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A signicant amount of energy stored in the form of salinity in seawater reverse osmosis (SWRO) brine can
be harvested by a pressure retarded osmosis (PRO) process for power generation. The crucial performance-
determining factor of the PRO process is the semi-permeable PRO membrane, which separates the SWRO
brine from a lower salinity solution and sustains the salinity dierence between the two solutions.
However, accumulation of solutes in the support membrane, namely internal concentration polarization
(ICP), signicantly reduces the eective salinity dierence and thus severely limits the eciency of
conventional PRO membranes. In this paper, we report the fabrication and optimization of thin-lm
nanober composite PRO (TNC-PRO) membranes with a unique support membrane structure (inter-
connected, low tortuousness and highly porous properties), aiming to facilitate mixing of accumulated
solutes with a dilute feed stream and overcome the ICP problem. With such low structure parameter (S)
value (150 mm) nanober support membranes (NSMs), the optimum water permeability (A) and solute
permeability (B) of the TNC-PRO membrane for power generation were determined to be 4.1 L m2 h1
bar1 and 1.74 L m2 h1 respectively. This highly ecient TNC-PRO membrane can achieve a power
density of 15.2 W m2 and maximum energy recovery of 0.86 kW h m3, using synthetic brackish water
(80 mM NaCl, p 3.92 bar) and seawater brine (1.06 M NaCl, p 51.8 bar) as feed and draw solution,
Received 2nd September 2012
Accepted 28th January 2013
respectively. For a more dilute synthetic river water (0.9 mM NaCl, p 0.045 bar) feed solution, the
same membrane can achieve a higher power density of 21.3 W m2. The main performance limiting
DOI: 10.1039/c3ee23349a
factors in PRO application such as ICP, External Concentration Polarization (ECP) and Reverse Solute
www.rsc.org/ees Permeation (RSP) are quantied and their values are related to A, B and S values of TNC-PRO membranes.
Broader context
The high mechanical strength thin-lm nanober pressure retarded osmosis (TNC-PRO) membrane sustains an ideal interconnected pore structure to break the
bottleneck of ICP for ecient osmotic power production from otherwise wasted seawater brine. This process has great potential to turn the hazardous brine
waste into energy. The maximum energy recovery rate of 0.94 kW h m3 (river water feed solution) is approximately 20% of the energy required to produce fresh
water from seawater. If incorporated with reverse osmosis technologies, this PRO process can signicantly reduce the cost of seawater desalination.
This journal is The Royal Society of Chemistry 2013 Energy Environ. Sci., 2013, 6, 11991210 | 1199
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harvests the energy driven by a salinity gradient. With the PRO In this work, highly ecient TNC-PRO membranes with a
membrane separating a high salinity draw solution from a low low S value nanober support membrane structure were
salinity feed solution, water naturally permeates from the feed designed and fabricated for the rst time. The TNC-PRO
solution side to the draw solution side while solutes are selec- membranes were modied with chlorine to attain a series of
tively rejected. The trans-membrane water ux, JW, drives a water permeability coecient (A) and solute permeability coef-
hydroturbine mounted on the draw solution side and generates cient (B) values. Performance limiting phenomena, such as
power (Fig. S1). The signicance of the water ux, JW, depends internal concentration polarization (ICP), external concentra-
on the eective salinity dierence across the membrane selec- tion polarization (ECP), and reverse solute permeation (RSP),
tive layer. Past studies have concluded that the salinity in were quantied and elucidated with experimental data and
seawater is able to sustain a commercial scale PRO plant as long theoretical studies. The optimization protocols to achieve high
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as the ecient PRO membranes could be developed with a W > 5 eciency energy recovery from seawater brine using brackish
W m2.810 water as feed solution were systematically studied. The
The PRO process can be applied at the estuarial area where the maximum energy recovery rate using TNC-PRO membranes
river water mixes with the seawater. A recent study on the ther- were calculated using variable DP and constant DP models.
