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dc
dx
+ K
c
cJ
v
(1)
S
i
)
C
p
C
b
)
S
exp
(
J
v
k
)
(1 - exp(-Pe))(1 - S
) + S
exp
(
J
v
k
)
(2)
Environ. Sci. Technol. 2005, 39, 5022-5030
5022 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 13, 2005 10.1021/es0501363 CCC: $30.25 2005 American Chemical Society
Published on Web 05/19/2005
where Ak is membrane surface porosity, x is the effective
distance traveledby solute or solvent throughthe membrane
pore(accountingfor tortuosity), andPMis solutepermeability
coefficient, which is the measure of solute transport due to
diffusion. Membrane phenomenological parameters (S and
PM) andfeedside mass transfer coefficient (k) were obtained
by fitting eq 2 to experimental measurements of Cp over a
wide range of volumetric fluxes (Jv) at a constant feed flow
rate and feed concentration (18). Further, hydrodynamic
models of hindered convection in cylindrical pores (20) and
slit pores (15) were used to relate S and pore radius or half
pore width.
Membrane Pore Size and Pore Size Distribution Ob-
tained from(Hindered) Convection Calculations. Because
the log-normal distribution may be most appropriate for
membranes (18, 21, 22) it was used as the basis for PSD
calculations. A linear combination of a maximum of 2 log-
normal distributions was used to quantify the entire range
of pore sizes that were encountered:
The coefficients h
i are non-negative and ihi ) 1, fi(r)
represents the ith log-normal distribution based on pore
number with mean r ji and standard deviation SPi and r is the
pore radius. hi represents the sieving contribution of the ith
distribution.
First, using a semiempirical approach adopted by several
authors (18, 21-24), we assume that solute rejectionis purely
due to geometric considerations. This approach, wherein a
solute of radius r* permeates through all the pores whose
radii are larger thanitself (r* to) provides consistent results
(23) even though it explicitly ignores any additional drag the
solute may experience in the confined environment of the
membrane pore. The sieving coefficient according to this
purely sieving model is
Next, we have employeda mechanistic approach(19) that
accounts for the hydrodynamic lag and steric effects by
normalizing the convective hindrance coefficient for each
type of pore on the basis of volumetric flow rate through
cylindrical and slit shape pores to calculate an average
asymptotic sieving coefficient, S
A
k
x
J
v
)
K
c
P
M
J
v
(3)
f(r) )
i)1
2
h
i
f
i
(r) )
i)1
2
h
i
S
Pi
r2
exp
(
-
(ln(r) - ln(r j
i
))
2
2S
Pi
2 )
(4)
S
(r*) )
i)1
2
h
i
r*
1
S
Pi
r2
exp
(
-
(ln(r) - ln(r j
i
))
2
2S
Pi
2 )
dr
(5)
S
(K
c
) f(r) r
n
dr
f(r) r
n
dr
(6)
P
M
) D
N
0
x
K
d
f(r)r
2
dr (7)
x )
p
L (8)
p
(r*) ) 1 +
4
5
(
n)1
n
(
3
4
)
n-1
(
r*
K
d
f(r)dr)
n
(9)
)
1
N
0
(10)
VOL. 39, NO. 13, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 5023
commercially available software (Chem 3D, Cambridgesoft
Corp., v. 5). Details of MMR estimation and a comparison
of solute size parameters are given in the Supporting
Information.
Experimental Work
Membranes. Two commercially available, polyamide thin
film composite membranes denoted as DL (Osmonics,
Minnetonka, MN) and TFCS (Koch Fluid Systems, San
Diego, CA) were employed. The manufacturers provided no
information regarding possible surface chemical modifica-
tions. Operationally, sodium chloride rejection for DL and
TFCS membrane (at 1 mequiv/L concentrationand 345 kPa)
were52%and77%, respectively. Theselowrejections indicate
that the DL and TFCS membranes should be considered as
porous or loose nanofilters.
