at high temperature. For example, Nakayama et al. demonstrated that some
types of glycol ethers including di(ethylene glycol) n-hexyl ether (DEH), propylene glycol n-butyl
ether (PB) and di(propylene glycol) n-propyl ether (DPP) can be used as draw solutes [17]. LCST ionic
liquids as draw solutes were reported to be able to treat feed solutions with NaCl concentrations of up
to 1.6 molL1 by Cai et al. [18]. Besides using heat sources, the recovery of draw solutes can also be
achieved by cooling. Zhong et al. employed ionic liquid with an upper critical solution temperature as
the draw solute [19]. In the proposed process by Zhong et al., the FO process is operated at 60 C while
the draw solute recovery is carried out via cooling to room temperature. From the above discussions, it
can be seen that many types of draw solutes with different recovery schemes are available for the FO
process. So, it is important to evaluate the performance of the FO process for the selection of draw solutes.
For the FO process with NH3 -CO2 draw solute, the modeling results from McGinnis et al. by
chemical modeling software HYSYS showed that the FO process had the lowest equivalent work
requirement among MSF, MED, and RO desalination when a low-grade heat was available [20].
Mazlan et al. compared the energy consumption of FO with nanofiltration (NF) or ultrafiltration (UF)
draw solute recovery and reverse osmosis (RO) [21]. The results suggest that there is practically no
difference in the specific energy consumption of FO-NF (or FO-UF) and RO even if the membrane is
theoretically perfect. The switchable polarity solvent forward osmosis process modelled by Wendt
et al. was found to be a competitive desalination technology that could be applied to a feed solution
with NaCl concentrations of up to 4.0 molal [14]. Park et al. integrated the FO process with the gas
turbine cycle so the recovery step could utilize the waste heat from the turbine to improve the energy
efficiency of the integrated process [22]. According to their simulation results, the FO-gas turbine
system has an advantage on gain output ratio (GOR) and water production capacity compared with
the MSF-gas turbine system. Although there are some existing works on modeling the FO process,
a comprehensive platform is still lacking for the evaluation of the FO performance using different draw
solutes. A directly comparison of the performance of various draw solutes has not been investigated
comprehensively, but this comparison important in the future development of draw solutes.
In the presented work, thermodynamic simulation based on Aspen Plus software was adopted
to model the FO process. Several draw solutes including NH3 -CO2 , sodium sulfate (Na2 SO4 ), and
organic solutes with LCST points were selected. For each draw solute, different recovery methods
were designed with respect to their properties. For example, the distillation column was used for
the recovery of NH3 -CO2 draw solute. The simulations were carried out at different feed and draw
solution concentrations to study the influence of concentrations on the energy consumption of the FO
process using specific draw solutes. The energy consumptions as well as the equivalent works were
calculated to give a basic comparisons among those draw solutes.

2. Materials and Methods

2.1. FO Unit Operation Model

This study was mainly focused on evaluating the energy consumption of the FO process using
certain draw solutes under ideal conditions. Therefore, this work did not involve the analysis of
membrane permeability for reducing the complexity of the simulation. The membrane was assumed to
Water 2017, 9, 189 3 of 17

be theoretically perfect and completely rejecting the solutes, so internal concentration polarization and
the back-leak of draw solutes were not considered. The following equation was applied to estimate
the theoretical minimum energy consumption for an FO process:

draw = f eed + min (1)

where draw represents the osmotic pressure of the draw solution side, f eed is the osmotic pressure of
feed side. min is the minimum osmotic pressure difference above which noticeable flow rate could be
observed. The term min ensures the osmotic pressure of the draw solution side is always larger than
the feed side.
The mathematical model for the customized FO unit operation was built with the Fortran
programming interface of the Aspen Plus software. The concentrations of inlet streams in the
customized FO model which are the initial concentrations of the feed and draw solutions, were
given by the simulation flowsheet. The concentrations of outlet streams are manipulated by changing
the amount of water migrated from the feed to the draw side, until osmotic equilibrium is reached.
The osmotic pressure was calculated by the activity of water which will be discussed in the next
Section 2.2. Taking the thermodynamic restriction and draw solution recovery into consideration,
the simulation approach with this customized FO unit model can achieve rigorous evaluation of the
energy consumption of the FO process with different draw solutes.
For a better understanding on the influence of draw solutes on the FO performance, the term
RWATER was used, as shown below:

moles of water transferred

RWATER = (2)
moles of water in draw solution
Considering an FO process with draw solution recovery, energy must be used to change the state
of the diluted draw solution, i.e., thermal energy is required for heating up the diluted NH3 -CO2
solution for thermal decomposition. In this process, not only does the transferred water result in energy
consumption, so too does the water in the draw solution. If the FO process is operated at steady-state,
the amount of transferred water would be equal to the quantity of produced water. So RWATER can be
used to evaluate the energy efficiency of the FO process. Higher RWATER values means more energy
is used for desalination rather than being wasted on draw solution.

2.2. Osmotic Pressure

The prediction of osmotic pressure is vital for modeling the FO process. The most commonly
used method in the previous studies is based on the vant Hoff theory, which the osmotic pressure is
calculated by the following equation:
= nCRT (3)

where n is the vant Hoff factor representing the number of moles of a solute dissociated in the
solution (for example, n = 2 for NaCl and n = 3 for MgCl2 ). C is the molar concentration (molL1 )
of the solution. R is the gas constant which is equivalent to 8.314 Jmol1 K1 and T is the absolute
temperature (in Kelvin). However, the vant Hoff equation is only suitable for dilute solutions. When
dealing with concentrated solutions or solutions with multi components, noticeable deviations may be
encountered if the vant Hoff equation is employed to calculate the osmotic pressure. Besides the vant
Hoff equation, the osmotic pressure is defined as a function of the activity of water in thermodynamics:


= RT/Vw ln aw (4)

where Vw is the partial molar volume of water and aw represents the activity of water.
This thermodynamic approach allows the determination of osmotic pressure in concentrated electrolyte
solution and even the solution with multiple solvents.
Water 2017, 9, 189 4 of 17

The activity of water is calculated by thermodynamic models. The Electrolyte-NRTL [23] (eNRTL)
model was employed for electrolyte systems, while the UNIQUAC [24] model was used for systems
containing organic solvents. The eNRTL model, developed by Chen and his coworkers, has been
successfully applied to many electrolyte systems. Detailed description of the eNRTL model can be
found elsewhere [25,26], so only a brief introduction is presented in this paper. The excess Gibbs free
energy in the eNRTL model is expressed as a sum of three terms:
ex
GNRTL G ex G ex G ex
= PDH + Born + lc (5)
RT RT RT RT
where the notation * indicates that the excess Gibbs free energy is the unsymmetrical. The subscripted
PDH, Born, and lc represent Pitzer-Debye-Huckel, Born, and local composition contributions, respectively.
There are three types of binary parameters in the eNRTL model: molecule-molecule,
molecule-electrolyte, and electrolyte-electrolyte binary parameters. Here, an electrolyte does
not mean the salt dissolved into the solution, but an ion pair composed of a cation and an
anion. For an electrolyte system, the binary parameters are expressed as a and . Normally,
the symmetric nonrandom factor parameter a is ranges from 0.1 to 0.5, and often is set to 0.2 for
molecule-electrolyte interaction. While the unsymmetrical binary interaction energy parameter is
dependent on temperature:
 0
T T
 
D T
=C+ +E + ln 0 (6)
T T T
The reference temperature T 0 is 273.15 K. C, D, and E are adjustable parameters. Thus,
for modeling a draw solution containing electrolytes, the adjustable parameters C, D, and E for
each type of binary interaction energy parameters (molecule-molecule, molecule-electrolyte, and
electrolyte-electrolyte) would need to be regressed with respect to experimental thermodynamic data.
Although eNRTL can also be used to calculate the thermodynamic properties of organic solution,
we found that the UNIQUAC model based on group contribution theory was more convenient and
provided better results for calculating the osmotic pressure of water in organic solutions. Besides, the
UNIQUAC model enables us to do a rough estimation of the model parameters from the structure of
organic solvents when there are no experimental data available to do regression. So the UNIQUAC
model was employed for the aqueous propylene glycol mono-butyl ether and dipropylamine solutions.
In the UNIQUAC model, the excess Gibbs free energy is calculated as a sum of a combinatorial
and a residual term: ex
GUNIQUAC G ex G ex
= combinatorial + residual (7)
RT RT RT
And the combinatorial term is expressed as:
!" #
ex
Gcombinatorial Z
RT
= ni xi ln xii + 2 qi xi ln ii (8)
i i i