modynamic eciency of PRO power extraction from the mixing
of river water and seawater revealed that aer deducting the 2 Materials and methods
process losses and ineciencies, the technology can extract a net
1370 TW h per year of renewable energy to fulll the electrical 2.1 Fabrication of nanober support membrane (NSM)
consumption of 520 million people.11 However, this seawater 2.1.1 Electrospinning of nascent NSM. Polyacrylonitrile
river water PRO strategy is not feasible in water-scarce regions (PAN) nanober support membranes (NSMs) were electrospun
such as Singapore, where river water is primarily used as the tap from 8% w/w PAN (Mw 150 000 g mol1) in N,N-dimethyl
water source.12 Brackish water (5000 ppm TDS), on the other formamide using a custom-built rotating drum electrospinning
hand, could represent a better alternative since it is a readily device.26 As a key measure to improve the mechanical strength
available source for low cost feed solution, owing to the world- of the NSM, tetraethylorthosilicate was dissolved in the PAN
wide distribution of water reclamation plants from waste- precursor solution (6% w/w) and the resultant solution was
water.1316 In addition, seawater brine with high salinity, which is vigorously stirred for at least an hour. Then 2% w/w of acetic
conventionally considered as a waste stream which could severely acid (AA) was slowly dropped into the solution. The total mixed
impair the ecological environment in oceans, may be used as a solution was continuously stirred for 2 hours at 80 C and
more ecient and low cost draw solution.17,18 Furthermore, since another 24 hours at room temperature prior to electrospinning.
seawater brine is pre-treated prior to the reverse osmosis process, Typically, a DC voltage of 30 kV was applied between a stainless
most of the foulants detrimental to membranes are removed thus steel spinneret orice (diameter 0.7 mm) and a collecting
leaving only a concentrated salt content in the brine.19 The stainless steel rotating drum (300 rpm), which is 15 cm beneath
strategy of using brackish water and seawater brine as feed and the orice. The rotating drum was driven by a horizontally
draw solutions respectively for the PRO process could potentially oscillating actuator (60 cm min1) simultaneously. Prior to
turn these waste streams into energy and hence can be adopted electrospinning, the stainless steel rotating drum (length
by the conventional reverse osmosis desalination plants to diameter 20 cm 10 cm) was wrapped with a poly(ethylene
reduce the cost of seawater desalination.20 terephthalate) (PET) non-woven substrate (Ahlstrom Grade
Generally, a W value of 5 W m2 is required for the 3257). The non-woven substrate was pre-wetted with N-methyl-
commercialization of the PRO process using seawater and river pyrrolidone (Acros Organics) to ensure the NSM is bonded with
water as draw and feed solution respectively.19,21 However, due the substrate. The PAN solution was then fed to the spinneret by
to the lack of highly ecient PRO membranes, the harvested W a syringe pump with a constant rate of 40 mL min1. Under the
was far below the benchmark value.2224 Recently, Chou et al. inuence of an electrical eld, the polymer solution was
reported that a high W of 5.7 W m2 could be harvested by a continuously electrospun into ultrane nanobers. The nano-
hollow ber composite polyamide membrane from synthetic bers dried out and were spun-bounded to be a nascent nano-
seawater and river water.14 A study by another group showed an ber support membrane with a maximum eective area of 600
enhancement of the membrane water permeability which has cm2 (length width 30 cm 20 cm). The membrane was
resulted in a higher W of 10 W m2 through a composite poly- sandwiched between two pieces of clear glass (10 mm thick) and
amide membrane in a at sheet form which was modied with heat-treated at 120 C for 2 hours, resulting in a stabilized
chlorine.6 However, these membranes possessed high structure nanober membrane. Chemicals (if not specied) were
parameter (S) values ranging from 350 to 1000 mm.13,25 When purchased from Sigma-Aldrich.