Solutes Employed. Tracers such as sugars and alcohols
which have well-defined transport properties were chosen
because of the need to quantify membrane morphology
rather thantheir presence inwater supplies. All experiments
were conducted using reagent grade neutral organic solutes
viz. methanol, ethanol, ethylene glycol, tert-butyl alcohol,
dextrose, and sucrose (EM Science Gibbstown, NJ), xylose,
glycerol, raffinose 5-hydrate, and R-cyclodextrin as well as
poly(ethylene glycol)s (PEGs) of 20 kDa, 35 kDa, and100 kDa
(Sigma Aldrich Company, St. Louis, MO). These alcohols,
sugars, and PEGs are often employed in studies of hindered
transport across membranes (16, 18, 30, 32). Similar to other
studies (4, 34), the target feedwater concentration for all
solutes was set at 20 mg/L total organic carbon (TOC). This
value facilitated easy, accurate, and precise measurements
of both feed and permeate concentrations necessary to
calculate rejection. The concentrations of all solutes were
analyzed using a TOC analyzer (TOC5050A, Shimadzu,
Columbia, MD). All results reported are an average of four
or five injections with a coefficient of variation < 2%.
Bench-Scale Cross-Flow Experimental Apparatus. All
experiments were conducted at constant cross-flowvelocity
but varying flux using a pressurized cell (Sepa CF cell,
Osmonics, Minnetonka, MN) that accommodates a 19 cm
14 cmflat membrane sheet (effective filtrationarea 155 cm
2
).
The retentate and permeate streams were recycled to the
feedtank containing 20Lof water witha single organic solute
maintaining a constant feed concentration 20 mg/L TOC.
A positive displacement gear pump (model 74011-11, Cole-
Parmer, Chicago, IL) minimized pressure fluctuations. The
cross-flow velocity was maintained constant at 9.6 and 19.2
cm/s for DL and TFCS membrane, respectively. Inert
materials such as Teflon or stainless steel were used for all
tubing, connections, pump-heads, and the membrane cell.
Filtrationpressureandtemperatureweremonitoredusing
analogue transducers (PX303-200G5VandTJ120 CPSS 116G,
OmegaEngineeringCompany, Stamford, CT). For purewater
permeability measurements, filteredwater was continuously
collected on a digital weighing balance (Ohaus Navigator
N1H110, Fisher Scientific, Houston, TX). The built-in RS232
port in the balance was directly connected to a computer to
obtain the digital signal corresponding to the weight. These
analogue and digital signals were acquired at a rate of 1 per
minute using LabVIEW (Version 5.1, National Instruments,
Austin, TX). Permeateandretentateflows werealsomanually
measured.
The complete cross-flowfiltration apparatus was housed
in a chamber whose temperature was adjusted to 5, 15, 23,
35, and 41 C. The entire apparatus including the water was
equilibrated to the chosentemperature for a minimumof 30
h prior to the commencement of experiments.
Conduct of Experiments. Freshmembranecoupons were
first soakedfacedowninultrapurewater that was replenished
3 or 4 times over a 24 h period. This coupon was then placed
in the membrane holder, and ultrapure water was passed
through the entire apparatus at 750-800 kPa pressure for
24 h. Following this membrane-setting period, steady-state
fluxes were measured for pressures in the range 100-760
kPa.
All experiments wereconductedat lowfeedwater recovery
(<1%) inconjunctionwithhighcross-flowvelocity toreduce
changes inbulkconcentration. Thepermeateconcentrations
were measured as a function of volumetric flux after the
attainment of steady-state by varying pressure in random
order to reduce systematic errors in our experimental
measurements. Five tosevendifferent pressures inthe range
100-760 kPa were used for each combination of solute,
membrane, and temperature. This pressure range resulted
ininitial fluxes between0.77 and10 m/s at 23 C. After both
permeate flux and solute rejection were maintained at their
steady-state values for at least 5-10 h, five separate 10 mL
samples of permeate water were collected for TOC analysis.
Thus, eachphenomenological coefficient corresponds to25-
35 measurements of solute rejection allowing increased
precision of parameter estimates. The retentate flow rate
and concentration were also measured in order to conduct
mass balances.
More details onthe materials andexperimental protocols
can be found in ref 18.
Results and Discussion
Pores in nanofilters can be conceived as the polymer free
(void) spaces in the membrane matrix through which solute
and water transport occurs (35). Such a system can be
characterized by calculating the number and diameter of
cylindrical or slit pores, which would have the same total
volume as well as flowand transport properties as the actual
membrane itself (24, 30). Hence, membrane morphological
parameters including pore size distribution, pore density,
ratio of pore density to effective thickness, tortuosity, and
pore spacing calculated using hydrodynamic transport
models (eqs 5-10) should only be interpreted as being
effective values. In other words, the exact values of
membrane morphological parameters obtainedby fittingthe
transport model to experimental data should be cautiously
interpreted, and only the trends with changing temperature
are emphasized in this paper.