The residual term is expressed as:

!" !#
ex
Gresidual
RT
= ni qi xi ln j ij (9)
i i j

where:
qi xi
i = (10)
qj xj
j

ri xi
i = (11)
rj xj
j
 i =
q x
j
j j
(10)

ri xi
i =
Water 2017, 9, 189 rj xj
j
(11)
5 of 17

ijij =
= exp (

ij
+ bbij /T
exp aaij +
ij
+ ccij ln
/ T+
ij
+ ddijTT ++eeij //T
lnTT +
ij ij
T 22)
(12)(12)

qi and ri areri the

qi and aresurface area area
the surface and volume size size
and volume parameters, which
parameters, are related
which to the
are related to structure of the
the structure
molecule. The coordination number Z is set to 10. aij , bij , cij , dij , and eij are the unsymmetrical binary
of the molecule. The coordination number Z is set to 10. aij , bij , c ij , dij , and e ij are the
adjustable interaction parameters between species i and j.
unsymmetrical
With suitablebinary
modeladjustable interaction
parameters, parameters
the activity between
of water and thespecies i and
osmotic j.
pressure of a certain draw
With suitable model parameters, the activity of water and the osmotic
solution can be calculated. Because the molality concentration (moles per weight of pressure of asolvent)
certain draw
is more
solution can be calculated. Because the molality concentration (moles per weight of solvent) is more
convenient in thermodynamic calculation, the concentration of feed and draw solutions are expressed
convenient in thermodynamic calculation, the concentration of feed and draw solutions are expressed
in molality rather than molarity (moles per volume of solution) in the following section.
in molality rather than molarity (moles per volume of solution) in the following section.
2.3. FO Process Design
2.3. FO Process Design
NH3 -CO2 , Na2 SO4 , and organic solutes were used in this study and different draw solute recovery
NH3-CO2, Na2SO4, and organic solutes were used in this study and different draw solute
schemes were required with respect to their properties. The FO process diagram using NH3 -CO2 as
recovery schemes were required with respect to their properties. The FO process diagram using NH3-
the draw solute is shown by Figure 1. The original feed and draw solutions were input parameters for
CO2 as the draw solute is shown by Figure 1. The original feed and draw solutions were input
theparameters
customized FO unit operation model, where the water in the feed side was transferred into the
for the customized FO unit operation model, where the water in the feed side was
draw
transferred into thetodraw
side according osmotic
side pressure
accordingequilibrium. Multistage
to osmotic pressure distillation
equilibrium. columns decomposed
Multistage distillation
NH 3 -CO2 more
columns completely
decomposed NH3-COand maximized the water production, but required a heat source of
2 more completely and maximized the water production, but required
higher
a heattemperature [20]. temperature
source of higher Assuming an[20].available
Assuming heat an
source withheat
available the temperature of more
source with the than 110of C,
temperature
a multistage
more thandistillation column was
110 C, a multistage used for the
distillation decomposition
column was used forof the
thediluted NH3 -COof
decomposition 2 draw solution.
the diluted
TheNHdistillation
3-CO2 drawcolumn with
solution. 15 distillation
The stages was column
modelled by the
with RadFrac
15 stages wasunit operation
modelled by model in the unit
the RadFrac Aspen
Plus. From the
operation bottom
model of the
in the distillation
Aspen column,
Plus. From water with
the bottom of thea distillation
low amountcolumn,
of ammonia
waterand
withcarbonate
a low
was produced.
amount The NHand
of ammonia 3 and CO2 gases
carbonate wasfrom the topThe
produced. of the
NHdistillation
3 and CO2 gasescolumn were
from the cooled
top of down
the
anddistillation
then mixedcolumn
withwere
watercooled down and
to regenerate thethen
drawmixed with water
solution. to regenerate
The eNRTL model the
wasdraw solution.
selected for the
The eNRTL
calculation model was selected
of thermodynamic for the calculation
properties, and the modelof thermodynamic
parameters were properties,
retrievedand
fromthethe
model
Aspen
parameters were
default databank. retrieved from the Aspen default databank.

Figure1.1.Aspen
Figure Aspen Plus
Plus flowsheet
flowsheet of
of the
the forward
forward osmosis (FO) process
process using
using NH
NH33-CO
-CO2 2asasthe
thedraw
drawsolute.
solute.

The outline of the FO process using Na2SO4 as the draw solute is displayed in Figure 2. The
The outline of the FO process using Na2 SO4 as the draw solute is displayed in Figure 2.
Na2SO4 was precipitated out from the diluted draw solution, in the form of glauber salt, via cooling
The Na2 SO4 was precipitated out from the diluted draw solution, in the form of glauber salt, via cooling
down to 0 C. The crystallization of the Na2 SO4 was simulated by the Crystallizer model in Aspen
Plus. After crystallization, the solids were separated from the solution via filtration for draw solution
recovery. The clear solution was sent to reverse osmosis (RO) for the production of water. For the
calculation of thermodynamic properties, the eNRTL model parameters in the default databank
were used.
 down to 0 C. The crystallization of the Na2SO4 was simulated by the Crystallizer model in Aspen
down to 0 C. The crystallization of the Na2SO4 was simulated by the Crystallizer model in Aspen
Plus. After crystallization, the solids were separated from the solution via filtration for draw solution
Plus. After crystallization, the solids were separated from the solution via filtration for draw solution
recovery. The clear solution was sent to reverse osmosis (RO) for the production of water. For the
recovery. The clear solution was sent to reverse osmosis (RO) for the production of water. For the
calculation of thermodynamic properties, the eNRTL model parameters in the default databank were
calculation
Water 2017, 9, 189of thermodynamic properties, the eNRTL model parameters in the default databank were 6 of 17
used.
used.

Figure 2. Aspen Plus flowsheet of the FO process using Na2SO4 as the draw solute.
Figure
Figure 2. 2.Aspen
AspenPlus
Plusflowsheet
flowsheetof
of the
the FO
FO process using
usingNa
Na2SO 4 asas
2 SO 4 the draw
the solute.
draw solute.

Figure 3 demonstrates the Aspen Plus flowsheet of the FO process using organic solutes with an
Figure 3 demonstrates the Aspen Plus flowsheet of the FO process using organic solutes with an
LCST point3asdemonstrates
Figure the Aspen
the draw solutes. Plus flowsheet
The Decenter model in of the FO
Aspen Plusprocess using organic
was employed for thesolutes
simulationwith an
LCST point as the draw solutes. The Decenter model in Aspen Plus was employed for the simulation
LCST point as the separator,
of a liquid-liquid draw solutes.
which The Decenter
enables model
rigorous in Aspenof
calculation Plus was employed
liquid-liquid phasefor the simulation
separation by
of a liquid-liquid separator, which enables rigorous calculation of liquid-liquid phase separation by
ofthermodynamic
a liquid-liquid separator,
modelling. which enables
After liquid-liquid rigorous calculation
separation, of
the water liquid-liquid
phase was sent
thermodynamic modelling. After liquid-liquid separation, the water phase was sent into the RO
phase separation
into the RO by
model for the production
thermodynamic of water. The organic phase was therecycled as a new drawintosolution.
the ROThe
model for the modelling.
production After liquid-liquid
of water. The organic separation,
phase was water phase
recycled as awas
newsent draw solution. model
The
UNIQUAC
forUNIQUAC model
the production parameters
of parameters for
water. The organicPB were regressed
phaseregressed with
was recycled respect to experimental liquid-liquid
model for PB were withasrespect
a new to draw solution. The
experimental UNIQUAC
liquid-liquid
equilibrium
model data, as
parameters forthe
PB Aspen
were databank with
regressed (Aspen Plus, to
respect v7.6, Aspen Technology,
experimental Inc., Bedford,
liquid-liquid equilibrium MA,data,
equilibrium data, as the Aspen databank (Aspen Plus, v7.6, Aspen Technology, Inc., Bedford, MA,
asUSA)
the does not
Aspen have such
databank parameters.
(Aspen Plus, Unfortunately,
v7.6, Aspen we cannot find
Technology, Inc., enough
Bedford, data
MA,
USA) does not have such parameters. Unfortunately, we cannot find enough data to obtain the vapor-
to obtain
USA) the vapor-
does not have
liquid
such parameters
parameters. for the estimation
Unfortunately, we cannotof osmotic pressure; so previous regressed liquid-liquid
liquid parameters for the estimation of find enough
osmotic data to so
pressure; obtain the vapor-liquid
previous parameters for
regressed liquid-liquid
parameters
the estimation were used which
of osmotic may so
pressure; cause someregressed
previous uncertainty in the simulation.
liquid-liquid parameters Thewere
liquid-liquid
used which
parameters were used which may cause some uncertainty in the simulation. The liquid-liquid
parameters
may in
cause some the default databank for dipropylamine (DP) were employed to calculate its liquid-
parameters in uncertainty in the simulation.
the default databank The liquid-liquid
for dipropylamine (DP) were parameters
employed in to
thecalculate
default databank
its liquid-for
liquid equilibrium properties. In addition, the osmotic pressure of DP was calculated by the vapor-
liquid equilibrium
dipropylamine (DP) properties.
were employed In addition, the osmotic
to calculate pressure ofequilibrium
its liquid-liquid DP was calculated by the
properties. In vapor-
addition,
liquid parameters for a better result.
theliquid parameters
osmotic pressurefor ofaDP
better
wasresult.
calculated by the vapor-liquid parameters for a better result.