brackish water is used as feed solution, these membranes tend 2.1.2 Coating of poly(vinyl alcohol). At the nal step of
to have signicantly lower W because of severe internal fabrication of NSMs, the nascent NSMs were dip-coated with 1%
concentration polarization (ICP) (Fig. S1).13,19 It has been w/w of PVA (Mw 89 00098 000, 99+% hydrolyzed, Sigma-
proposed that a membrane with an S value around 150 mm is Aldrich) aqueous solution for 5 minutes. An air knife (Exair
ideal for a PRO membrane in an osmotic power plant.10 To date, PVDF super air knife, USA) was employed to drain excess PVA
highly ecient PRO membranes with suciently low S values to solution from the NSM surface. The NSM was then dried at 90
overcome the ICP limitation have not been reported. C in an oven for 5 min. Subsequently, the PVA-coated NSM was
1200 | Energy Environ. Sci., 2013, 6, 11991210 This journal is The Royal Society of Chemistry 2013
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cross-linked in a tank with 0.5% w/w glutaraldehyde in acetone/ images were obtained using a Joel JSM 7600F thermal eld
DI water (50/50) for 30 minutes. Aer the cross-linking reaction, emission SEM (FESEM). Exposed cross-sections were obtained
the NSM was cured again at 90 C in the oven for 5 minutes, by fracturing the samples immediately aer ash-freezing by
washed substantially and then preserved in deionized (DI) water liquid nitrogen. An EMITECH SC7620 sputter coater was
at 5 C until further test. utilized to coat all samples with gold for 4560 seconds. The
The NSMs without PVA coating and SiO2 are designated as topology of a typical TNC-PRO membrane was probed by a Park
NSM-0, the NSMs with PVA coating but no SiO2 are designated XE-100 Atomic Force Microscope (AFM) in non-contact mode.
as NSM-1, whereas the NSMs with both PVA coating and SiO2 Contact angle measurements were determined by an OCA
are designated as NSM-2. Contact Angle System (DataPhysics, Germany) and reported as
an average of 10 measurements. The mechanical strength of the
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2.2 Interfacial polymerization NSMs was tested using a Zwick 0.5KN Universal Testing
Interfacial polymerization was performed on the top surface of Machine. The pore size distribution was evaluated by a capillary
NSMs. An NSM was rst immersed into isopropanol for better ow porometer (model CFP 1500A, Porous Materials Inc., Sin-
wetting ability. The recipe for the interfacial polymerization was gapore) through bubbling point and gas permeation tests.
adopted from the literature with some modications.27 Typi-
cally, the NSM, being taped to a glass with four sides sealed, was
2.5 Determination of membrane intrinsic parameters
rinsed with DI water for several times and was soaked in 3% m-
phenylenediamine aqueous solution (with 1.1% w/w triethyl- The value of intrinsic water permeability coecient (A) was
amine and 2.3% w/w camphor sulfonic acid) for 2 minutes. An determined by a bench scale cross-ow RO unit (SEPA CF II, GE,
air knife (Exair PVDF super air knife, operated at 0.2 bar), held eective area is 140 cm2).26 The intrinsic solute permeability
approximately 10 mm above the support membrane surface, coecient (B) and structure parameter (S) were calculated based
was used to drain excess m-phenylenediamine aqueous solution on the monitored water ux, JW, and solute ux, JS, in a custom-
from the saturated NSMs. A complete pass of the air knife over a built cross-ow FO system. A FO module with an eective
15 cm-long membrane coupon took about 10 seconds. The membrane area of 23.8 cm2 was used to mount the TNC-PRO
surface of the membrane quickly became dull and dry. Then, membrane coupons. Cross-ow velocities at both feed and draw
0.15% w/w trimesoyl chloride in hexane was introduced onto solution sides were maintained by gear pumps (Cole-Palmer) at
the surface of the NSMs. Aer 1 minute of reaction, the nascent 15.4 cm s1. Spacers (Sepa CF feed spacer, 17 mil) were inserted
composite membrane was allowed to sit for 30 min and then in the 2 mm deep channels on both sides. The protocols to
cured at 95 C for 3 minutes in an oven in order to dehydrate the deduce the B and S values based on the monitored data are
membrane and improve the integrity of the polyamide layer. explained in the ESI with reference to a previous study.6
This journal is The Royal Society of Chemistry 2013 Energy Environ. Sci., 2013, 6, 11991210 | 1201
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where P is the power in kW, r is the density of water, g is the cross ow velocity (CFV) and temperature, the value of di is
local gravity, Q is the water ow in m3 s1, and H is the water predominantly dependent on the draw and feed solutions
head in meter. Dened as the power generated by a unit area of (CD,b, CF,b) and membrane intrinsic characteristics (A, B, S).