Pore Size Distributions Incorporating Hindered Con-
vection. Experimental sieving coefficients for all solutes
decreasedwithincreasingflux(pressure) at eachtemperature.
For example, Figure 1 depicts sieving coefficients and model
(eq 2) fits at 23 C. As observed, excellent fits of the
phenomenological model were obtained for all solutes in
the flux range employed. Similar results were obtainedat the
other temperatures investigated. Further, eq 2 predicts that
at very high fluxes (Pe f ) S
i f S corresponding to the
y-intercept in Figure 1. As shown in Figure 1, 25-35
experimental measurements of the sieving coefficient ob-
tained over a range of fluxes at each temperature were used
to calculate the asymptotic value (S) for each solute using
eq 2, which were used next to calculate membrane pore size
distributions.
Thediscretepoints inFigure2correspondtotherespective
S values for each solute at room temperature. The curves
in Figure 2 correspond to calculations of the S as a function
of the mean molecular radius using hydrodynamic models
of cylindrical (Figure 2a) and slit (Figure 2b) pore geometry
using eq 6. Correlation coefficients for PSDs employing all
solutes for both pore geometries were not excellent (R
2
P
solute dependent tortuosity
water viscosity (ML
-1
T
-1
)
Acknowledgments
David Paulson and Peter Eriksson of Osmonics Inc. and
Randolph Truby and Tom Stocker of Koch Membrane
Systems Inc. generously donatedmembranesamples. Prasad
Taranekar and Rigoberto Advincula fromthe Department of
Chemistry assisted with molecular mechanics simulations.
The detailed comments generated during anonymous peer
review of this manuscript are greatly appreciated. This
research has been funded by a grant from the National
Science Foundation CAREER program (BES-0134301). The
contents do not necessarily reflect the views and policies of
the sponsors nor does the mention of trade names or
commercial products constitute endorsement or recom-
mendation for use.
Supporting Information Available
Estimation of molecular width and mean molecular radius,
choice of appropriate solute size parameter, experimental
reproducibility and quality assurance protocols, effect of
temperatureonPSD, andtemperatureeffects onN0/xusing
water permeability measurements (Tables S1 and S2 and
Figures S1-S3). This material is available free of charge via
the Internet at http://pubs.acs.org.
Literature Cited
(1) Tan, L.; Amy, G. L. Comparing Ozonation and Membrane
Separation for Color Removal and Disinfection By-Product
Control. J. Am. Water Works Assoc. 1991, 83, 74-79.
(2) Nilson, J. A.; DiGiano, F. A. Influence of NOM Composition on
Nanofiltration. J. Am. Water Works Assoc. 1996, 88, 53-66.
(3) Kimura, K.; Toshima, S.; Amy, G.; Watanabe, Y. Rejection of
Neutral Endocrine Disrupting Compounds (EDCs) and Phar-
maceutically Active Compounds (PhACs) by ROMembranes. J.
Membr. Sci. 2004, 245, 71-78.
(4) Nghiem, L. D.; Schafer, A. I.; Elimelech, M. Removal of theNatural
Hormones by Nanofiltration Membranes: Measurement, Mod-
eling, and Mechanisms. Environ. Sci. Technol. 2004, 38, 1888-
1896.
(5) Kiso, Y.; Kon, T.; Kitao, T.; Nishimura, K. Rejection Properties
of Alkyl Phthalates with Nanofiltration Membranes. J. Membr.
Sci. 2001, 182, 205-214.
(6) Devitt, E. C.; Ducellier, F.; Cote, P.; Wiesner, M. R. Effects of
Natural Organic Matter and the Raw Water Matrix on the
Rejection of Atrazine by Pressure-Driven Membranes. Water
Res. 1998, 32, 2563-2568.
(7) Lee, S.; Lueptow, R. M. Membrane Rejection of Nitrogen
Compounds. Environ. Sci. Technol. 2001, 35, 3008-3018.
(8) Waypa, J. J.; Elimelech, M.; Hering, J. G. Arsenic Removal by RO
and NF Membranes. J. Am. Water Works Assoc. 1997, 89, 102-
114.
(9) Ventresque, C.; Turner, G.; Bablon, G. Nanofiltration: from
Prototype to Full Scale. J. Am. Water Works Assoc. 1997, 89,
65-76.
(10) Taniguchi, M.; Kimura, S. Estimation of Transport Parameters
of ROMembranes for Seawater Desalination. AIChEJ. 2000, 46,
1967-1973.