Figure 3. Aspen Plus flowsheet of the FO process using organic solutes with a LCST point as the draw
Figure
Figure 3. 3.Aspen
Aspen Plus
Plus flowsheet
flowsheetofofthe FOFO
the process using
process organic
using solutes
organic with awith
solutes LCSTa point
LCSTaspoint
the draw
as the
solute.
solute.
draw solute.

3. Results

3.1. FO Process Using NH3 -CO2 as Draw Solute

NH3 -CO2 draw solution is regenerated via thermally decomposing the diluted draw solution
into NH3 and CO2 gases at elevated temperature, then absorbing the gases by water to regenerate a
concentrated draw solution [12]. The dissolved NH3 and CO2 gases in solution present in various
forms including NH4 + , NH2 COO , HCO3 , and CO3 2 ions, together with NH3 (0) and CO2 (0) neutral
3. Results

3.1. FO Process Using NH3-CO2 as Draw Solute

NH3-CO2 draw solution is regenerated via thermally decomposing the diluted draw solution
into
Water NH and
2017,3 9, 189 CO2 gases at elevated temperature, then absorbing the gases by water to regenerate a
7 of 17
concentrated draw solution [12]. The dissolved NH3 and CO2 gases in solution present in various
forms including NH4+, NH2COO, HCO3, and CO32 ions, together with NH3(0) and CO2(0) neutral
molecules. The
molecules. The osmotic
osmotic pressure
pressure of of the
the NHNH33-CO-CO22 solution
solution is is influenced
influenced by by the
the distribution
distribution of of those
those
species, which can be affected by the concentrations
species, which can be affected by the concentrations of NH of NH and CO
3 3 and CO and also their ratio. An
2 2 and also their ratio. An 3NH NH -CO32-
solution
CO with a higher NH3 to CO
2 solution with a higher NH23ratioto CO composed from ammonia salts like ammonium carbonate and
2 ratio composed from ammonia salts like ammonium
ammonium carbamate can provide higher
carbonate and ammonium carbamate can provide higher driving forces for the FO
driving process
forces dueFO
for the to its higherdue
process osmotic
to its
pressure [27]. However, the high pH of those solutions
higher osmotic pressure [27]. However, the high pH of those solutions3 with highwith high NH to CO 2 ratios might become
NH3 to CO2 ratios
a problem
might become for athe membrane.
problem for theNH 4 HCO3 solutions
membrane. NH4HCO with the NH3 to the
3 solutions with
CONH2 ratio of 1 was preferred
3 to CO2 ratio of 1 was
by some other researchers because it is less corrosive to
preferred by some other researchers because it is less corrosive to the membrane the membrane [13]. In this simulation, the
[13]. In this
performancethe
simulation, ofperformance
the FO process wasFO
of the theprocess
first concern
was thesofirst
a high ratio so
concern of a
2.4 wasratio
high selected.
of 2.4 was selected.
To illustrate the influence of the feed concentration on
To illustrate the influence of the feed concentration on the process performance, NaCl the process performance, NaCl
concentrations ranged from 0.1 to 1 mol kg 1 . The draw solution was composed of 12 molkg1
concentrations ranged from 0.1 to 1 molkg1. The draw solution was composed of 12 molkg1 NH3
NH35and
and molkg5 mol kg
1 CO
1 CO . The results are presented in terms of RWATER and energy consumption
2. The 2results are presented in terms of RWATER and energy consumption per
per quantity
quantity of produced
of produced water.
water. It can
It can be be seenseenin in Figure
Figure 4 thatRWATER
4 that RWATERand andthe
theenergy
energy consumption
consumption
clearly showed a reverse trend with an increase of feed concentration.
clearly showed a reverse trend with an increase of feed concentration. RWATER is decreased RWATER is decreased while the
while
energy
the consumption
energy consumption per per
water increases
water increases withwith
increasing NaClNaCl
increasing concentration.
concentration.WithWiththe increasing feed
the increasing
concentration, the osmotic pressure differences across the membrane
feed concentration, the osmotic pressure differences across the membrane decreased. As a decreased. As a consequence,
a lower amount
consequence, of water
a lower would
amount be migrated
of water would to bethe draw side
migrated to the before
drawosmotic
side beforepressure
osmotic equilibrium
pressure
was reached, which leads to a low RWATER value. The low RWATER
equilibrium was reached, which leads to a low RWATER value. The low RWATER values mean values mean that more extra
that
energy was needed to heat up the draw solution.
more extra energy was needed to heat up the draw solution.

800

Energy
20
760
RWater

Energy (MJ/ton)
RWATER

15 720

10 680

640
5

0.0 0.2 0.4 0.6 0.8 1.0

NaCl (mol/kg)

Figure
Figure 4.
4. The
The effect
effect of
of feed
feed solution concentration on
solution concentration on the
the FO
FO process
process performance
performance using
using NH
NH3-CO
-CO2 as
3 2 as
the draw solute.
the draw solute.

The FO performance at different NH3-CO2 concentrations is illustrated in Figure 5. The feed

The FO performance at different NH3 -CO2 concentrations is illustrated in Figure 5. The feed
concentration was fixed at 0.5 molkg1 NaCl, which has an osmotic pressure of 2.22 MPa. The
concentration was fixed at 0.5 molkg 1 NaCl, which has an osmotic pressure of 2.22 MPa.
concentration of CO2 in the draw solution ranged from 1.0 to 10.0 molkg1, and the NH3 to CO2 ratio
The concentration of CO2 in the draw solution ranged from 1.0 to 10.0 molkg1 , and the NH3 to CO2
was kept at 2.4. It can be seen in Figure 5 that increasing the draw solution concentration would have
ratio was kept at 2.4. It can be seen in Figure 5 that increasing the draw solution concentration would
a very positive effect on improving the energy efficiency. As discussed above, the increasing osmotic
have a very positive effect on improving the energy efficiency. As discussed above, the increasing
pressure difference is the main reason for the improved FO performance at higher draw solution
osmotic pressure difference is the main reason for the improved FO performance at higher draw
concentrations. The osmotic pressure of the NH3-CO2 solution at different concentrations was plotted
solution concentrations. The osmotic pressure of the NH3 -CO2 solution at different concentrations
in Figure 6. The osmotic pressure of a draw solution containing 2.4 molkg1 NH3 and 1.0 molkg1
was plotted in Figure 6. The osmotic pressure of a draw solution containing 2.4 molkg1 NH3 and
CO2 is 6.201MPa, which would generate an osmotic pressure difference of 4.00 MPa when the feed
1.0 molkg CO2 is 6.20 MPa, which would generate an osmotic pressure difference of 4.00 MPa when
the feed solution contains 0.5 molkg1 NaCl. By increasing the NH3 and CO2 concentrations to 24.0
and 10.0 molkg1 , an osmotic pressure difference of 59.2 MPa can be obtained.
Water 2017, 9, 189 8 of 17
Water 2017, 9, 189 8 of 17

solution
Water 2017,contains
9, 189 0.5 molkg1 NaCl. By increasing the NH3 and CO2 concentrations to 24.0 and 10.0
solution contains 0.5 molkg1 NaCl. By increasing the NH3 and CO2 concentrations to 24.0 and8 10.0
of 17
molkg 1, an osmotic pressure difference of 59.2 MPa can be obtained.
1
molkg , an osmotic pressure difference of 59.2 MPa can be obtained.
20 1400
20 1400

