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Abstract
Forward (direct) osmosis (FO) using semi-permeable polymeric membranes may be a viable alternative to reverse osmosis as a lower cost and
more environmentally friendly desalination technology. The driving force in the described FO process is provided by a draw solution comprising
highly soluble gases—ammonia and carbon dioxide. Using a commercially available FO membrane, experiments conducted in a crossflow, flat-
sheet membrane filtration cell yielded water fluxes ranging from 1 to 10 m/s (2.1 to 21.2 gal ft−2 d−1 or 3.6 to 36.0 l m−2 h−1 ) for a wide range of
draw and feed solution concentrations. It was found, however, that the experimental water fluxes were far lower than those anticipated based on
available bulk osmotic pressure difference and membrane pure water permeability data. Internal concentration polarization was determined to be
the major cause for the lower than expected water flux by analysis of the available water flux data and SEM images of the membrane displaying
a porous support layer. Draw solution concentration was found to play a key role in this phenomenon. Sodium chloride rejection was determined
to be 95–99% for most tests, with higher rejections occurring under higher water flux conditions. Desalination of very high sodium chloride feed
solutions (simulating 75% recovery of seawater) was also deemed possible, leading to the possibility of brine discharge minimization.
© 2005 Elsevier B.V. All rights reserved.
Keywords: Forward osmosis; Osmosis; Desalination; Concentration polarization; Internal concentration polarization; Draw solution
1. Introduction ing force for water transport through the membrane, the FO
process utilizes an osmotic pressure gradient. A “draw” solution
A worldwide shortage of unimpaired freshwater has forced having a significantly higher osmotic pressure than the saline
the tapping of saline water sources in water-starved countries. feed water flows against the permeate side of the membrane,
Current desalination technologies, such as reverse osmosis (RO), and water naturally transports across the membrane by osmo-
are, however, expensive and energy intensive. Limited recovery, sis. The osmotic driving forces in FO can be significantly greater
typically 35–50% for seawater [1], is another drawback of RO. than hydraulic driving forces in RO, potentially leading to higher
The remaining liquid, now concentrated brine, is discharged into water flux rates and recoveries. The lack of hydraulic pressure
the ocean. This is a critical environmental drawback to RO and may make the process less expensive than RO, while the min-
limits its use to coastal areas since brine from brackish ground- imization of brine discharge reduces the environmental impact
water desalination cannot be disposed of inland in an economical of the desalination process.
manner. Previous work on osmosis through semi-permeable mem-
Forward (or direct) osmosis (FO) is a technology that may branes, while limited, still exposed the two significant drawbacks
be able to desalinate saline water sources at a reduced cost and of FO. Membrane technology has advanced around the prospect
at high recovery. In forward osmosis, like RO, water transports of RO, not FO. Research conducted on osmotic processes con-
across a semi-permeable membrane that is impermeable to salt. cluded that RO membranes were not ideal for osmosis as water
However, instead of using hydraulic pressure to create the driv- flux was found to be low [2–5]. Finding easily separable draw
solutes is the second drawback of FO. Several patents describe
different configurations for the use and removal of FO draw
∗ Corresponding author. Tel.: +1 203 432 2789; fax: +1 203 432 2881. solutes [6–14]. Choosing a tailored FO membrane as well as
E-mail address: menachem.elimelech@yale.edu (M. Elimelech). an appropriate draw solute is critical in making the desalination
0376-7388/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2005.10.048
J.R. McCutcheon et al. / Journal of Membrane Science 278 (2006) 114–123 115
2.1. Ammonia–carbon dioxide draw solution and sodium Fig. 2 depicts the apparatus employed in our laboratory-scale
chloride feed solution FO experiments. The crossflow membrane unit is a SEPA cell
(GE Osmonics, Trevose, PA), modified to have channels on both
The draw solution is made by mixing ammonium bicarbonate sides of the membrane. The ammonia–carbon dioxide draw solu-
(NH4 HCO3 ) and ammonium hydroxide (NH4 OH) with deion- tion is flowing on the permeate side and the NaCl solution on
ized water at proper proportions to produce a solution of the the feed (active layer) side. Co-current flow is used to reduce
desired concentration of ammonium salts [15,16]. Higher con- strain on the suspended membrane. Mesh spacers are inserted
centrations of ammonia and carbon dioxide salts require a higher within both channels to improve support. The spacers also pro-
ratio of ammonia to carbon dioxide, which favors the formation mote turbulence and mass transport. Variable speed peristaltic
of ammonium carbamate, a highly soluble ammonium salt. The pumps (Manostat, Barrington, IL) are used to pump the liquids.