the membrane, Am, the power density, W, can be calculated by:
0
1fC
2.8 Modeling of JW, W, ECP, ICP and RSP E C0 DP=Ct 2 dC (5)
C0
The trans-membrane water ux, JW, can be further expressed
as:22 where, C0 is the initial CD,b at t 0, Ct is the CD,b at time t,
(1 f)C0 represents the nal CD,b when PRO operation ends
JW A(Dpeff DP) A(bRgTDCm DP) (3) and DP is the applied hydraulic pressure at the draw solution
side. The optimum DP is a function of CD,b (Fig. S6). The ratio
where, Dpe is the eective osmotic pressure driving force between the initial volume of the feed solution and the total
across the membrane selective layer. The term (Dpe DP) initial volume of the feed and draw solutions, f, has been
represents the net driving force across the membrane selective dened in a previous study.11
layer. b is the vant Ho factor,8 Rg is the gas constant and T is
the thermodynamic temperature. DCm is the solute concentra-
tion dierence across the membrane selective layer, which can 3 Results and discussion
be further expressed as:13
3.1 Nanober support membrane (NSM) characteristics
CD;b expJW =k CF;b expJW S=D
DCm A suitable NSM for high pressure applications such as PRO
1 B=JW expJW S=D 1 B=JW 1 expJW =k
should sustain a proper mechanical strength and possess an
(4)
ideal pore structure with a suciently low S value. Hence, in
where, CD,b and CF,b are the concentrations of bulk draw solu- this work, we designed and tailored a composite NSM to cater
tion and feed solution respectively. k is the mass transfer coef- specially for this interest. The appearance of a typical NSM-2 is
cient; the value of k can be deducted from the combination of shown in Fig. 1a. The NSM was designed following a hierar-
eqn (3) and (4). D is the diusion coecient of the draw solute. chical 2-level strategy. The rst level referred to the individual
As suggested in eqn (4), DCm is determined by 3 mass transfer nanober which was strengthened by nano-SiO2 and the second
phenomena, as illustrated in Fig. S1: (i) ECP, which is caused level referred to the strengthened bonds between nanobers or
by the decrease of CD,m with respect to CD,b: CD,m nanober layers.
CD,bexp(JW/k), as the water permeates across a dense selective The SiO2/PAN composite nanobers were fabricated by a co-
layer into the draw solution side and dilutes the solute electrospinning method with a SiO2 precursor and acid cata-
concentration. (ii) ICP, which is caused by the increase of CF,m lysts. Although the change of strength for a single nanober was
with respect to CF,b: CF,m CF,bexp(JWS/D), as the retained too subtle to be measured, the mechanical strength for NSM as
solutes at the feed solution side accumulate within the support a whole can be evaluated by employing a tensile strength test.
