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Hollow Fiber Membrane Contactors

Article in Journal of Membrane Science July 1999

DOI: 10.1016/S0376-7388(99)00040-X

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 Journal of Membrane Science 159 (1999) 61106

Hollow ber membrane contactors

Alan Gabelmana, Sun-Tak Hwangb,*
a
Givaudan Roure Flavors, Cincinnati, OH 45216, USA
b
Department of Chemical Engineering, University of Cincinnati, Cincinnati, OH 45221-0171, USA

Received 26 March 1998; received in revised form 13 January 1999; accepted 13 January 1999

Abstract

A membrane contactor is a device that achieves gas/liquid or liquid/liquid mass transfer without dispersion of one phase
within another. This is accomplished by passing the uids on opposite sides of a microporous membrane. By careful control of
the pressure difference between the uids, one of the uids is immobilized in the pores of the membrane so that the uid/uid
interface is located at the mouth of each pore. This approach offers a number of important advantages over conventional
dispersed phase contactors, including absence of emulsions, no ooding at high ow rates, no unloading at low ow rates, no
density difference between uids required, and surprisingly high interfacial area. Indeed, membrane contactors typically offer
30 times more area than what is achievable in gas absorbers and 500 times what is obtainable in liquid/liquid extraction
columns, leading to remarkably low HTU values.
Although a number of membrane module geometries are possible, hollow ber modules have received the most attention. In
general, tube side mass transfer coefcients can be predicted with reasonable accuracy; on the other hand, shell side
coefcients are more difcult to determine, and several research groups are currently addressing this problem.
Membrane contactor technology has been demonstrated in a range of liquid/liquid and gas/liquid applications in
fermentation, pharmaceuticals, wastewater treatment, chiral separations, semiconductor manufacturing, carbonation of
beverages, metal ion extraction, protein extraction, VOC removal from waste gas, and osmotic distillation. This paper provides
a general review of hollow ber membrane contactors, including operating principles, relevant mathematics, and applications.
# 1999 Elsevier Science B.V. All rights reserved.

Keywords: Microporous and porous membranes; Organic separations; Membrane contactors

1. Introduction interfacial area as possible. For packed columns this

Gas/liquid and liquid/liquid contacting operations
are traditionally done using some type of tower,
column or mixersettler. Usually, the main challenge
in designing and operating these devices is to max-
imize the mass transfer rate by producing as much
*Corresponding author. Tel.: +1-513-556-2691; fax: +1-513-
556-3473; e-mail: shwang@alpha.che.uc.edu
requires judicious selection of packing material and
uniform distribution of uids before they enter the
packed bed. Alternatively, for devices with moving
internals the design challenge is to minimize the
bubble or droplet size of the dispersed phase and
maximize the number of bubbles or droplets.
Although columns and other traditional uid/uid
contactors have been workhorses of the chemical
industry for decades, an important disadvantage is