15 1200
15 1200

(MJ/ton)
Energy(MJ/ton)
RWATER
RWATER
10 RWater 1000
10 RWater 1000

Energy
5
5 800
800

Energy
0 Energy
0 600
0 2 4 6 8 10 600
0 2 4 6 8 10
CO2 (mol/kg)
CO2 (mol/kg)
Figure 5. The
The effect
effect of
of draw
draw solution
solution concentration on
on the FO
FO process performance
performance using NH
NH3-CO2 as
Figure
Figure 5.
5. The effect of draw solution concentration
concentration on the
the FO process
process performanceusing
using NH33-CO
-CO22 as
as
the
the draw solute.
the draw
draw solute.
solute.
70
70

60
60
(MPa)
Pressure(MPa)

50
50

40
OsmoticPressure

40

30
30
Osmotic

20
20

10 1 mol/kg NaCl
10 1 mol/kg NaCl
0.1 mol/kg NaCl
0 0.1 mol/kg NaCl
0
0 2 4 6 8 10
0 2 4 6 8 10
CO2 (mol/kg)
CO2 (mol/kg)
Figure 6. Osmotic pressure of draw solution at difference CO2 concentrations.
Figure 6.
Figure 6. Osmotic pressure of
Osmotic pressure of draw
draw solution
solution at
at difference
difference CO
CO22 concentrations.
concentrations.

3.2. FO Process Using Na2SO4 as Draw Solute

3.2. FO
3.2. FO Process Using Na
Process Using Na2SO 4 as Draw Solute
2 SO4 as Draw Solute
As a draw solute, Na2SO4 would not only generate considerable osmotic pressure, but would
As aa draw
draw solute, Na Na2SO SO4 would
would not only generate considerable
considerable osmotic
osmotic pressure,
pressure, but
but would
would
also Ashave a lowsolute, draw solute 2 4 back-leak notbecause
only generate
the SO42 ion does not easily penetrate the FO
also have a
also have a[28,29]. low
low drawdraw solute
solute back-leak because the SO 422
ion does not easily penetrate the FO
membrane Because the back-leak
solubility of because
Na2SOthe SO4
4 was sharply
iondecreased
does not at easily penetrate the
the temperature FO
range
membrane
membrane [28,29].
[28,29]. Because
Because the solubility
the solubility of Na
of Na 2SO4 was sharply decreased at the temperature range
of 0 to 32 C, it gives the chance of recycling Na22SO wascrystallization
SO44 via sharply decreased at the
at a low temperature range
temperature.
of 0 to
of 0 to 32
32 FOC,
it
C, it gives the chance
gives the chance of recycling
of recycling Na 2SO4 via crystallization at a low temperature.
The performance at different feed Na 2 SO4 via
solution crystallizationisatdisplayed
concentrations a low temperature.
in Figure 7. The
The FO performance atatdifferent feed solution concentrations is displayed in Figure 7. The
concentration of draw solution was set 2.9 molkg 1, which is close to the displayed
The FO performance different feed solution
1 concentrations is maximum in Figure
solubility 7.
of
concentration
The concentration of draw
of draw solution
solution was was set 2.9
set molkg
2.9 mol kg , which is close to the maximum solubility
1 , which is close to the maximum solubility of of
Na2SO4 in water. Similar to the situation of NH3-CO2, high feed concentration had a negative
Na2SO
Na 4 in water. Similar to the situation of NH3-CO2, high feed concentration had a negative
2 SO4 inon
influence water. Similar to the situation
FO performance. The value of of
NH 3 -CO2 , high
RWATER feed concentration
decreased from 9.77 had a negative
to 1.49 molmol influence
1 while
influence
on FO on FO performance.
performance. The value Theof value of RWATER
RWATER decreased decreased
from 9.77 from
to 9.77mol
1.49 to 1.49
mol molmol
while
1 while1energy
energy consumption increased from 138 to 324 MJton1 when the concentration of feed solution
energy consumption
consumption increased from 138ton
to 324
1 when MJton 1 when the concentration of changed
feed solution
changed fromincreased
0.1 molkg from 138 to
1 NaCl to324 MJ
1 molkg 1. Figure the concentration
8 shows of feed solution
the FO performance at draw from
solution
changed
0.1 mol from
kg 1 0.1
NaCl molkg
to 1 mol
1 NaCl to 1 molkg1. Figure 8 shows the FO performance at draw solution
kg 1 . Figure 8 shows the FO performance at draw solution concentrations
concentrations from 1 to 2.9 molkg 1, with feed solution of 0.5 molkg 1 NaCl. The value of RWATER
1 1
concentrations
from 1 to almost
2.9 mol from
kg11to, with
2.9 molkg , with feed solution
molkgof 10.5 molkgThe NaCl.
value The value of RWATER
increased linearly withfeed solution
increasing Naof 0.5 NaCl. of RWATER
2SO4 concentration, and the energy consumption sharply
increased
increased almost linearly with increasing Na 2SO4 concentration, and the energy consumption sharply
almost linearly with increasing Na2 SO4 concentration, and the energy consumption sharply decreased.
decreased.
decreased.
Water 2017, 9, 189 9 of 17
Water 2017, 9, 189 9 of 17
Water 2017, 9, 189 9 of 17
350
10 350
10 Energy
300
RWater Energy
8
300
RWater

(MJ/ton)
8

RWATER
250

(MJ/ton)
6

RWATER
250

Energy
6
200
4

Energy
200
4
2 150

2 150

0 100
0.0 0.2 0.4 0.6 0.8 1.0
0 100
0.0 0.2 NaCl (mol/kg)
0.4 0.6 0.8 1.0
NaCl (mol/kg)
Figure 7. The effect of feed solution concentration on the FO process performance using Na2SO4 as the
Figure 7. The effect of feed solution concentration on the FO process performance using Na2 SO4 as the
Figuresolute.
draw 7. The effect of feed solution concentration on the FO process performance using Na2SO4 as the
draw solute.
draw solute.
4.0 500