membranes. (iii) RSP, which is caused by the reverse diusion The results, which are listed in Table 1, show that the strain at
of solutes from the draw solution into the feed solution. The break has improved signicantly from 9 3 MPa (NSM-1) to
adverse coupling of RSP with ECP or ICP, which could be 17 2 MPa (NSM-2). The stiness of the NSM has increased
arithmetically expressed as B[1 exp(JW/k)]/JW and B slightly concurrently as validated by the decreased elongation at
[exp(JWS/D) 1]/JW, further reduces DCm. break from 20 4% to 15 5%. This mechanical strength
Based on eqn (4), the limiting eect of ECP, ICP and RSP improvement could be explained by the adsorption anity
could be isolated assuming the elimination of RSP between the SiO2 nanoparticles which were strapped to the PAN
(B/JW[exp(JWS/D) exp(JW/k)] 0), ICP (exp(JWS/D) 1 0) or polymer chains.35,36 A typical TEM image of a representative
ECP (1 exp(JW/k) 0) respectively.13 A Loss Factor (LF) has single nanober strain (inset, bottom le, Fig. 1c) clearly shows
been proposed to indicate the Wp loss because of the limiting the abundant SiO2 nanoparticles which were evenly dispersed
eect of phenomena i (LFi 1 Wp/Wp,no-i, i ECP, ICP or along the nanober. The SiO2 nanoparticles appear darker than
RSP).13 In this study, a more straightforward contribution the bulk PAN polymer phase, implying that the nanoparticles
coecient indicator, d, is derived based on the value of LF (di were composed of heavier elements (i.e. Si) than that of the PAN
P P
LFi/ LFi and di 1). The value of d symbolizes a comparative polymer (C, N, O). In accordance with the TEM picture, the
contribution of each phenomenon to the total limiting eect. FESEM image of a typical nanober cross-section (inset, bottom
For example, when dECP dICP dRSP, the three phenomena right, Fig. 1c) reveals some spherical and oval shaped particles
contribute equally in limiting Wp. In a system with a constant which were indicative of SiO2 particulate matters. EDX mapping
1202 | Energy Environ. Sci., 2013, 6, 11991210 This journal is The Royal Society of Chemistry 2013
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Fig. 1 (a) The slightly yellowish SiO2/PAN composite NSM; (b) FESEM image of the SiO2/PAN composite NSM shows nanober strains with narrow size distribution, the
inset picture (bottom left) shows the pore size distribution of the NSM centers at around 500 nm. (c) FESEM image of nanober cross-sections showing that the
nanober strains are welded together. The inset pictures are TEM images of a single SiO2/PAN nanober strain (bottom left) and an enlarged FESEM image of a typical
cross-section of a single nanober (bottom right), showing that SiO2 particulate matters are evenly dispersed in the PAN polymer matrix. (d) The EDX mapping of a
typical cross-section showing the even distribution of Si, N and O elements.
Table 1 Pore size distribution and mechanical strength for nanober support membranes
of a cross-section of a typical nanober (Fig. 1d) further veries several nanobers were observed to be bonded with some
that the distribution of SiO2 nanoparticles was very uniform. overlapped areas. The coating and cross-linking reactions with
The inter-connectivity between the nanobrous strains was PVA have further strengthened the interconnectivities, as sug-
facilitated by the hot-press post treatment and further gested by the increasing strain at break which increased from
strengthened by coating and cross-linking reactions with PVA. 7 1 MPa (NSM-0) to 9 3 MPa (NSM-1) (Table 1).
During the hot-press treatment, the heated residue solvent Fig. 1b (inset, plot) shows that NSM-2 had a narrow unim-
molecules inside the nascent nanobers diused outward to odal size distribution centered at around 500 nm. This corre-
the nanober surface and partially dissolved the polymer. sponded well with a narrow nanober size distribution as
Subsequently, the solvent molecules evaporated and le the depicted in Fig. S3 where more than 70% of nanobers were in
joint areas between nanobers welded. This could be validated the range of 100200 nm and 98% of nanobers were in the
by the FESEM images in Fig. 1c where the cross-sections of range of 100300 nm. The narrow size distribution would
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eliminate unexpected defects usually induced by big pores at angle.26,39,40 AFM analysis (Fig. 2e) shows that the roughness of a
high hydraulic pressures. As such, unlike the conventional typical TNC membrane surface (Ra 54.8 nm) had a similar
phase-inversion support membranes which possess more value to the commercial RO membranes with polyamide selec-
tortuous pore structures, NSM-2 was endowed with an inter- tive layers.38,4144 Nonetheless, this value was higher than a
connected, scaold-like pore structure (porosity 74%) across recently published PES/sPSf TFC-FO membrane (Ra 44.1 nm),
the entire thickness of the support membrane thus facilitating a which has lower A and B values than that of the as-prepared
better mixing between the accumulated solutes with the con- TNC-PRO membranes in this study.45 An earlier positron anni-
vectively permeated dilutive water ux, JW.26,37 hilation spectroscopic study suggested that a higher surface
roughness of a polyamide membrane may relate to higher A and
3.2 TNC-PRO membrane characteristics B values.46
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Fig. 2 (a) The picture shows a typical appearance of a TNC-PRO membrane. (b) The cross-section micro-image of the TNC-PRO membrane shows a 3-tier structure with
the bottom PET non-woven microber as the mechanical support, the nanober layer as the intermediate layer, and the top ultrathin polyamide layer as the selective
layer. (c) The enlarged cross-section micro-image shows that the polyamide selective layer is closely bonded with the nanober support membrane. The nanober
support membrane has an interconnected scaold-like pore structure. (d) The top polyamide layer has a typical rough polyamide structure. The inset picture shows that
the contact angle of the TNC-PRO membrane surface was determined to be 59.6 3.5 . (e) The regional averaged roughness of the TNC-PRO membrane surface was
determined to be 54.8 nm by AFM imaging.