0376-7388/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 6 - 7 3 8 8 ( 9 9 ) 0 0 0 4 0 - X
62 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
the interdependence of the two uid phases to be
contacted, which sometimes leads to difculties such
as emulsions, foaming, unloading and ooding. An
alternative technology that overcomes these disadvan-
tages and also offers substantially more interfacial
area than conventional approaches is non-dispersive
contact via a microporous membrane. Using a suitable
membrane conguration such as a hollow ber or a at
sheet, uids to be contacted ow on opposite sides of
the membrane and the uid/uid interface forms at the
mouth of each membrane pore. Mass transfer occurs
by diffusion across the interface just as in traditional
contacting equipment.
However, unlike most membrane operations, the
membrane imparts no selectivity to the separation, i.e.,
it has no impact on the partition coefcients
[28,61,98,109]. Furthermore, as opposed to more
conventional membrane applications such as micro-
ltration, ultraltration and reverse osmosis, the driv-
ing force for separation is a concentration rather than a
pressure gradient; indeed only a very small pressure
drop across the membrane is required to ensure that
the uid/uid interface remains immobilized at the
mouth of the pore.
Advantages membrane contactors offer over col-
umns and other conventional mass transfer equipment
include the following:
 The available surface area remains undisturbed at
high and low flow rates because the two fluid
flows are independent. This is useful in applica-
tions where the required solvent/feed ratio is very
high or very low. In contrast, columns are subject
to flooding at high flow rates and unloading at low
ones.
 Emulsion formation does not occur, again because
there is no fluid/fluid dispersion.
 Unlike traditional contactors, no density differ-
ence is required between fluids; membrane con-
tactors can accommodate fluids of identical
density and can be operated in any orientation.
 Scale-up is more straightforward with membrane
contactors. That is, membrane operations usually
scale linearly, so that a predictable increase in
capacity is achieved simply by adding membrane
modules (subject of course to the limitations of
support equipment such as transfer pumps, piping,
etc.). On the other hand, scale-up with conven-
tional equipment is not nearly as straightforward.
 Modular design also allows a membrane plant to
operate over a wide range of capacities. That is,
small or large capacities can be obtained simply by
using few or many modules.
 Aseptic operation is possible, a feature which can
be advantageous in processes such as fermentation
(see Section 6.5). For example, during fermenta-
tion the broth can be circulated through a mem-
brane contactor then back into the fermenter,
while a suitable extraction solvent passes through
the contactor on the opposite side of the mem-
brane. In this manner the product of interest is
continuously removed, so that product inhibition is
relieved and productivity is improved. In principle,
a traditional contactor could be used here instead
of a membrane contactor, but in practice aseptic
operation is much more difficult with the former.
 Membrane contactors can also be used to increase
conversion with equilibrium-limited chemical
reactions in general. That is, by circulating the
reactor contents through the contactor against a
suitable extraction solvent or stripping gas, the
products are removed and the reaction equilibrium
shifts to the right.
 Interfacial area is known and is constant, which
allows performance to be predicted more easily
than with conventional dispersed phase contactors.
On the other hand, interfacial area is quite difficult
to determine in dispersive contactors because the
bubble or droplet size distribution depends on
operating conditions and fluid properties, which
is why the mass transfer coefficient and interfacial
area are usually lumped together (e.g., kGa, kLa) in
mass transfer calculations. With packed columns
the interfacial area per unit volume may be known,
but it is often difficult to determine the loading,
i.e., what fraction of the available surface is actu-
ally used.
 Substantially higher efficiency (as measured by
the height of a transfer unit or HTU) is achieved
with membrane contactors than with dispersive
contactors, as discussed in more detail below.
 Solvent holdup is low, an attractive feature when
using expensive solvents.
 Unlike mechanically agitated dispersed phase col-
umns, membrane contactors have no moving parts.
On the downside, membranes also have disadvan-
tages:
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
 The membrane introduces another resistance to
mass transfer not found in conventional opera-
tions: the resistance of the membrane itself. How-
ever, this resistance is not always important, and
steps can be taken to minimize it.
 Membrane contactors are subject to shell side
bypassing, which results in a loss in efficiency.
Often bypassing is not a problem in the laboratory
but becomes an issue upon scale-up to larger
contactors. Fortunately, several design improve-
ments have been proposed to address this problem,
as explained below (see Sections 5.2.3 and 5.2.4).
 Membranes are subject to fouling, although this
tends to be more of a problem with pressure-driven
devices than with concentration-driven ones such
as membrane contactors.
 Membranes have a finite life, so that the cost of
periodic membrane replacement needs to be con-
sidered.
 The potting adhesive (e.g., epoxy) used to secure
the fiber bundle to the tubesheet may be vulnerable
to attack by organic solvents.
 The achievable number of equilibrium stages is
limited by pressure drop constraints, as explained
below under Sections 3.2 and 5.4.
These relatively few disadvantages are often out-
weighed by the numerous advantages cited above. For
this reason, membrane contactors have attracted the
attention of many interested parties from both acade-
mia and industry for a diverse range of applications.
As a result, our level of understanding of the technol-
ogy has improved remarkably since early studies of
blood oxygenation were performed in the 1970s and
early 1980s [38,135]. The discussion below provides
a general review of membrane contactors with the
primary focus on hollow ber modules since that
conguration has been used for the majority of work
reported to date.
Some applications of hollow ber membrane con-
tactors have been reviewed by others and are only
briey mentioned here. Membrane distillation, a ther-
mally driven process for transferring a solvent across a
non-wetted membrane, was reviewed by Sirkar [123].
Membrane perstraction, a process where one or more
components of a liquid feed solution diffuse across a
non-porous membrane into a stripping or sweep
liquid, was discussed by Sirkar [124]. Osmotic dis-
tillation is discussed briey in Section 6.11.
63
2. Commercially available modules for industrial
applications
Although mass transfer operations can be con-
ducted using a number of different membrane cong-
urations, including at sheet, spiral wound, rotating
annular, and hollow ber, the latter has received the
most attention. Hollow ber modules targeted for
industrial applications (as opposed to medical ones,
e.g., blood oxygenation) are available from a variety
of sources, although some are designed for pressure-
driven ltration processes (see below) rather than
concentration-driven mass transfer.
The most well-known module designed for con-
centration-driven mass transfer is the Liqui-Cel1
Extra-Flow module offered by CELGARD LLC
(Charlotte, NC; formerly Hoechst Celanese), shown
in Fig. 1. This module uses Celgard1 microporous
polypropylene bers that are woven into a fabric and