4.0 500
3.5 450
3.5 450
3.0
400

(MJ/ton)
3.0
2.5 400
RWATER

350

(MJ/ton)
2.5 RWater
RWATER

2.0
350

Energy
300
2.0
1.5
RWater

Energy
300
1.5 250
1.0
250
1.0 Energy 200
0.5

0.5 Energy 200

0.0 150
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0
0.0 150
Na21.8
0.8 1.0 1.2 1.4 1.6 SO4 2.0
(mol/kg)
2.2 2.4 2.6 2.8 3.0
Na2SO4 (mol/kg)
Figure 8. The effect of draw solution concentration on the FO process performance using Na2SO4 as
Figuresolute.
draw 8. The effect of draw solution concentration on the FO process performance using Na2SO4 as
Figure 8. The effect of draw solution concentration on the FO process performance using Na2 SO4 as
draw solute.
draw solute.
3.3. FO Process Using Solvents with LCST Points
3.3. FO Process Using Solvents with LCST Points
An organic
3.3. FO Process Usingsolute withwith
Solvents a low critical
LCST solution temperature (LCST) point is completely miscible
Points
with An organic
water belowsolute with atransition
the phase low critical solution temperature
temperature, (LCST) point
making it possible is completely
to provide enough miscible
osmotic
An
withorganic
water
pressure solutethe
below
to withdraw with
phase
the a low
water critical
transition
from feed solution
solutionstemperature
temperature, making
[30]. (LCST)
At anitelevated
possible topoint
provide
temperature is completely
enough
above the miscible
osmotic
LCST
pressure
with point,
waterthe to
below withdraw
miscible the water
theorganic-water
phase from feed
solution
transition solutions
would
temperature, [30].
exhibit At liquid-liquid
the
making an elevated
it possible temperature
phase above
separation.
to provide the LCST
Then
enough two
osmotic
point,
liquid the miscible
phases are organic-water
formed, includingsolution
the would exhibit
organic-rich the
phase
pressure to withdraw the water from feed solutions [30]. At an elevated temperature above liquid-liquid
with phase
concentrated separation.
draw solute,Then
and two
the the
liquid phases
water-rich are
phase. formed,
Therefore, including
the draw the organic-rich
solute can be phase
separated with
from
LCST point, the miscible organic-water solution would exhibit the liquid-liquid phase separation. concentrated
water by draw
varying solute,
the and
temperature the
water-rich
for phase. Therefore,
the liquid-liquid the draw solute
phase separation. can besolute
The draw separated from water
recovery by varying
of organic solutesthe temperature
with an LCST
Then two liquid phases are formed, including the organic-rich phase with concentrated draw solute,
for theonly
point liquid-liquid phase separation.
needs a simple liquid-liquid Theseparator,
draw solute whichrecovery
would of operate
organic moresoluteseasily
with than
an LCST the
and the water-rich phase. Therefore, the draw solute can be separated from water by varying the
point only columns
distillation needs afor simple liquid-liquid of
the decomposition separator,
NH3-CO2 which solution. would operate the
Furthermore, more easily than and
transportation the
temperature forcolumns
distillation
re-condensation the ofliquid-liquid
for the
gases can bephase
decomposition
avoided separation.
soofthat
NHit3-CO The
would draw
makesolute
2 solution.
recovery
Furthermore,
the process theof
operation organic
transportation solutes
more easy. As with
and
an LCST point
are-condensation
result, onlysolutes
organic needs
of acan
gaseswith simple
be
LCST liquid-liquid
avoided
pointssotend
thattoit separator,
would
be make
promising which
the
draw would
process operatemore
soluteoperation
candidates more easily
andeasy.
receiveAs than
the distillation
considerable columns
a result, organic for
solutes
research the decomposition
with
attention. LCST points tend oftoNH -CO2 solution.
be3promising Furthermore,
draw solute candidates theand
transportation
receive
and re-condensation
considerable
Two organic of gases
research can be propylene
attention.
solvents, namely avoided so thatmono-butyl
glycol it would make ether the
(PB)process operation more
and dipropylamine (DP), easy.
were Two organic
selected as thesolvents,
draw namely
solutes. propylene
PB was once glycol mono-butyl
evaluated by ether
Nakayama
As a result, organic solutes with LCST points tend to be promising draw solute candidates and (PB)
et and
al. [17]dipropylamine
and the (DP),
advantages receive
were selected
of using glycol
considerable as
research the
ethers draw solutes. PB was once evaluated by Nakayama et al. [17]
as draw solutes include low viscosities, low pH values, low volatilities, etc. On
attention. and the advantages
of using
the
Two glycolthe
contrary,
organic ethers
highaspH
solvents, draw solutes
value
namely of the include
propylene aqueous lowDP
glycol viscosities,
solutionlow
mono-butyl pH
might values,
cause
ether (PB) low
andvolatilities,
potential damageetc.
dipropylamine On (DP),
to the
the contrary, the high pH value of the aqueous DP solution might
membrane, and more caution needs to be taken during the operation because of the volatility and cause potential damage to the
were selected as the draw solutes. PB was once evaluated by Nakayama et al. [17] and the advantages
membrane,
toxicity andSo,
of DP. moreDP caution
is not a needs
very goodto bedraw
takensolution
during the operation
in the because
real world, but of in the
this volatility
case DP was and
of using glycol ethers as draw solutes include low viscosities, low pH values, low volatilities, etc.
toxicity of
selected to DP. So, DP is the
demonstrate not effect
a veryofgood drawliquid-liquid
different solution in the real world,on
equilibriums butthein FO
this performance.
case DP was
On the contrary,
selected
Figure 9 to the high pH
demonstrate
demonstrates thethevalue
effectofofthe
liquid-liquid aqueous
different DPdiagram
solution
liquid-liquid
equilibrium ofmight
equilibriums cause
the solvent on +thepotential damage
FO performance.
water systems. Theto the
membrane, and more
Figure 9 demonstrates
feasibility caution needs
the liquid-liquid
of using the UNIQUAC to be taken
modelequilibrium during
to estimate diagram the operation
of the solvent
the thermodynamic because of the
+ waterofsystems.
properties volatility
The and
the organic
toxicity of DP. So, DP is not a very good draw solution in the real world,
feasibility of using the UNIQUAC model to estimate the thermodynamic properties of the organic but in this case DP was selected
to demonstrate the effect of different liquid-liquid equilibriums on the FO performance. Figure 9
demonstrates the liquid-liquid equilibrium diagram of the solvent + water systems. The feasibility
of using the UNIQUAC model to estimate the thermodynamic properties of the organic solutions
Water 2017, 9, 189 10 of 17
Water 2017, 9, 189 10 of 17

was verified
solutionsbywas comparing the calculated
verified by comparing liquid-liquid
the calculated equilibrium
liquid-liquid data with
equilibrium literature
data with data
literature data[31,32].
In addition, theaddition,
[31,32]. In calculatedtheresults agree
calculated well agree
results with published results. Itresults.
well with published can beItseen
can that the that
be seen solubility
the of
watersolubility of water in the
in the organic-rich organic-rich
phase of the DPphase of the
+ water DP + water
mixture shows mixture shows
a greater a greater dependence
dependence on temperature
Water 2017, 9, 189 than PB, which suggests that larger RWATER values, thus lower 10energy of 17
than on
PB, temperature
which suggests that larger RWATER values, thus lower energy consumption, may be obtained
whenconsumption,
using DP. may be obtained when using DP.
solutions was verified by comparing the calculated liquid-liquid equilibrium data with literature data
[31,32]. In addition, the calculated results agree well with published results. It can be seen that the
solubility of80water in the organic-rich phase of the DP80+ water mixture shows a greater dependence
on temperature
70 than PB, which suggests that larger 70 RWATER values, thus lower energy
consumption, 60 may be obtained when using DP. 60
exp
exp
50 50 cal
cal

Temp ( C)
Temp ( C)

40 40

o
o

80 80
30 30
70 70
20 20
60 60
10 exp
exp 10
50 50 cal
cal
0 0

Temp ( C)
Temp ( C)

40 40

o
o

-10 -10
30 30
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
20 20
mole fraction of PB mole fraction of DP
10 10

0 (a) 0 (b)
-10 -10
Figure 9. Liquid-liquid equilibrium
0.0 0.1 0.2 0.3 0.4 0.5 0.6 diagram
0.7 0.8 0.9 of
1.0a lower critical solution temperature (LCST) organic
Figure 9. Liquid-liquid equilibrium diagram of a lower0.0critical
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
solution temperature (LCST) organic
solvents + water system;mole
(a)fraction of PB
propylene glycol n-butyl ether (PB) +mole
water; (b)
fraction dipropylamine (DP) +
of DP
solvents + water system; (a) propylene glycol n-butyl ether (PB) + water; (b) dipropylamine
water.
(DP) + water. (a) (b)