1204 | Energy Environ. Sci., 2013, 6, 11991210 This journal is The Royal Society of Chemistry 2013
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TNC-1 1.23 0.15 0.28 0.07 149 17 25.3 0.4 20.5 0.3 10.7 8.6
TNC-2 3.82 0.40 1.19 0.20 135 14 36.0 2 27.0 1.4 15.2 11.4
TNC-3 5.31 0.26 3.86 0.45 140 9 24.3 5.8 18.3 3.9 10.3 7.7
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The experimental JW as a function of DP for the TNC-1, TNC-2 (blue square) was the feed solution. As suggested by eqn (2), W is
and TNC-3 membranes are plotted in the upper section of Fig. 3 the product of JW and DP. Thus at equal DP value, the magni-
from le to right respectively. The JW exhibited a near linear tude of W follows the same order of JW, with the TNC-2
increase as DP decreased from 15.2 to 0 bar. At equal DP, the JW membranes harvesting a higher W (15.2 W m2 for RW feed
with RW as the feed solution (green triangle) was constantly solution and 11.4 W m2 for BW feed solution) than the other
higher than the JW with BW (blue square) as the feed solution. two types of membranes.
For both feed solutions, TNC-2 membranes had substantially
higher JW than TNC-1 membranes (Table 2). This could be
explained by the more permeable nature of the TNC-2 3.4 Mass transfer phenomena and their contribution to Wp
membrane (i.e. higher A value). However for the TNC-3 loss
membrane which was even more permeable, JW gradually lev- The performance of TNC-PRO membranes could be predicted
eled o or even decreased (especially at high DP). Among all the by a model proposed by a previous study, which includes
three TNC-PRO membranes, the TNC-2 membranes attained synergistic limiting eects of ECP, ICP and RSP.13 As a
the highest JW of 36.0 L m2 h1 with RW feed solution and the comparison with the experimental data, the modeled JW and W
highest JW of 27.0 L m2 h1 with BW feed solution at a DP of are represented with green dotted dashed lines (RW feed solu-
15.2 bar. In the lower section of Fig. 3, the corresponding W is tion) and blue dotted dashed lines (BW feed solution) in the JW
plotted as a function of DP when RW (green triangle) or BW DP plot and WDP plot in Fig. 3. For example, a gure and
Fig. 3 Experimental JW and the corresponding W (green triangles and blue squares) as a function of applied hydraulic pressure, DP, for TNC-PRO membranes treated in
200 ppm (left), 1000 ppm (center), 2000 ppm (right) of NaClO. The data are summarized in Table 2. The respective membrane characteristic parameters: intrinsic water
permeability, A, solute permeability, B, and support membrane structural parameter, S, are plotted in the above charts. Synthetic seawater brine was used as the draw
solution (pdraw 51.8 bar) while river water (pfeed 0.045 bar, green lines) and brackish water (pfeed 3.92 bar, blue lines) were used as feed solutions. Dashed lines
represent modeled JW and W. The red triangles and squares represent the JW when the membrane had not been conditioned with high pressure.