wrapped around a central tube feeder that supplies the
shell side uid. Woven fabric allows more uniform
ber spacing, which in turn leads to higher mass
transfer coefcients than those obtained with indivi-
dual bers (see Section 5.2.4). Typically the ber
inside diameter and wall thickness are 240 and
30 mm, respectively. The bers are potted into a
solvent-resistant epoxy or polyethylene tubesheet,
and the shell casing is polypropylene, PVDF or
316L stainless steel [116,117,126,138].
As shown in Fig. 1, the Extra-Flow module contains
a central shell side bafe, a feature which offers two
advantages. First, the bafe improves efciency by
minimizing shell side bypassing; second, it provides a
component of velocity normal to the membrane sur-
face, which results in a higher mass transfer coefcient
than that achieved with strictly parallel ow (see
Section 5.2). The smallest Liqui-Cel modules are 212
inches in diameter and contain 1.4 m2 of contact area,
while the largest are 10 in. in diameter and offer
130 m2 of contact area by virtue of 225 000 bers.
The large modules can handle liquid ow rates of
several thousand liters per minute [116,117,126,138].
Membrane Corporation (Minneapolis, MN) offers
modules designed for bubble-free gas/liquid mass
transfer, which provides advantages over conventional
aeration methods in applications such as bioremedia-
tion and wastewater treatment (see Section 6.8).
These modules t within standard PVC pipes and
64 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
Fig. 1. The Liqui-CelTM Extra-Flow membrane contactor from CELGARD LLC. The central baffle minimizes shell side bypassing and
provides a component of velocity normal to the fibers (redrawn from [125]).
contain multiple ber bundles, each containing about
500 bers. The bers are potted into polyurethane at
one end only, and individually sealed at the other end,
so that there is no exhaust gas stream. That is, all
entering gas exits by diffusing across the membrane
into the surrounding water, leading to 100% gas
transfer efciency. The ber bundles are uidized
by the owing liquid, and rapid uidization is facili-
tated by the use of bundles which are at instead of
cylindrical. The packing density is only 10%; this
provides plenty of room for uidization, which in turn
leads to high gas/liquid mass transfer rates, low pres-
sure drop, and free passage of solids. The bers are
composed of a 1 mm layer of polyurethane sandwiched
between two layers of microporous polyethylene;
inside and outside diameters are 220 and 270 mm,
respectively [110].
W.L. Gore & Associates (Elkton, MD) also markets
a module designed for bubble-free gas/liquid mass
transfer primarily for ozonation of semiconductor
cleaning water (see Section 6.10). Their DISSO3L-
VETM module features expanded polytetraouroethy-
lene (PTFE) bers that are compatible with highly
corrosive chemicals such as ozone. Although a variety
of module sizes are available, the one suitable for
many semiconductor applications is 10 cm in dia-
meter, 80 cm in length and contains about 100 bers
housed in a PVDF shell. Each ber has an inside
diameter of 1.7 mm, a wall thickness of 0.5 mm, and a
pore size of 0.003 mm. The bers are arranged as a
helix, a geometry which offers higher shell side mass
transfer coefcients than one with bers parallel to the
shell. Furthermore, the nature of expanded PTFE
allows each ber to serve as a point-of-use particle
lter, an important advantage in semiconductor man-
ufacturing. Gas and liquid ow rates of 3 and 10
20 l min1 are typical, with the gas on the tube side
[142].
Pall Corporation (East Hills, NY) offers the Sepa-
relTM (a trademark of Dainippon Ink and Chemicals)
EFM-530 module for use in ultrapure water applica-
tions (see Section 6.10). The product is made from
non-porous polyolen bers that are woven into a
fabric and wrapped around a central core. Water
introduced through the central core ows normal to
the bers, which are either maintained under vacuum,
ushed with nitrogen sweep gas, or both. The shell is
made from a clean type of PVC known as Eslo-
cleanTM, but PVDF will also be available in the near
future. The non-porous membrane sets this product
apart from the others discussed in this section, which
all use microporous membranes. Non-porous mem-
branes give higher selectivity of oxygen and other
dissolved gases over water [66].
Hollow ber modules designed for pressure-driven
ltration are generally congured as parallel ow
devices such as the contactor shown in Fig. 2, where
the two uids ow parallel to each other on opposite
sides of the membrane. In principle, there is no reason
why these ltration modules cannot be used for con-
centration-driven uid/uid mass transfer, where their
simplicity (hence ease of manufacture) would be an
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
Fig. 2. A parallel flow hollow fiber module (redrawn from [137]).
important advantage. On the other hand, congura-
tions such as those discussed in the preceding para-
graphs offer substantially higher mass transfer rates;
this topic is explored in more detail below (Sec-
tions 5.2.3 and 5.2.4). Commercially available ltra-
tion modules which would be suitable for
concentration-driven processes are described in
Table 1.
3. Theoretical considerations
3.1. Resistance-in-series model
The schematic in Fig. 3 depicts mass transfer for a
typical membrane contactor in liquid/liquid extraction
service. Here the membrane is hydrophobic, so that
the pores are wetted by the organic uid. The solute of
interest encounters three resistances in series upon
transfer from the aqueous to the organic phase: the
aqueous phase boundary layer, the membrane and the
organic phase boundary layer [58]. The concentration
prole is discontinuous at the interface according to
the equilibrium relationship
Cio mi Ciw : (1)
Here Cio and Ciw are the solute concentrations in the
organic and aqueous phases, respectively, and mi is the
partition coefcient.
For a hydrophobic membrane with the organic
phase on the shell side, the driving force based on
the organic phase concentration, and no chemical
reaction, the resistance-in-series equation is
1=Ko di 1=kos do 1=kmo dlm mi =kwt di : (2)
65
Here Ko is the overall mass transfer coefcient, kos,
kmo and kwt are the individual mass transfer coef-
cients, and do, dlm, and di are the outside, log mean and
inside diameters, respectively. For the driving force
based on the aqueous phase concentration,
1=Kw di 1=kwt di 1=mi kmo dlm 1=mi kos do : (3)
For a hydrophilic membrane with aqueous ow
through the tubes and no chemical reaction, the equa-
tions are
1=Ko do 1=kos do mi =kmw dlm mi =kwt di (4)
for the driving force based on the organic phase
concentration, and
1=Kw do 1=kwt di 1=kmw dlm 1=mi kos do (5)
for the driving force based on the aqueous phase
concentration. The terms on the right-hand side of
Eqs. (2), (3), (4) and (5) correspond to the resistances
of the two boundary layers and the membrane. Ana-
logous equations can be written for the organic phase
on the tube side, and corresponding sets can be written
for gas absorption/stripping, with the partition coef-
cient mi replaced by the Henry's law constant. The
complete sets of equations are given by Prasad and
Sirkar [93] and Sirkar [122] for liquid/liquid and gas/
liquid contactors, respectively.
Eqs. (2), (3), (4) and (5) assume the following [96]:
 The system is at steady state.
 Equilibrium exists at the fluid/fluid interface.
 Pore size and wetting characteristics are uniform
throughout the membrane.
 The curvature of the fluid/fluid interface does not
significantly affect the rate of mass transfer, the
 66
A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
Table 1
Characteristics of commercially available parallel flow hollow fiber modulesa