ToFigure 9. Liquid-liquid
investigate equilibrium
the influence diagram
of feed of a lower critical
concentration on FOsolution temperature the
performance, (LCST) organic
temperature for
separationsolvents
was+kept
wateratsystem;
80 C. The (a) propylene
results glycol n-butyl ether (PB) + water; (b) Figure
dipropylamine (DP)From
+
To investigate the influence of feedare shown
concentrationin Figure on10FO for PB and
performance, 11the
for DP.
temperature the for
results, water.
it can be expected that the energy consumption of the FO process using organic draw solute
separation was kept at 80 C. The results are shown in Figure 10 for PB and Figure 11 for DP. From
would increase by increasing the feed concentration, because the osmotic pressure difference is
the results,To it can be expected
investigate the influencethat the energy
of feed consumption
concentration on FOofperformance,
the FO process using organic
the temperature for draw
decreased. Comparing the FO performance when using PB as a draw solute with that when using DP,
solute would
separationincrease
was kept byatincreasing the feed
80 C. The results are concentration,
shown in Figure 10 because
for PB and the Figure
osmotic pressure
11 for DP. From difference
the is
it is clearly demonstrated that much more energy is required for the PB draw solute. This can be
decreased.results, it can be expected
Comparing the FO that the energy consumption
performance when using of the
PB FO
as process
a draw using
solute organic
with draw
that solute
when using
explained by their difference in liquid-liquid equilibrium behavior. The mole fraction concentration of
iswould
DP, itthe clearly increase by increasing
PB drawdemonstrated
solution in the organicthat the
much feed concentration,
rich more
phase energy
is 0.409 atisbecause
required
the
thefor
temperature
osmotic
theofPB pressure
draw
80 C.
difference
solute.
In addition, Thisis can be
it will
decreased. Comparing the FO performance when using PB as a draw solute with that when using DP,
explained
reach by their difference
pressure in liquid-liquidat theequilibrium behavior. ifThe mole fraction concentration of
it isthe osmotic
clearly demonstrated equilibrium
that much more concentration
energy of 0.381,
is required for the thePBorganic rich phase
draw solute. Thisiscanused
C. In addition,
be as
the PB draw
drawsolution
theexplained solution in
and the
the organic
feed rich
solution phase
is is
composed 0.409of at
0.5 the temperature
molkg 1 NaCl. Onof
by their difference in liquid-liquid equilibrium behavior. The mole fraction concentration of the80 contrary, the change it will
reachinthe concentration
the osmotic
PB draw solutionfor DP
pressure draw
in equilibrium
the solution
organic rich is
thefrom
atphase 0.751attothe0.579
concentration
is 0.409 at the ifsame
of 0.381,
temperature ofthe condition.
80 organic
C. richThe
In addition, ithigher
phasewill is used
concentration
as the draw solution
reach the of DP
osmoticand in the organic
the feed
pressure rich
solution
equilibrium phase
at the after phase
isconcentration
composed of separation
0.5 mol
of 0.381, means
if the 1
kgorganic it can
NaCl. produce
On the
rich phase a higher
contrary,
is used as the
changeosmotic
the
in drawpressure
concentration compared
solution andfortheDP todraw
feed that ofsolution
solutionPB.isThus, isafrom
composed greater RWATER
of0.751
0.5 molkg value
1 NaCl.
to 0.579 andthe
On
at the a better
same FO performance
contrary, the change
condition. The higher
were achieved by using
in concentration DPdrawas draw solute.is from 0.751 to 0.579 at the same condition. The higher
concentration of DP inforthe DP organicsolution
rich phase after phase separation means it can produce a higher
concentration of DP in the organic rich phase after phase separation means it can produce a higher
osmotic pressure compared to0.20 that of PB. Thus, a greater RWATER value and a better FO performance
osmotic pressure compared to that of PB. Thus, a greater RWATER value and a better FO performance
were achieved by using DP DP as0.18draw 16000
were achieved by using as drawsolute.
solute.
RWater Energy
0.16 14000
0.20
Energy (MJ/ton)

16000
RWATER

0.14
0.18 12000
RWater Energy
0.12
0.16 14000
10000
Energy (MJ/ton)
RWATER

0.14
0.10 12000
8000
0.12
0.08
10000
0.10
0.06 6000
8000
0.08
0.0 0.2 0.4 0.6 0.8 1.0
NaCl (mol/kg)
0.06 6000

Figure 10. The effect of feed0.0solution

0.2 concentration
0.4 0.6on the0.8
FO process
1.0 performance using PB as the
draw solute. NaCl (mol/kg)

Figure 10. The effect of feed solution concentration on the FO process performance using PB as the
Figure 10. The effect of feed solution concentration on the FO process performance using PB as the
draw solute.
draw solute.
Water 2017, 9, 189 11 of 17
Water 2017, 9, 189 11 of 17

Water 2017, 9, 189 11 of 17

1.35
2450
1.35
1.30
RWater Energy 2450
2400
1.30

(mol/kg)
1.25 RWater Energy 2400
2350

(MJ/ton)
(mol/kg)
1.25 2350
2300
1.20

(MJ/ton)
RWATER
1.20 2300
2250

Energy
1.15

RWATER
2250
2200

Energy
1.15
1.10
2200
2150
1.10
1.05 2150
2100
1.05
1.00 2100
2050
0.0 0.2 0.4 0.6 0.8 1.0
1.00 NaCl (mol/kg) 2050
0.0 0.2 0.4 0.6 0.8 1.0
NaCl (mol/kg)
Figure 11. The effect of feed solution concentration on the FO process performance using DP as the
Figure 11. The effect of feed solution concentration on the FO process performance using DP as the
draw solute.
drawFigure
solute.11. The effect of feed solution concentration on the FO process performance using DP as the
draw solute.
As the organic rich phase is used as a draw solution, the concentration of draw solution using
As theAs organic
organic solute
the organicrich
with an phase
richLCST is is
used
point
phase asasaadraw
is controlled
used drawbysolution, theconcentration
the separation
solution, the concentration
temperature. of draw
ofThe
draw solution
temperature
solution wasusing
using
manipulated
organic solute
organic to study
withwith
solute an LCST its
an LCST effect
point on
point the FO performance
isiscontrolled
controlled by using DP
the separation
by the as draw
separationtemperature.solute.
temperature. It
TheThecan be seen from
temperature
temperature was was
the results
manipulated
manipulated shown
to study
to study ineffect
its Figure
its on12on
effect the that
the
FOFOthe RWATER value
performance
performance usingincreases
using DPas
DP asdrawwith
draw increasing
solute.
solute. It cantemperature.
It can bebeseen
seenfrom
from the
However,
the resultsthe energy
shown in consumption
Figure 12 was
that first
the decreased
RWATER thenincreases
value increasedwith
with increasing
increasing temperature.
temperature,
results shown in Figure 12 that the RWATER value increases with increasing temperature. However,
and achieve
However, thea minimal
energy was value at around
consumption was76first
C.decreased
Although athengreater RWATER
increased withcan be obtained
increasing at higher
temperature,
the energy consumption first decreased then increased with increasing temperature, and achieve a
temperatures because value
and achieve a minimal of theatmore
around concentrated drawa solution.
76 C. Although More thermal
greater RWATER energy would
can be obtained at higherbe
minimal value
required
at around
to heat
76 C. Although
up the solution.
a greater RWATER
As aconcentrated
consequence of
can be obtained
thesesolution.
two effects, an thermal
optimized
at higher temperatures
temperature
temperatures because of the more draw More energy would for be
because of the more
liquid-liquid concentrated
separation might be draw solution. More thermal energy would be required to heat
required to heat up the solution. As found for certain
a consequence FO processes
of these using
two effects, draw
an optimizedsolutes with LCST
temperature for
up the solution.
points. As a consequence of these two effects, an optimized temperature
liquid-liquid separation might be found for certain FO processes using draw solutes with LCST for liquid-liquid
separation
points.might be found for certain FO processes using draw solutes with LCST points.
3000
3.0
3000
3.0
2.5 2800

2.5 2800
(MJ/ton)
RWATER

2.0
RWater 2600
(MJ/ton)
RWATER

2.0
1.5
Energy

RWater 2600
1.5
Energy

2400
1.0
Energy 2400
1.0
0.5
Energy 2200
0.5
0.0 2200
60 70 80 90 100
0.0 o
60 70 Temp
80 ( C) 90 100
Temp
Figure 12. The effect of separation temperature (oC)FO process performance using DP as the draw
on the
solute. 12. The effect of separation temperature on the FO process performance using DP as the draw
Figure
Figure 12. The effect of separation temperature on the FO process performance using DP as the
solute.
drawFigure
solute.13 gives a direct comparison of the energy consumptions of the FO processes using
different draw
Figure 13 solutes.
gives a Itdirect
shows that the energy
comparison of theconsumptions of FO processes
energy consumptions of theusing PB and Na
FO processes 2SO4
using
were
Figure more
different13drawsensitive
givessolutes.to feed concentration
a directIt comparison
shows that the changes.
ofenergy The FO
consumptions
the energy process
of FO of
consumptions using PB
processes exhibited
the FO using the
PB and
processes highest
using SO4
Na2different
energy
were consumption
more sensitive among
to feed the four investigated
concentration changes.draw
Thesolutes,
FO whichusing
process was about
PB ten times
exhibited thethe value
highest
draw solutes. It shows that the energy consumptions of FO processes using PB and Na2 SO4 were
of the NH 3-CO2 process. Compared with NH3-CO2draw
, the Na 2SO4 process showed a much lower theenergy
moreenergy consumption
sensitive among
to feed concentrationthe four investigated
changes. solutes,
The FO process which PB
using was about ten times
exhibited the highest value
energy
value. However, it should be noted that the cooling operation is
of the NH3-CO2 process. Compared with NH3-CO2, the Na2SO4 process showed a much lower achieved normally with the
energy
consumption
utilization
among the
of electric
four investigated
power which is a that
draw
high the
grade
solutes, which
energy,
was about
while a low-grade
ten
heat
times the
source was
value of the
value. However, it should be noted cooling operation is achieved normally withused
the
NH3 -CO
for 2 process.
the Compared
decomposition with
of the which
NH NH3 -CO2 , So,
3-CO
theequivalent
Na2 SO4 process showed for a much lower energy
utilization of electric power is 2asolution.
high grade energy, work
while is necessary
a low-grade the comparison
heat source was used
value.for
However,
of total it should
energy consumption,
the decomposition be noted that the
as discussed
of the NH cooling operation is achieved normally with
later. So, equivalent work is necessary for the comparison
3-CO2 solution.
the utilization
of electric
of totalpower
energy which is a high
consumption, grade energy,
as discussed later. while a low-grade heat source was used for the
decomposition of the NH3 -CO2 solution. So, equivalent work is necessary for the comparison of total
energy consumption, as discussed later.
Water 2017, 9, 189 12 of 17
Water 2017, 9, 189 12 of 17