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related discussion showing the signicance of the performance severe dilution of the draw solution (i.e., CD,bexp(JW/k)
limiting factors for the TNC-2 membrane (BWSB) can be found signicantly decreases). At the same time, the signicance of
in Fig. S5 (ESI). On the basis of this model, we propose a more ICP dwindled and dICP has a nearly equivalent value to that of
straightforward contribution coecient, d, to indicate the dRSP. This was ascribed to the signicantly low CF,b for dilute
comparative contribution of each limiting factor (ECP, ICP or river water in which the reversely permeated solutes were the
RSP) to the loss of eective osmotic driving force (detailed dominant species in inducing the ICP. As the coupled behavior
deduction is in Section 2.2). of ICP with RSP dominated, similar values between dICP and dRSP
In the BWSB conguration, the (dECP, dICP, dRSP) for TNC-1, were obtained. This was consistent with the modeled results in
TNC-2 and TNC-3 membranes was (0.77, 0.19, 0.04), (0.65, 0.26, a previous study.13
0.09) and (0.52, 0.30, 0.18) respectively. The three groups of The modeled signicance of limiting phenomena for TNC-
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coecients correspond to three coordinates, represented by the PRO membranes is compared with that of the conventional
red circles, in the ternary plot of ECP, ICP and RSP (Fig. 4). As phase inversion PRO membranes in Fig. 4 by employing an
determined from the d value, the signicance of the limiting ECP-ICP-RSP ternary plot. Comparable A and B values of the
factor follows the order ECP > ICP > RSP for all of the TNC-PRO chlorine modied phase inversion PRO membranes (LP, MP
membranes. As the membrane permeability was increased, and HP) were adopted from the literature.6 The modeled S
both dICP and dRSP increased while dECP decreased. Nonetheless, value of 350 mm was the lowest value amongst the developed
the values of dRSP for all TNC-PRO membranes were constantly phase inversion support membranes in the literature as of
lower than the equivalent value of dICP. This suggested that the today.13 Values of other parameters and test conditions were
limiting eect of reversely permeated solutes was minor for the kept the same as that of the TNC-PRO membranes. The
TNC-PRO membranes. Meanwhile the accumulation of solutes modeling results show that all phase inversion PRO
predominantly from brackish feed solution accounted for a membranes had a more signicant value of dICP (green and red
more signicant Wp loss. triangles) than their equivalent TNC-PRO membranes. In
In the RW-SB conguration, the (dECP, dICP, dRSP) for TNC-1, detail, phase inversion PRO membranes had dICP values of
TNC-2 and TNC-3 membranes was (0.92, 0.04, 0.04), (0.81, 0.09, around 0.5 in the BWSB conguration (red triangles). Owing
0.10) and (0.61, 0.18, 0.21) respectively. The above coordinates to a signicantly lower S value of 150 mm, all TNC membranes
are represented by green circles in Fig. 4. Unlike in the BWSB had dICP values of less than 0.3, as can be seen in the purple
conguration, the limiting eect of ECP in the RW-SB cong- dotted line of Fig. 4 where all coordinates were lower than the
uration was more severe, indicated by the more prominent boundary line of dICP 0.3. In contrast with the lower dICP
value of dECP. This was because higher JW would induce a more values, the dECP values for TNC-PRO membranes are all higher
than 0.5. This suggests that the ICP limitation has been
eectively overcome in the TNC-PRO membranes, while the
ECP has been the major limiting factor of Wp.
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Fig. 5 (a) Contour plot of peak power density (indicated by a colored gradient), Wp, as a function of water permeability (horizontal axis), A, and solute permeability
(vertical axis), B. The AB trade-o curve (dashed blue line, B bA3, b 0.025 bar3 m4 h2 L2) is tted from experimentally determined A and B values of TNC-1, TNC-2
and TNC-3 (hollow blue circles). (b) Contour plot of Wp as a function of A (horizontal axis) and membrane structure parameter, S (vertical axis). Purple dashed lines
indicate S values of 150 and 350 mm. The tangent point of the Wp contour line with the purple dashed line indicates the highest Wp, Wp,max, at the corresponding S
value. The dotted white line connects all AS pairs where Wp,max is reached. (c) Contour plot of Wp as a function of A and mass transfer coecient, k. The dotted white
line connects all Ak pairs where Wp,max is reached. (d) Contour plot of Wp as a function of A and draw solution concentration, CD,b. The dotted white line connects all A
CD,b pairs where Wp,max is reached. Unless specied as variables in the plots, parameters fulll the following conditions: pdraw 51.8 bar and pfeed 3.92 bar, S 150
mm, k 76.7 L m2 h1 (CFV 6.5 cm s1), B bA3 (b 0.025 bar3 m4 h2 L2) and D 1.48 109 m2 s1 at 25 C.