Manufacturer Materials of construction Fiber diameter Surface Pore size Module

(mm) area (m2) length (cm)
Fiber Housing Potting

A/G Technology Polysulfone Polysulfone Epoxy 0.253 0.001528 1000 NMWCb-0.65 mm 18.5120
(Needham, MA)
Koch Membrane Polysulfone, PVC, polysulfone, Epoxy 0.53.2 0.01969.7 1000 NMWC-0.2 mm 17.8182.9
Systems polyacrylonitrile, 316LSSc,
(Wilmington, MA) inorganic carbon ARMYLOR1d
Microdyn Technologies Polypropylene, Polypropylene, Polyurethane, 0.25.5 0.0225 10 000 NMWC-0.4 mm 25304.9
(Wuppertal, Germany) sulfonated polyether 316LSS polypropylene
sulfone, polyethylene,
regenerated cellulose
Millipore Polysulfonee Polysulfone Epoxy, polyurethane 0.51.1 0.035 3000 NMWC-0.1 mm 63.8109.2
(New Bedford, MA)
a
These are commercially available filtration modules which could be used for concentration-driven mass transfer; see text (Section 2). Information in this table was obtained from
conversations with the manufacturers or from their literature.
b
Nominal molecular weight cutoff.
c
Type 316L stainless steel.
d
A PTFE-lined steel.
e
With polypropylene fiber wrap.
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
Fig. 3. Resistance-in-series model for a hydrophobic membrane.
equilibrium solute distribution or the interfacial
area.
 No bulk flow correction is necessary, i.e., mass
transfer is described adequately by simple film-
type mass transfer coefficients.
 No solute transport occurs through the non-porous
parts of the membrane.
 The two fluids are virtually insoluble in each other.
 The equilibrium solute distribution is constant
over the concentration range of interest.
It is clear from Eqs. (2), (3), (4) and (5) that high
and low values of the partition coefcient mi result in a
controlling resistance. For example, consider the
extraction of a high mi solute with a hydrophobic
membrane, where the organic phase lls the pores.
We see from Eq. (3) that for high values of mi, both the
organic boundary layer and the membrane resistances
become negligible, so that the aqueous boundary layer
resistance controls. For a hydrophilic membrane,
where the aqueous phase lls the pores, we see from
Eq. (5) that both the aqueous boundary layer and the
membrane resistances are important. On the other
hand, with a low mi solute and a hydrophobic mem-
67
brane, Eq. (2) indicates that both the organic boundary
layer and the membrane resistances are signicant.
From Eq. (4), only the organic phase boundary layer
resistance is important if a hydrophilic membrane is
used.
These observations make sense intuitively: a high
mi solute has a higher afnity for the organic phase, so
that one expects minimal mass transfer resistance
there. Similarly, minimal resistance is expected
through the aqueous boundary layer for low mi solutes
since they have a higher afnity for water. The results
of D'Elia et al. [34] illustrates this point nicely. These
workers used a hydrophobic membrane to study the
extraction of (1) p-nitrophenol from water into amyl
acetate, and (2) acetic acid from water into methyl
amyl ketone with the organic phase on the shell side in
each case. They found that in the rst case the aqueous
boundary layer resistance controlled, while in the
second case both the organic layer and the membrane
resistances were important. The results follow from
Eqs. (3) and (2) along with the mi values, which were
70 (high) and 0.4 (low) for the nitrophenol and acetic
acid extractions, respectively.
68 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
In general, the membrane resistance is important.
However, as discussed in more detail below, usually
this additional resistance is more than offset by the
higher interfacial area compared to conventional con-
tactors.
3.2. Breakthrough pressure
In membrane contactor operation the pores are
lled with the uid that wets the membrane. Non-
polar uids will wet a hydrophobic membrane such as
polypropylene, while polar uids will wet a hydro-
philic one such as polyacrylonitrile. To prevent the
wetting uid from permeating into the non-wetting
uid, the pressure of the latter is maintained slightly
higher. Furthermore, the non-wetting uid does not
displace the uid in the pores as long as the pressure
on the non-wetting side is kept below some critical
value known as the breakthrough pressure [61,62,96].
For liquid/liquid extraction the breakthrough pressure
is given by [102]:

p 2
cos =r; (6a)
while for gas/liquid contacting the correct equation is

p 2 cos =r: (6b)
Here
is the interfacial tension,  the surface  Coat the microporous fibers with a thin, highly
tension,  the contact angle and r is the pore radius.
The contact angle  is the angle formed between the
wetting uid and the membrane pore, as measured in
the wetting uid [82]. This angle increases with
increasing polarity difference between the membrane
material and the uid. For example, water formed a
contact angle of 1008 with an 80/20 copolymer of
tetrauoroethylene and chlorotriuoroethylene at
208C, while the contact angle formed by benzene
and this hydrophobic polymer was only 458 [39].
From Eqs. (6a) and (6b), a higher contact angle leads
to a lower breakthrough pressure, which makes sense
intuitively. That is, since the higher contact angle is
indicative of a higher polarity difference between the
uid and the membrane, one would expect that less
energy would be needed to remove the wetting uid
from the pore, hence the lower breakthrough pressure.
The effect of interfacial tension
(or surface ten- mical system, given by Eqs. (6a) and (6b). However,
sion ) also makes sense. As the interfacial tension
increases, more energy is required to bring the two
uids together, hence more pressure is needed to
displace one uid from the pores with the other.
The role of the pore radius r is related to the ratio
of the pore surface to its volume. This ratio increases
as the pore radius decreases; the importance of the
solid/uid interaction increases accordingly, resulting
in a higher breakthrough pressure.
Prasad and Sirkar [96] tabulated values of break-
through pressure for a variety of membrane types and
chemical systems; values range from about 100 to
500 kPa. Reed et al. [102] presented a table describing
the relative magnitude of breakthrough pressure for
various congurations of gas/liquid and liquid/liquid
systems; factors considered include membrane type
(hydrophobic or hydrophilic), uid polarity (e.g., aqu-
eous, polar organic, non-polar organic), and the wet-
ting uid (e.g., gas, aqueous, organic).
A troublesome reduction in breakthrough pressure
can occur in the presence of even trace levels of
surfactant, which cause a reduction in interfacial or
surface tension. Breakthrough can also be a problem
with solvent systems where the interfacial tension is
already low (e.g., water/n-butanol), or with a solvent
that behaves like a surfactant (e.g., the pharmaceutical
compound MK-819, mevinolinic acid) [96,102].
Three approaches to this problem have been sug-
gested:
permeable polymer or gel. Such a layer effectively
addresses the breakthrough issue by stopping flow
through the pores, yet it has no significant effect on
diffusion [35,102].
 Add a compound (e.g., isopropanol) which
increases the interfacial tension [94].
 Use a smaller pore size, which increases the break-
through pressure in accordance with Eqs. (6a) and
(6b). However, small pores can lead to hindered
diffusion of large molecules such as proteins,
causing a substantial reduction in mass transfer
rate [96].
The majority of work on microporous hollow ber
membrane contactors reported to date has been with
membranes having a uniform pore diameter across the
entire membrane thickness. Such membranes have a
characteristic breakthrough pressure for a given che-
some work with asymmetric membranes has been
reported, e.g., Sirkar et al. [127] studied solvent
extraction using microporous hydrophilic alumina
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
tubes with pore diameters of 40100 A on the inside
and up to 100 000 A on the outside. Such a membrane
has no single breakthrough pressure; instead the
breakthrough pressure varies with position as the
pore radius changes, in accordance with Eqs. (6a)
and (6b).
By exceeding the breakthrough pressure on the side
of the membrane with the smaller pore radius but not
the larger, one can immobilize the interface within the
pore rather than that at its mouth; such an approach has
advantages in certain situations:
 If the membrane resistance is significant, the
interface can be shifted so that more of the pore
volume is occupied by the fluid offering the lower
resistance to mass transfer.
 As mentioned above, hindered diffusion of large
molecules can occur with small pores. In this case,
the small pore radius on one side of an asymmetric
membrane provides a workable breakthrough
pressure, while the increasing pore radius across
the membrane thickness leads to a substantial
reduction in hindered diffusion [60,96].
Unlike dispersed phase contactors, with membrane
contactors the pressure difference between uids gen-
erally has no signicant effect on the mass transfer
coefcient [91,93,96].
4. Mass transfer performance: comparison with
conventional equipment
As with conventional contacting equipment, with
membrane contactors the task of the design engineer is
to determine the contactor length necessary to achieve
the desired extent of mass transfer. The well-known
equation for traditional multistage contacting devices
also applies here:
L HTU  NTU: (7)
In the literature, LTU is sometimes used instead of
HTU since the membrane contactor is not necessarily
oriented vertically. NTU is dened in terms of the uid
ow rates, equilibrium solute distribution (i.e., parti-
tion coefcient or Henry's Law constant), inlet con-