(11) Abdel-Jawad, M.; El-Sayed, E. E. F.; Ebrahim, S.; Al-Saffar, A.;
Safar, M.; Tabtaei, M.; Al-Nuwaibit, G. Fifteen Years of R and
DProgramin Seawater Desalination at KISR Part II. ROSystem
Performance. Desal. 2001, 135, 155-167.
(12) Mehdizadeh, H.; Dickson, J. M.; Eriksson, P. K. Temperature
Effects onthe Performance of Thin-FilmComposite, Aromatic
Polyamide Membranes. Ind. Eng. Chem. Res. 1989, 28, 814-
824.
(13) Schaep, J.; Van der Bruggen, B.; Uytterhoven, S.; Croux, R.;
Vandecasteele, C.; Wilms, D.; Van Houtte, E.; Vanlerberghe, F.
Removal of Hardness from Groundwater by Nanofiltration.
Desal. 1998, 119, 295-302.
(14) Her, N.; Amy, G.; Jarusutthirak, C. Seasonal Variations of
Nanofiltration(NF) Foulants: IdentificationandControl. Desal.
2000, 132, 143-160.
(15) Deen, W. M. Hindered Transport of Large Molecules in Liquid-
Filled Pores. AIChE J. 1987, 33, 1409-1424.
(16) Aimar, P.; Meireles, M.; Sanchez, V. A Contribution to the
Translationof RetentionCurves intoPore Size Distributions for
Sieving Membranes. J. Membr. Sci. 1990, 54, 321-338.
(17) Combe, C.; Molis, E.; Lucas, P.; Riley, R.; Clark, M. M. The Effect
of CA Membrane Properties on Adsorptive Fouling by Humic
Acid. J. Membr. Sci. 1999, 154, 73-87.
(18) Sharma, R. R.; Agrawal, R.; Chellam, S. Temperature Effects on
SievingCharacteristics of Thin-FilmCompositeNanofiltration
Membranes: PoreSizeDistributions andTransport Parameters.
J. Membr. Sci. 2003, 223, 69-87.
(19) Mochizuki, S.; Zydney, A. L. Theoretical Analysis of Pore Size
Distribution Effects on Membrane Transport. J. Membr. Sci.
1993, 82, 211-227.
(20) Bungay, P. M.; Brenner, H. TheMotionof aCloselyFittingSphere
in a Fluid Filled Tube. Int. J. Multiphase Flow 1973, 1, 25-56.
(21) Singh, S.; Khulbe, K. C.; Matsuura, T.; Ramamurthy, P. Membrane
Characterization by Solute Transport and Atomic Microscopy.
J. Membr. Sci. 1998, 142, 111-127.
(22) Michaels, A. S. Analysis and Prediction of Sieving Curves for
Ultrafiltration Membranes: A Universal Correlation? Sep. Sci.
Technol. 1980, 15, 1305-1322.
(23) Kassotis, J.; Shmidt, J.; Hodgins, L. T.; Gregor, H. P. Modeling
of the Pore Size Distribution of Ultrafiltration Membranes. J.
Membr. Sci. 1985, 22, 61-76.
(24) Van der Bruggen, B.; Schaep, J.; Dirk, W.; Vandecasteele, C. A
Comparison of Models to Describe the Maximal Retention of
Organic Molecules in Nanofiltration. Sep. Sci. Technol. 2000,
35, 169-182.
(25) Tezel, A.; Sens, A.; Mitragotri, S. Description of Transdermal
Transport of Hydrophilic Solutes during Low-Frequency Sono-
phoresis basedona ModifiedPorous Pathway Model. J. Pharm.
Sci. 2003, 92, 381-393.
(26) International Critical Tables of Numerical Data, Physics, Chem-
istry and Technology, 1st ed.; Washburn, E. W., Ed.; McGraw-
Hill Book Company, Inc.: New York and London, 1929.
(27) Hayduk, W.; Laudie, H. Prediction of Diffusion Coefficients for
Non-Electrolytes in Dilute Aqueous Solutions. AIChE J. 1974,
20, 611-615.
(28) Wang, X.-L.; Tsuru, T.; Togoh, M.; Nakao, S.-I.; Kimura, S.
Evaluation of Pore Structure and Electrical Properties of
Nanofiltration Membranes. J. Chem. Eng. Jpn. 1995, 28, 186-
192.