ammonia to carbon dioxide molar ratios used ranged from 1.2 A constant temperature water bath (Neslab, Newington, NH)
for the 1.1 M draw solution to 1.4 for the 6 M draw solution. is used to maintain the feed solution temperature, whereas the
The feed solution was composed of NaCl dissolved in deion- draw solution temperature is kept constant by a heating mantle
ized water. Concentrations ranged from 0.05 to 2 M. The 2 M (Glas-Col, Terre Haute, IN). Both the feed and draw solutions
NaCl concentration is indicative of 75% recovery of a 0.5 M were held at the same temperature (50 ◦ C) during the FO tests
NaCl solution, which is close to an initial seawater concentra- and were controlled to within ±1 ◦ C.
tion. The temperature of the feed solution was 50 ◦ C.
2.4. Water flux and salt rejection measurements
2.2. Forward osmosis membrane
Water flux is determined by measuring the weight change
The membrane tested in this work was provided by Hydration (Ohaus, Pine Brook, NJ) of the draw solution over a selected
Technologies Inc. (Albany, OR). The proprietary FO membrane, time period at the initial stage of the process. As water transports
denoted as CA in this paper, is thought to be made from a by osmosis across the membrane from the saline feed water
116 J.R. McCutcheon et al. / Journal of Membrane Science 278 (2006) 114–123
Fig. 2. Schematic diagram of the laboratory-scale forward osmosis system. Co-current crossflow of the feed NaCl and draw solutions is used. A scale connected to
a PC measures the mass of water permeating into the draw solution, from which permeate water flux is calculated.
into the draw solution, the draw solution weight increases. The the membrane. The channel has dimensions of 7.7 cm length,
rate at which the volume increases (determined from the weight 2.6 cm width, and 0.3 cm height, providing an effective mem-
change) divided by the membrane area yields the water flux. brane area of 20.0 cm2 . The crossflow velocity during the testing
For determining NaCl rejection, a sample of draw solution was 21.4 cm/s. An RO cell with similar dimensions was used to
is taken after a complete FO run and is boiled until all water determine the pure water hydraulic permeability for comparison.
evaporates. During the boiling process, the dissolved ammo- To conduct the osmotic permeability measurements, NaCl
nium salts decompose into NH3 and CO2 gases. The remaining solution was used on the active layer side of the membrane,
solid NaCl is hydrated with a known volume of deionized water, while deionized water ran along the backing (support) layer side.
and the NaCl concentration is measured by a chloride selective Osmotic flux data were collected for NaCl concentrations rang-
electrode (Cole-Parmer, Vernon Hills, IL). Based on the amount ing from 0.05 to 2 M, corresponding to the feed solutions that
of water passed into the draw solution over the course of the were used in the FO experiments described above. The tem-
experiment and the final amount of NaCl in the draw solution, perature of both solutions was maintained at 50 ◦ C, which was
the permeate NaCl concentration is determined. The percent salt the temperature used for the FO and pure water permeability
rejection, R, is then calculated from experiments.