centrations and outlet concentrations [133]. An
expression for the length L can be obtained by per-
forming a differential solute balance, and then inte-
grating over the length of the contactor. When the
69
results are combined with the dening expression for
NTU, the following equation for HTU is obtained from
Eq. (7):
HTU v=Ka; (8)
where v is the uid velocity, K the overall mass
transfer coefcient, and a is the interfacial area avail-
able for mass transfer [96]. As in conventional mass
transfer equipment, the HTU value can be based on
either the organic or the aqueous phase concentration
driving force.
As mentioned earlier, membrane contactors offer
substantially lower HTU values than conventional
mass transfer devices. Interestingly, the enhanced
efciency is not the result of a higher mass transfer
coefcient; indeed the mass transfer coefcients
obtained with membrane contactors are usually about
the same or even slightly lower than those obtained
with traditional dispersive contactors. Instead the
improved performance results from the plethora of
interfacial area, which remains constant with changes
in operating conditions or uid physical properties.
Membrane contactors offer up to 30 times more area
than what is achievable in ordinary gas absorbers and
500 times what is obtainable in liquid/liquid extraction
columns [28].
Qi and Cussler [98] explained that the HTUs
obtained in conventional towers all tend towards the
same value (within a factor of 10 or so). This observa-
tion can be explained by considering Eq. (8). Gen-
erally the mass transfer coefcient increases with
increasing ow rate (i.e., v), and the interfacial area
decreases with decreasing ow rate; as a result, the
HTU remains about the same over a wide range of v.
On the other hand, with membrane contactors the mass
transfer coefcient drops slightly at low ow rates but
the interfacial area remains unchanged, leading to very
low values of HTU.
Several authors have compared mass transfer per-
formance of membrane contactors to that of conven-
tional equipment. For example, Ding et al. [35]
determined the mass transfer coefcient obtained with
a hollow ber contactor in the extraction of d-leucine
from a racemic aqueous mixture into a 1-octanol
solution of N-n-dodecyl-l-hydroxyproline, then com-
pared their results to those reported by others for
dispersed phase contactors. The ka values were
0.053, 0.0007 and 0.00005 s1 for the membrane
70 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
contactor, a high-efciency rotating column [132] and
a conventional extractor [133], respectively.
Sims et al. [121] used a membrane contactor to
extract orange aroma into near-critical carbon dioxide,
then compared their results to those obtained by
Schultz et al. [107] with a Schiebel column. The
extract from the membrane contactor contained sub-
stantially higher levels of key components such as
ethyl butyrate, ethyl acetate, octanal, terpinen-4-ol and
citronellal, and the membrane contactor was report-
edly an order of magnitude more efcient. Similarly,
Seibert and Fair [108] found that the extraction of
hexanol from water into octanol was 10 times more
efcient with a hollow ber membrane contactor than
with a column containing type 2 structured packing;
the authors attributed the higher efciency to the
signicantly greater mass transfer area.
Reed et al. [102] gave the following values of
interfacial area per unit volume (ft1) for various
types of contactors:
 Free dispersion columns: 110.
 Packed/trayed columns: 10100.
 Mechanically agitated columns: 50150.
 Membranes: 5002000.
Prasad and Sirkar [93] reported HTU values as a
function of ow rate for liquid/liquid extractions with
chemical systems covering a range of partition coef-
cients (0.01350) for both hydrophilic and hydropho-
bic membranes. Values as low as 23 cm were obtained,
and HTU was found to be independent of interfacial
tension. Similarly, Prasad and Sirkar [95] reported
HTU values of 315 cm in the simultaneous extraction
of 4-methylthiazole (MT) and 4-cyanothiazole (CNT)
from an actual process stream provided by Merck
(Rahway, NJ), using a hydrophobic membrane and
either toluene or benzene as the extraction solvent. As
explained by the authors, these HTU values were
probably lower than any values reported in the litera-
ture on packed and agitated columns in solvent extrac-
tion service. The closest literature value reported was
17 cm, obtained by Steiner and Hartland [130] in
their work with an enhanced coalescence plate agi-
tated column operated at high agitator speed
(250 rpm).
Prasad and Sirkar [94] compared the cost of hollow
ber membrane contactors and conventional extrac-
tors for the extraction of the pharmaceutical com-
pound mevinolinic acid or MK-819. The compound is
extracted from isopropyl acetate into water at high pH,
then back-extracted into isopropyl acetate at low pH.
For the high pH extraction, the cost of a centrifugal
extractor (e.g., a Podbielniak) would be 320 times
higher than that of a membrane contactor for a mem-
brane life of 0.53 years. Similarly, for the low pH
extraction the cost of a mixersettler would also be 3
20 times higher. This work is discussed in more detail
in Section 6.7.
Kreulen et al. [64] compared the performance of a
bubble column to that of a microporous polypropylene
hollow ber membrane contactor for the absorption of
oxygen into glycerol/water solutions of various con-