10000 NH3-CO2
Na2SO4
PB
DP

Energy (MJ/ton)
1000

100
0.0 0.2 0.4 0.6 0.8 1.0
NaCl (mol/kg)

Figure
Figure 13.
13. Energy
Energyconsumption of of
consumption thethe
FOFO
process using
process different
using drawdraw
different solutes as a function
solutes of NaCl
as a function of
concentrations.
NaCl concentrations.

3.4. Equivalent Work for FO

3.4. Equivalent Work for FO
In order to compare the total value of the FO processes using different grades of energy, a
In order to compare the total value of the FO processes using different grades of energy, a method
method of involving the calculation of equivalent work, in which the energy consumed was
of involving the calculation of equivalent work, in which the energy consumed was assigned an
assigned an electrical work value, was considered. For the FO processes using NH3-CO2 and organic
electrical work value, was considered. For the FO processes using NH3 -CO2 and organic solutes
solutes with LCST points, thermal energy is required for the recovery of draw solutions. In the case
with LCST points, thermal energy is required for the recovery of draw solutions. In the case where
where no low grade heat source is available, fuel energy would be directly charged to the FO process.
no low grade heat source is available, fuel energy would be directly charged to the FO process. So,
So, the equivalent work is associated to the electrical work produced by the fuel energy [31], which
the equivalent work is associated to the electrical work produced by the fuel energy [31], which can be
can be calculated by the following equation:
calculated by the following equation:
W = Q + W (13)
Weqeq= Qdd pd
pd pump
+ Wpump (13)
Q means the thermal energy supplied to the FO process, pd is the overall power plant efficiency,
Qdd means the thermal energy supplied to the FO process, pd is the overall power plant efficiency, and
W
and Wpump is the electrical energy requirements for pumping work.
pump is the electrical energy requirements for pumping work.
Figure 14. gives an example where low grade thermal energy from a cogeneration power desalting
Figure 14. gives an example where low grade thermal energy from a cogeneration power
plant [32] is available for the FO process. The steam supplied to the FO process is extracted from the
desalting plant [32] is available for the FO process. The steam supplied to the FO process is extracted
low pressure turbine. In this case, the equivalent work to the thermal energy Qd is relevant to the
from the low pressure turbine. In this case, the equivalent work to the thermal energy Q d is relevant
electrical work produced by the low pressure turbine:
to the electrical work produced by the low pressure turbine:
Weq = Qd LP + Wpump (14)
Weq = Qd LP + Wpump (14)
where LP means the low pressure turbine efficiency for producing electrical work. In addition, if
where
assumed LPthatmeans the Rankine
the ideal low pressure
cycleturbine efficiency
is employed forlow
by the producing
pressureelectrical
turbine, work. In addition,
the equivalent work if
assumed that the
can be further ideal Rankine
calculated as: cycle is employed by the low pressure turbine, the equivalent work
can be further calculated as:
h h2
Weq = Qd 1 Eturbine + Wpump (15)
hh1 hh3
Weq = Qd 1 2
Eturbine + Wpump (15)
where h1 is the enthalpy of the steam used hto1 h3
provide process heat input, h2 is the enthalpy of the
steam at the turbine outlet, and h3 is the enthalpy of the steam at the condenser outlet. In this study,
where h1 is the
the condenser enthalpy of
temperature wastheassumed
steam used
to beto35
provide
C. E process heat input, h2 is the enthalpy of the
turbine is the turbine efficiency which is assumed
at the turbine outlet, and h3 is the enthalpy of the steam at the condenser outlet. In this study,
to be 85%.
steam
the condenser temperature was assumed to be 35 C. Eturbine is the turbine efficiency which is
assumed to be 85%.
Water 2017, 9,
Water 2017, 9, 189
189 13
13 of
of 17
17

Wt We

Qf

Qd LP Turbine
HP Turbine

FO Process

Figure 14. Schematic

Figure 14. Schematic diagram
diagram of
of cogeneration
cogeneration power
power desalting
desalting plant.
plant.

For the FO
FO process
process using
usingNa 2SO
Na 4, electrical
2 SO work
4 , electrical is required
work for draw
is required solute
for draw recovery.
solute The
recovery.
equivalent work for the heat removal by the refrigerator system is expressed as:
The equivalent work for the heat removal by the refrigerator system is expressed as:

Qdd
Q
Weqeq==
W ++W
Wpump
pump
(16)
(16)
COP
COP
whereCOP
where COP (Coefficient
(Coefficient of Performance)
of Performance) is theisratio of cooling
the ratio or heating
of cooling to energy
or heating consumption.
to energy consumption.COP
is largely dependent on operating conditions, like the cooling
COP is largely dependent on operating conditions, like the cooling and ambient temperatures, and ambient temperatures, coolant
medium,
coolant medium,the efficiency of the heat
the efficiency pump,
of the heatetc.
pump,In thisetc.study,
In thisCOP is assumed
study, COP is to assumed
be 4.5 forto cooling
be 4.5 thefor
diluted
cooling draw solution
the diluted from
draw room temperature
solution to 0 C, and atoglycol
from room temperature 0 C, refrigeration system was used.
and a glycol refrigeration system
The results of equivalent work at different draw solution concentrations are displayed in
was used.
Figures The1517.
resultsIn ofthose calculations,
equivalent work atall the feed
different solutions
draw solution consisted of 0.5 mol
concentrations kg1 NaCl.
aredisplayed in For
Figuresthe
draw
1517.solute
In those of NH 3 -CO2 , theall
calculations, boiler temperature
the feed solutionswas approximated
consisted at 1001 NaCl.
of 0.5 molkg C under Forambient
the draw pressure
solute
so low grade steams of 110 and 130 C were used. Because the temperature for liquid-liquid separation
of NH3-CO2, the boiler temperature was approximated at 100 C under ambient pressure so low grade
of DP +of water solutions C, a heat source of 90 C can be used for the FO process
steams 110 and 130 Cwas were below
used.80Because the temperature for liquid-liquid separation of DP +
using a draw solute of DP. It can
water solutions was below 80 C, a heat source of 90 C be seen in Figure 15 can
thatbethe equivalent
used for the FO work was using
process from 60.5
a draw to
117.6 kWh ton 1 for NH -CO when the heat was directly supplied by fuel energy. When a low grade
solute of DP. It can be seen 3 in2Figure 15 that the equivalent work was from 60.5 to 117.6 kWhton for 1