High driving forces and correspondingly high water fluxes
Cp
R = 100 1 − (1) can cause severe concentration polarization effects, which occur
CF on the permeate side of the membrane (in this case, the active
where Cp and CF are the permeate and feed NaCl concentrations, layer). To account for this phenomenon, the extent of concentra-
respectively. tion polarization was calculated from film theory. The Sherwood
number, Sh, was first determined by using either the laminar or
2.5. Dependence of membrane water permeability on feed turbulent flow correlation for a rectangular channel [19,20]:
NaCl concentration
dh 0.33
Sh = 1.85 ReSc (2)
L
Osmotic permeability measurements to determine weather
the water permeability coefficient changes at high feed NaCl Sh = 0.04Re0.75 Sc0.33 (3)
concentrations were taken with a redesigned FO cell having
well-controlled hydrodynamics. The crossflow cell is of plate- where Re is the Reynolds number, Sc the Schmidt number, dh
and-frame design with a rectangular channel on each side of the hydraulic diameter, and L is the length of the channel. By
J.R. McCutcheon et al. / Journal of Membrane Science 278 (2006) 114–123 117
Table 1
Water flux, performance ratio, and NaCl rejection results for the FO runs carried out in this study under the stated feed and draw solution concentrations (and the
corresponding osmotic pressures)
Feed πF (atm) Draw πD (atm) π (atm) Theoretical flux in Experimental flux in Performance Rejection
concentration concentration m/s (or gfd) m/s (or gfd) ratio (%)
(M) (M)
0.05 2.5 1.1 47.4 44.9 25.8 (57.9) 5.3 (11.2) 0.204 97.90
0.05 2.5 3 127.6 125.1 72.0 (152.9) 8.6 (18.3) 0.120 99.45
0.05 2.5 6 249.5 236.2 136.0 (288.6) 10.1 (21.4) 0.071 98.77
0.2 9.8 1.1 47.4 37.6 21.6 (45.91) 4.1 (8.7) 0.188 93.72
0.2 9.8 3 127.6 117.8 67.8 (144.0) 6.8 (14.5) 0.101 97.34
0.2 9.8 6 249.5 228.8 131.7 (279.7) 9.4 (19.9) 0.068 98.12
0.5 24.8 1.1 47.4 22.6 13.0 (27.6) 0.9 (2.0) 0.074 86.53
0.5 24.8 1.6 73.3 48.4 27.9 (59.2) 2.8 (6.0) 0.102 96.03
0.5 24.8 2 94.5 69.7 40.1 (85.1) 3.1 (6.6) 0.078 96.40
0.5 24.8 3 127.6 102.8 59.2 (125.6) 4.6 (9.7) 0.077 98.07
0.5 24.8 4.5 193.3 168.5 97.0 (205.9) 5.9 (12.5) 0.061 97.14
0.5 24.8 6 249.5 213.8 123.1 (261.3) 6.4 (13.5) 0.049 98.70
1 51.5 3 127.6 76.1 43.8 (93.0) 2.3 (4.8) 0.052 93.89
1 51.5 4.5 193.3 141.8 81.6 (173.2) 4.4 (9.4) 0.054 95.92
2 113.8 4.5 193.3 79.5 45.8 (97.2) 1.1 (2.3) 0.024 90.14
2 113.8 6 249.5 124.9 71.9 (152.7) 2.0 (4.3) 0.026 96.85
assumption regarding the water permeability coefficient. It is 3.2.1. External concentration polarization
also assumed that σ ≈ 1 as discussed earlier in the paper. In In pressure-driven membrane processes, convective perme-
all experiments presented in Fig. 3, the measured water flux ate flow causes a buildup of solute at the membrane active layer
was lower than the theoretical flux. We define the performance surface. Referred to as CP, this reduces permeate water flux
ratio as the experimental water flux divided by the theoretical due to increased osmotic pressure that must be overcome with
water flux. This ratio is equivalent to the percentage of the bulk hydraulic pressure [24–26]. Permeate convection, and hence CP,
osmotic pressure difference that is effectively generating water is not limited to pressure-driven membrane processes and also
flux across the FO membrane. occurs in FO on the membrane feed side. This may in part explain
Table 1 summarizes the FO experimental data, including the the low performance ratios in Fig. 4. A similar but dilutive
feed and draw solution concentrations used, the corresponding effect occurs on the permeate (support layer) side, as permeat-
osmotic pressures and the osmotic pressure difference (π), the ing water dilutes the draw solution along the external membrane
calculated (theoretical) water flux based on the osmotic pressure backing layer surface. Higher concentration draw solutions will
difference, the measured water flux, and the performance ratio. increase the severity of this “dilutive” CP, since higher draw
Also included in this table are salt rejection data, to be dis- solution concentrations yield higher water flux rates. Combined,