centrations. The membrane module (interfacial area:
20 cm2/cm3; ber length: 18 cm) had the same liquid
holdup and liquid height as the bubble column (dia-
meter: 4 cm; liquid holdup: 200 cm3). In light of the
other examples cited in this section, it is somewhat
surprising that the kLa for the bubble column was
actually higher than that of the membrane contactor at
low glycerol concentrations. For example, with water
alone the kLa was 0.20 s1 for the bubble column vs.
0.023 s1 for the membrane contactor.
Both kLa values decreased with increasing glycerol
concentration, but the value for the bubble column
decreased faster. Values were higher for the membrane
contactor at high glycerol concentrations, e.g., 0.002
and 0.0012 s1 for the membrane contactor and the
bubble column, respectively, at 80% glycerol. The
authors explained that the increasing viscosity with
increasing glycerol concentration led to a reduction in
the mass transfer coefcient for both devices; how-
ever, the interfacial area decreased in the bubble
column while it stayed the same in the membrane
contactor, hence the slower degradation in kLa with
the latter.
Interestingly, when compared on the basis of degree
of saturation (i.e., approach to equilibrium), the mem-
brane contactor gave superior performance over the
entire range of glycerol concentrations studied. For the
bubble column the degree of saturation ranged from
84% at 0% glycerol to 20% at 80% glycerol, while the
membrane contactor provided saturations of 8770%
over the same concentration range. The authors
explained these results in terms of the type of gas/
liquid mixing: the bubble column behaved as a stirred
tank while the membrane contactor was better
described by plug ow.
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
Jansen et al. [52] looked at using a hydrophobic
membrane contactor for CO2 removal from ue gas in
applications like ammonia production and natural gas
separation. They proposed a design for 70% CO2
recovery from 600 m3/s of gas using a reactive solvent
such as monoethanolamine to minimize the liquid side
resistance to mass transfer. The authors assumed that
diffusion through the gas-lled pores controlled (see
Section 5.3) and estimated the mass transfer coef-
cient to be 0.02 m/s for a hollow ber with an outside
diameter of 1 mm.
The required membrane area turned out to be
35 500 m2; at a membrane cost of 50 D (about
$26)/m2, the equipment cost would be 30% lower
than that of conventional gas absorption, and the total
required investment would be 10% lower. Further-
more, the estimated pressure drop for the membrane
contactor was half that of the conventional absorber,
which would lead to a signicant reduction in energy
cost. The authors pointed out that detailed engineering
design would be required to conrm these estimates.
Additionally, problems with amine-based solvents
wetting the membrane pores have been encountered
by others studying this application [126].
Jansen et al. [52] also made a more general com-
parison of gas absorption with a membrane contactor
vs. a packed column, both using a reactive solvent.
Mass transfer coefcients for the packed column were
estimated from the correlation proposed by Onda et al.
[81]. For the membrane contactor, the membrane mass
transfer coefcient was taken to be 0.03 m/s based on
the authors' experimental work with commercially
available membranes, and the gas side coefcient
was estimated from Eq. (31); the liquid phase resis-
tance was assumed to be negligible for this reactive
system (see Section 5.3). The inside and outside ber
diameters were assumed to be 0.6 and 1.0 mm, respec-
tively, and the specic surface area of the packing was
taken as 108 m2/m3 (typical for a packing diameter of
2 in.). At a gas velocity of 3 m/s, the overall mass
transfer coefcient for the packed column was 1/3 or
1/5 of the value obtained for the membrane contactor,
assuming a membrane specic surface area of 470 or
750 m2/m3, respectively. The improvement increased
with decreasing gas velocity.
Karoor and Sirkar [56] used a microporous poly-
propylene membrane contactor to study the absorption
of pure CO2, pure SO2, CO2 from CO2/N2 mixtures,
71
and SO2 from SO2/air mixtures into water. They
obtained mass transfer coefcients ve and 10 times
higher than those typically obtained in packed towers
for absorption of CO2 and SO2, respectively. This
work is discussed in more detail in Section 6.2.
5. Design considerations
5.1. Experimental determination of mass transfer
coefficients
Overall and individual mass transfer coefcients
can be determined experimentally according to the
resistance-in-series model discussed above. While
the approach described in the text that follows is
for a liquid/liquid contactor, the procedure for a
gas/liquid contactor is completely analogous if the
partition coefcient mi is replaced by the Henry's Law
constant.
First the overall mass transfer coefcient is deter-
mined using the following form of the familiar ux
equation [93]:
Qo Cio1 Ko a
Cilm : (9)
Here Cio1 is the concentration of component i in the
organic phase leaving the module; the inlet concen-
tration is assumed to be zero. Note that Ko is the
average rather than the local mass transfer coefcient;
also, the organic phase ow rate Qo can be taken as
constant because the solute concentration is assumed
to be low. The log mean driving force in Eq. (9) is
given by