self-limiting JW phenomenon. Similar observations have been connected and highly porous structures of the nanober
revealed in previous studies.6,13,49,50 support membranes.26 With such a low S value, a higher Wp,max
This intrinsic AB trade-o relationship centralizes the of 15.2 W m2 is projected to occur at a higher A value of 4.1 L
importance of the S value in determining the Wp,max. As the S m2 h1 bar1 (B value 1.74 L m2 h1). This predominant
value decreases, both the ICP factor (i.e., exp(JWS/D) 1) and role of the support membrane structure in determining Wp,max
RSP factor (i.e., B/JW[exp(JWS/D) exp(JW/k)]) decrease signif- has necessitated a porous and interconnected support
icantly.6,13 This alleviates the limiting eect of ICP and RSP and membrane to be applied in PRO application. Endowed with an
enables the further benecial increase of the A value to achieve interconnected nanobrous structure and thus the lowest S
higher Wp,max. As suggested by the previous study, a Wp (A, S) value so far, the as-prepared TNC-PRO membrane herein is
contour plot could be employed to help with the interpreta- clearly a promising candidate for energy recovery from seawater
tion.13 As we can see in Wp (A, S) in Fig. 5b, Wp is lower for brine with an ecient osmotic power production without
membranes with a high S value (upper part) than that of the compromising on the mechanical strength.
membranes with a low S value (lower part). Till today, the 3.5.2 Operation conditions (k and DP). Aside from the
constraint for the reduction of the S value has always been the membrane intrinsic parameters, the selection of operation
technical diculty to develop ultrathin, porous and less conditions, such as k and DP, also aects Wp,max. The impor-
tortuous support membranes. The range of S values for tance of the analysis related to the k value is in line with the
currently developed phase inversion membranes was 3503000 previous conclusion that ECP was the major limiting factor for
mm for thin-lm at-sheet composite membranes and 6001400 the Wp of TNC-PRO membranes. A higher k value reduces the
mm for thin-lm hollow-ber composite membranes.51,52 When ECP factor, 1 exp(JW/k), and increases DCm (eqn (4)). The k
the S value is 350 mm (i.e. phase inversion PRO membrane), a value at the experimental conditions of this study (CFV 6.5 cm
Wp,max of around 11 W m2 is projected to occur at a lower A s1, feed and draw spacers inserted) was 76.7 L m2 h1. At this
value of 2.8 L m2 h1 bar1 (B value 0.55 L m2 h1). By k value (horizontal purple line, Wp (A, k) contour plot, Fig. 5C),
employing the electrospinning technique, TNC membranes Wp,max reaches 15.2 W m2 at an A value of around 4.1 L m2
have re-invented the wheel and were reported to possess the h1 bar1. If the k value could be enhanced to 180 L m2 h1,
lowest S value (150 mm) owing to uniquely low-tortuous, inter- Wp,max would reach 21.6 W m2 at approximately the same A
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1208 | Energy Environ. Sci., 2013, 6, 11991210 This journal is The Royal Society of Chemistry 2013
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the solution diusion theory to eciently predict the trans- DCm Eective solute concentration dierence
portation behavior for membranes with lower NaCl rejection (mol L1)
(e.g. TNC-2 and TNC-3 membranes).55 Ignoring s generally leads CD,m Draw solution concentration at a selective layer
to an over-estimated JW and under-estimated JS.55,56 surface
CD,b Draw solution concentration in bulk solution
CF,m Feed solution concentration at a selective layer
4 Concluding remarks surface
CF,b Feed solution concentration in bulk solution
TNC-PRO membranes oer a ray of hope that the technical
di Comparative contribution of phenomenon i to
limitation of 150 mm for PRO membranes can be overcome. The
Wp loss
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