cussed later. The variation of the performance ratio with draw the “concentrative” and dilutive external CP phenomena reduce
solution concentration for the different feed solution concen-
trations is shown in Fig. 4. The results demonstrate that the
performance ratio decreases with increasing draw and feed solu-
tion concentrations. At best, around 20% of the osmotic pressure
driving force is utilized, while at higher draw solution concen-
trations, as little as 5% or less of the osmotic pressure driv-
ing force is realized for the experimental conditions discussed
here.
the effective osmotic driving force. In a scaled up process, the feed NaCl concentrations (due to higher water fluxes), further
effects of the external CP phenomenon on driving force can mitigating the effect of external CP on the driving force. Exter-
be minimized by using crossflow filtration with hydrodynam- nal CP on the feed side of the membrane, therefore, can be ruled
ics designed to produce sufficient shear and turbulence at the out as the cause for the markedly lower than expected water flux.
membrane surface [27]. Dilutive external CP (i.e., on the outer support layer side) was
Our system (SEPA cell) incorporates a shallow channel not considered since the water permeating the backing layer of
(0.864 mm) and mesh spacers, minimizing both concentrative the membrane contained some concentration of the draw solute.
and dilutive external CP effects through high shear and increased This permeate concentration would mitigate the polarization
turbulence. For the experimental conditions of our FO runs effects on the backing side of the membrane since pure water is
(crossflow velocity of 30 cm/s and a temperature of 50 ◦ C), the not entering the bulk solution at the membrane surface. Polar-
concentration polarization modulus values were calculated from ization effects on the permeate side of the active layer within the
film theory for the feed side of the membrane. Reynolds num- porous support layer are considered in the next section.
bers in the system ranged from about 940 to 960 (the range is
due to viscosity and density variability over the range of NaCl 3.2.2. Internal concentration polarization
concentrations). When an osmotic pressure gradient is established across a
We calculated the mass transfer coefficients and the CP mod- completely rejecting dense symmetric membrane, as depicted in
uli for each of our tests based on Eqs. (2), (4), and (5). Note that Fig. 5a, the driving force is the difference in osmotic pressures
for this case, Eq. (5) has a positive exponent. We did not use the of the bulk solutions in the absence of concentrative and dilutive
turbulent correlation because the flow in this case is in the lam- external CP. When a composite or asymmetric membrane con-
inar regime. CP moduli for the various feed solutions and water sisting of a dense separating layer and a porous support layer is
fluxes ranged from 1.03 to 1.33, meaning that effective mem- used in forward osmosis, two phenomena can occur depending
brane surface concentration was not much greater than the bulk on the membrane orientation.
concentration. Since the feed NaCl concentration was always If the porous backing layer of an asymmetric membrane is
significantly less than the draw solution concentration, small facing the feed solution, a polarized layer is established along
increases in the NaCl surface concentration at the active layer the inside of the dense active layer as water and solute propagate
did not critically affect overall driving force. It is also important the porous support layer. Referred to as internal concentration
to note that the higher CP moduli were associated with the lower polarization [3,4], this phenomenon, illustrated in Fig. 5b, is
Fig. 5. Illustration of driving force profiles, expressed as water chemical potential, µW , for osmosis through several membrane types and orientations. (a) A
symmetric dense membrane. (b) An asymmetric membrane with the porous support layer against the feed solution; the profile illustrates concentrative internal CP.