steam of 110 C was used, the lowest equivalent work could be 21.1 kWhton1 which suggests that the
NH3-CO 2 when the heat was directly supplied by fuel energy. When a low grade steam of 110 C was
grade
used, of theheatlowestsources would have
equivalent worka significant
could be 21.1 influence
kWhton on 1
thewhich
process value. For
suggests thatthe thecase of Na
grade of2 SO
heat 4,
as shown in Figure 16, the minimum of equivalent work was 12.3 kWh ton 1 if the value of COP was
sources would have a significant influence on the process value. For the case of Na2SO4, as shown in
C, was in the 1 as
4.5.
Figure The16,equivalent
the minimum work of of DP using a work
equivalent steamwas of 9012.3 kWhton1 ifrange of 55.0
the value oftoCOP70.6 kWhwaston
4.5. The
shown
equivalent in Figurework17. of DPFor using
a direct comparison
a steam of 90 C,of the
wasequivalent
in the rangework of thetoFO
of 55.0 processes
70.6 kWhtonusing different
1 as shown in
draw
Figuresolutes,
17. Forthe minimum
a direct equivalent
comparison work
of the for each draw
equivalent worksolute
of the(for
FOexample,
processes the valuedifferent
using for NH3draw
-CO2
process
solutes, was obtained with
the minimum 10 molwork
equivalent kg1for COeach
2 and draw
C heat source) are presented in Figure 18.
110 solute (for example, the value for NH3-CO2
It can bewas
process seenobtained
that while a lower
with temperature
10 molkg 1 CO2 and steam 110can be employed
C heat source) are forpresented
the FO process using
in Figure 18.DP, the
It can
equivalent
be seen that work
while wasa still
lower larger than the one
temperature steamusing canNH -CO2 . The FO
be3employed for process
the FO using
process a draw
usingsolute
DP, the of
Na SO
equivalent
2 4 exhibited the lowest equivalent work among the draw solutes
work was still larger than the one using NH3-CO2. The FO process using a draw solute ofinvestigated in this study.
Na2SO The method the
4 exhibited developed in this work
lowest equivalent work provides
among the an draw
approach to investigated
solutes quickly estimate in thisthe energy
study.
consumption
The method of andeveloped
FO processin using
thiscertain
work drawprovides solute,
an therefore,
approach ittowouldquicklybe helpful
estimateforthescreening
energy
the draw solutes. However, it should also be noted that the assumptions
consumption of an FO process using certain draw solute, therefore, it would be helpful for screening in this study are based on
ideal
the draw conditions.
solutes.More However, factors it such
should as also
the membrane
be noted that permeability, long term
the assumptions stability,
in this studyand the price
are based on
of theconditions.
ideal energy need to befactors
More taken suchinto consideration
as the membrane for more practical long
permeability, operations. For example,
term stability, and the the FO
price
process using NH
of the energy need 3 -CO 2 may
to be taken be into
moreconsideration
attractive than forusing
moreNa 2 SO4 if abundant
practical operations. low Forgrade heat sources
example, the FO
at cheapusing
process pricesNH are3-CO
available.
2 may be more attractive than using Na2SO4 if abundant low grade heat sources

at cheap prices are available.

Water 2017, 9, 189 14 of 17
Water 2017, 9, 189 14 of 17
Water 2017, 9, 189 14 of 17
Water 2017, 9, 189 14 of 17
120
120
120
110
110 110ooC
110
100
110oC
130
110ooC

(kWh/ton)
100 130 CC

(kWh/ton)
100
90 Fuelo
130 C
Fuel

(kWh/ton)
90
90
80 Fuel
80

Work
80
70

Work
70

Work
70
60
Equiv
60
Equiv 60
50
Equiv
50
50
40
40
40
30
30
30
20
20
20 0 2 4 6 8 10
0 2 4 6 8 10
0 2 4 CO2 (mol/kg)
6 8 10
CO2 (mol/kg)
2
CO (mol/kg)
Figure 15.
15. Equivalent work of
Equivalent work of the FO
FO process using NH
NH3-CO
-CO222 as
as the
the draw
draw solute.
Figure
Figure 15. Equivalent work of the
the FO process
process using
using NH33-CO as the draw solute.
solute.
Figure 15. Equivalent work of the FO process using NH3-CO2 as the draw solute.
30
30
30
(kWh/ton)

25
(kWh/ton)

25
(kWh/ton)

25
Work

20
Work

20
Work

20
Equiv
Equiv
Equiv

15
15
15

10
10 1.0 1.5 2.0 2.5 3.0
10 1.0 1.5 2.0 2.5 3.0
1.0 1.5 Na2SO42.0
(mol/kg) 2.5 3.0
Na2SO4 (mol/kg)
Na2SO4 (mol/kg)
Figure 16. Equivalent work of the FO process using Na2SO4 as the draw solute.
Figure 16.
Figure 16. Equivalent work of
Equivalent work of the
the FO
FO process
process using
using Na
Na2SO
SO4 as
as the
the draw
draw solute.
solute.
Figure 16. Equivalent work of the FO process using Na22SO44 as the draw solute.

250 90ooC
250 90 oCo
250 110
90 C oC
110 C
Fuel
(kWh/ton)

o
Fuel C
110
(kWh/ton)

200 Fuel
(kWh/ton)

200
200
Work
Work

150
Work

150
Equiv

150
Equiv
Equiv

100
100
100

50
5058 60 62 64 66 68 70 72 74 76 78 80 82
5058 60 62 64 66 68 70 72 74 76 78 80 82
58 60 62 64 66 68 70(ooC)
Temp 72 74 76 78 80 82
Temp ( oC)
Temp ( C)
Figure 17. Equivalent work of the FO process using DP as the draw solute.
Figure 17. Equivalent work of the FO process using DP as the draw solute.
Figure
Figure 17.
17. Equivalent
Equivalent work
work of
of the
the FO
FO process
process using
using DP as the
DP as the draw
draw solute.
solute.
Water 2017, 9, 189 15 of 17
Water 2017, 9, 189 15 of 17

60

NH3-CO2
50
Na2SO4
DP

NH3-CO2 (kWh/ton)
40

30

20

10

0
Draw Solute

Figure
Figure 18.
18. Equivalent
Equivalent work
work comparison
comparison of
of the
the FO
FO process
process using
using different
different draw
draw solutes.
solutes.

4.
4. Conclusions
Conclusions
The
The energy
energy requirements
requirements of of the
the FO
FO process
process using
using various
various drawdraw solutes
solutes were
were presented
presented under
under
different
different feed and draw solution concentrations. It was found that the increasing feed
feed and draw solution concentrations. It was found that the increasing feed solution
solution
concentrations
concentrations would
would have
have aa negative
negative effect
effect on
on process
process performance.
performance. The The energy
energy consumption
consumption of of the
the
FO process decreased with increasing draw solution concentration. The
FO process decreased with increasing draw solution concentration. The NH3 -CO2 process had theNH 3-CO2 process had the

lowest
lowest thermal
thermal energy
energy requirement
requirement among
among the the three
three FOFO processes
processes because
because the
the draw
draw solute
solute recovery
recovery
was
was achieved by heating. On the contrary, the FO process using propylene glycol mono-butyl ether
achieved by heating. On the contrary, the FO process using propylene glycol mono-butyl ether
showed
showed aa relatively
relatively large
large energy
energy consumption
consumption due due toto its
its small
small solubility
solubility in
in water.
water. The
The FOFO process
process
using
using Na
Na22SO
SO44required
requiredthethelowest
lowest equivalent
equivalent work,
work, and
and the
the cooling
cooling efficiency
efficiency largely
largely depended
depended on on
operating conditions.
operating conditions.
For
For the
the future development of
future development of draw
draw solutes,
solutes, the
the NH
NH3-CO 2 system has high potential due to its
3 -CO2 system has high potential due to its
low
low thermal energy consumption and its ability to treat highly concentrated feed
thermal energy consumption and its ability to treat highly concentrated feed solutions.
solutions. Although
Although
Na
Na22SO
SO44seems
seemsto tobe
beaa promising
promising drawdraw solute
solute onon terms
terms of of the
the equivalent
equivalent work,
work, further
further studies,
studies, such
such
as
as the
the mass
mass transfer
transfer mechanism
mechanism across
across the
the membrane
membrane and and thethe crystallization
crystallization andand dissolution
dissolution rate
rate of
of
Na 2SO4 salt, are essential. For the development of draw solutes with LCST points, it is important to
Na2 SO4 salt, are essential. For the development of draw solutes with LCST points, it is important to
find
find an
an organic
organic solute
solute whose solubility in
whose solubility in water
water isis strongly
strongly dependent
dependent on on temperature.
temperature.

Acknowledgments:
Acknowledgments: The The support
support of
of the
the National
National Key
Key Technologies
Technologies R&D
R&D Program
Program of
of China
China (No.
(No. 2015BAE06B00)
2015BAE06B00)
is gratefully acknowledged.
Author Contributions:
Author The authors
Contributions: The authors contributed
contributed equally
equally to
to this
this work.
work.
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.

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