(29) Nakao, S.-i. Determination of Pore Size and Pore Size Distribu-
tion 3. Filtration Membranes. J. Membr. Sci. 1994, 96, 131-165.
(30) Bowen, W. R.; Mohammad, A. W.; Hilal, N. Characterization of
Nanofiltration Membranes for Predictive Purposes - Use of
Salts, Uncharged Solutes and Atomic Force Microscopy. J.
Membr. Sci. 1997, 126, 91-105.
(31) Tezel, A.; Mitragotri, S. On the Origin of Size-Dependent
Tortuosity for Permeation of Hydrophilic Solutes across the
Stratum Corneum. J. Controlled Release 2003, 86, 183-186.
(32) Tam, C. M.; Tremblay, A. Y. Membrane Pore Characterization
- Comparison Between Single and Multicomponent Solute
Probe Techniques. J. Membr. Sci. 1991, 57, 271-287.
VOL. 39, NO. 13, 2005 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 9 5029
(33) Giddings, J. C.; Kucera, E.; Russel, C.; Myers, M. N. Statistical
Theory for the Equilibrium Distribution of Rigid Molecules in
Inert Porous Networks: Exclusion Chromatography. J. Phys.
Chem. 1968, 72, 4397-4408.
(34) Seidel, A.; Waypa, J.; Elimelech, M. Role of Charge (Donnan)
Exclusion in Removal of Arsenic from Water by a Negatively
Charged Porous Nanofiltration Membrane. Environ. Eng. Sci.
2001, 18, 105-113.
(35) Kosutic, K.; Kastelan-Kunst, L.; Kunst, B. Porosity of Some
Commercial Reverse Osmosis and Nanofiltration Polyamide
Thin Film Composite Membranes. J. Membr. Sci. 2000, 168,
101-108.
(36) Marcus, Y. IonSolvation; JohnWiley &Sons Limited: NewYork,
1985.
(37) Van der Bruggen, B.; Schaep, J.; Wilms, D.; Vandecasteele, C.
Influenceof Molecular size, PolarityandChargeontheRetention
of Organic Molecules by Nanofiltration. J. Membr. Sci. 1999,
156, 29-41.
(38) Chan, K.; Matsuura, T.; Sourirajan, S. Effect of EvaporationTime
on Pore Size and Pore Size Distribution of Aromatic Polyami-
dohydrazide RO/UF Membranes. Ind. Eng. Chem. Prod. Res.
Dev. 1984, 23, 492-500.
(39) Nguyen, T. D.; Chan, K.; Matsuura, T.; Sourirajan, S. Effect of
Shrinkage on Pore Size and Pore Size Distribution of Different
Cellulosic Reverse Osmosis Membranes. Ind. Eng. Chem. Prod.
Res. Dev. 1984, 23, 501-508.
(40) Wendt, R. P.; Klein, E. Membrane Hetroporosity and the
Probability Function Correlation. J. Membr. Sci. 1984, 17, 161-
171.
(41) Chen, J. Y.; Nomura, H.; Pusch, W. Temperature Dependence
of Membrane Transport Parameters in Hyperfiltration. Desal.
1983, 46, 437-446.
(42) Chan, K.; Tinghui, L.; Matsuura, T.; Sourirajan, S. Effect of
Shrinkage on Pore Size and Pore Size Distribution of Cellulose
Acetate Reverse Osmosis Membranes. Ind. Eng. Chem. Prod.
Res. Dev. 1984, 23, 124-133.
(43) Koros, W. J.; Woods, D. G. Elevated Temperature Application
of Polymer Hollow-Fiber Membranes. J. Membr. Sci. 2001, 181,
157-166.
(44) Kosutic, K.; Kunst, B. Effect of Hydrolysis onPorosityof Cellulose
Acetate Reverse Osmosis Membranes. J. Appl. Polym. Sci. 2001,
81, 1768-1775.
(45) Kokubo, K.; Sakai, K. Evaluation of Dialysis Membranes Using
a Tortuous Pore Model. AIChE J. 1998, 44, 2607-2619.
(46) Van der Bruggen, B.; Geens, J.; Vandecasteele, C. Influence of
Organic Solvents on the Performance of Polymeric Nanofil-
tration Membranes. Sep. Sci. Technol. 2002, 37, 783-797.
Received for review January 20, 2005. Revised manuscript
received April 14, 2005. Accepted April 26, 2005.
ES0501363
5030 9 ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 39, NO. 13, 2005