(c) An asymmetric membrane with the dense active layer against the feed solution; the profile illustrates dilutive internal CP. The actual (effective) driving force is
represented by µW . External CP effects on the driving force are assumed to be negligible in this figure.
120 J.R. McCutcheon et al. / Journal of Membrane Science 278 (2006) 114–123
3.2.3. Does the membrane water permeability coefficient osmotic permeability runs exposing the active layer to increas-
change with feed NaCl concentration? ing NaCl feed concentrations (up to 2 M) while DI water was
Knowing the membrane water permeability at a given set of placed against the support layer.
system conditions is critical to calculating the theoretical flux Fig. 7 shows the flux data gathered, based on the experimental
and performance ratio as well as eliminating uncertainty in the procedure outlined in Section 2.5. As the NaCl bulk solution con-
cause of various flux behaviors. Previous studies on osmosis centration is increased, the flux behavior is not linear. This may
through asymmetric cellulose acetate membranes have reported suggest that the permeability of the membrane may be chang-
that membrane water permeability is often found to be signif- ing at higher NaCl concentrations. The water fluxes, however,
icantly lower than the corresponding hydraulic water perme- are quite high for the tests at high NaCl concentrations where
ability determined by RO [28–32]. Pusch [32] presented data nonlinearity is obvious, suggesting that dilutive external CP on
showing a precipitous drop in water permeability as the mem- the permeate side of the membrane may significantly reduce the
brane became exposed to more salt. Much of the data, however, osmotic driving force.
was in the form of observations of apparent permeability based To test our assumption that dilutive external CP rather than
on water flux and bulk solution driving force rather than the true reduction in membrane water permeability is the cause for the
membrane permeability. This behavior was attributed to inter- deviation from linearity, we carried out CP calculations as out-
nal concentration polarization effects within the porous support lined in Section 2.5. The Reynolds number was found to be
layer. A few studies, however, suggested that high salt concentra- around 2100 for the flow conditions in the new FO cell described
tions would actually lower the intrinsic water permeability of a above. With a Reynolds number on the cusp of the laminar flow
membrane through osmotic deswelling or other related phenom- regime, coupled with the mesh spacers, transition flow is likely
ena [29,30]. Our performance ratio data was calculated using the occurring. We therefore used Eqs. (2)–(5) to account for this
hydraulic water permeability coefficient obtained for pure water phenomenon and calculated the NaCl concentration at the mem-
with RO at 50 ◦ C. In order to test the influence of NaCl feed brane surface using the average of the turbulent and laminar CP
solution on the water permeability coefficient, we carried out modulus for each test [22]. The effective osmotic driving force is
J.R. McCutcheon et al. / Journal of Membrane Science 278 (2006) 114–123 121
Fig. 7. Flux data with NaCl draw solution on the active layer and deionized water
on the backing layer. Experiments were carried out with a specially designed Fig. 9. Flux data (for the FO experiments summarized in Table 1) plotted against
FO cell described in Section 2.5. Experimental conditions: crossflow velocity the logarithm of the ratio of feed and draw solution osmotic pressures. Experi-
and temperature of both feed and draw solution of 21.4 cm/s and 50 ◦ C, respec- mental conditions: SEPA cell with crossflow rate and temperature of both feed
tively. Note that a water flux of 10 m/s corresponds to 21.2 gal ft−2 d−1 (gfd) and draw solution of 30 cm/s and 50 ◦ C, respectively. Note that a water flux of
or 36.0 l m−2 h−1 . 10 m/s corresponds to 21.2 gal ft−2 d−1 (gfd) or 36.0 l m−2 h−1 .
Acknowledgements
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