Cilm
Ci1
Ci0 =ln
Ci1 =
Ci0 : (10)
The subscripts 1 and 0 refer to the respective ends of
the module, and

Ci mi Ciw Cio : (11)
The distribution coefcient mi is either obtained
from the literature or determined experimentally.
Typically the feed concentration and the interfacial
area are known, so that measurement of the ow rate
and outlet concentrations allows the mass transfer
coefcient to be calculated.
Individual mass transfer coefcients are determined
next. For unhindered diffusion through organic uid-
lled pores, Prasad and Sirkar [93] gave the following
72 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106

equation for the membrane mass transfer coefcient:
kmo Dio M =M do di =2:
Here the porosity M, the tortuosity  M and the
diameters are typically available from the membrane
manufacturer. Porosities range from 0.2 to 0.9 but
generally fall around 0.35, while tortuosities are typi-
cally 2 to 3. Although the pore size does not appear
explicitly in this equation, it appears implicitly
through the diffusivity. However, the effect of diffu-
sivity is generally minor, so the pore size is usually
unimportant as long as the diffusion is unhindered; the
exception is gas-lled pores where Knudsen diffusion
is important [102]. Prasad and Sirkar [93] gave a
similar equation for aqueous uid-lled pores.
As an alternative to Eq. (12), the Wilson plot
method [145] can be used to determine the membrane
resistance, and also to gain insight into the effect of
uid velocities on individual mass transfer coefcients
[93]. Here we assume that the individual coefcients
for the organic and aqueous boundary layers are
proportional to v, where  is an empirical constant.
In this case a plot of k1 vs. v gives a straight line;
(12)
such a plot is known as a Wilson plot.
For a hydrophobic membrane a low mi solute and/or
a high aqueous ow rate is used, so that the last term
on the right-hand side of Eq. (2) becomes negligible.
The overall mass transfer coefcient is determined as
a function of vo using Eqs. (9)(11), then the Wilson
plot of 1/Ko vs. 1=vo o is prepared. Here the value of o
is selected as the one that provides the best straight
line through the data points; the membrane resistance
is given by the intercept of the Wilson plot. The
approach is analogous for a hydrophilic membrane.
Fig. 4 shows the Wilson plot presented by Prasad and
Sirkar [93] for extraction of acetic acid from water into
xylene using a hydrophobic membrane with the
organic solvent on the shell side.
The boundary layer resistances can be determined
once the overall and membrane resistances are known.
Consider a hydrophobic membrane and a low mi
solute; to determine the organic boundary layer resis-

Fig. 4. Wilson plot for extraction of acetic acid from water into xylene using a hydrophobic hollow fiber module with the solvent on the shell
side (data of [93]).
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
tance, again the ow rate of the aqueous phase is
maintained at a high value. Since this eliminates the
aqueous phase resistance of Eq. (2), the overall resis-
tance is now just the sum of the organic boundary layer
and the membrane resistances. The overall resistance
is determined in the manner described above
(Eqs. (9)(11)), then the membrane resistance (known
from Eq. (12) or the Wilson plot) is subtracted to
obtain the organic boundary layer resistance. The
aqueous phase resistance is determined in the same
manner except the organic rather the aqueous phase
ow rate is maintained at a high value. The approach is
similar for a high mi solute (Eq. (3)) or a hydrophilic
membrane (Eqs. (4) and (5)).
Cooney and Poufos [22] suggested a different
approach. These researchers determined individual
resistances in the extraction of (a) phenol from water
into n-octanol, and (b) phenol from hexane into water,
using a hydrophilic membrane with the organic phase
on the shell side in both cases. Unlike most other work
cited in this review, the extracting solvent did not ow,
i.e., it was held stagnant. The proposed equation for
the mass transfer coefcient,
73
mass transfer coefcient was again measured as a
function of tube side ow rate, then the corresponding
membrane plus aqueous boundary layer resistances
(determined from the short run) were subtracted to
obtain the shell side resistances. In this manner Coo-
ney and Poufos [22] showed that the organic phase
boundary layer resistance was unimportant in the
phenol/water vs. n-octanol system, yet it was in fact
signicant for the phenol/hexane vs. water system.
These results are consistent with Eqs. (4) and (5) and
the mi values for phenol/water vs. n-octanol and
phenol/hexane vs. water which are 396 and 0.96,
respectively.
5.2. Prediction of individual mass transfer
coefficients
Correlations describing mass transfer coefcients
are important in the design of mass transfer equip-
ment, and membrane contactors are no exception. For
mass transfer devices in general and membrane con-
tactors in particular, mass transfer coefcients can be
predicted using correlations of the form
Ka Qf =SLlnCin =Cout (13)
was derived by writing a mass balance across a
differential section of the membrane contactor, then
integrating over the length of the contactor. Two types
of runs were performed: short and long. The short runs
did not allow enough time for a signicant amount of
solute to enter the extracting solvent, so that the
solvent boundary layer resistance was eliminated.
The sum of the other resistances might be expected
to vary linearly with 1/Q1/3 in analogy with the
equation of Sieder and Tate [120] for heat transfer:
Nu 1:86Re Pr d=L1=3 b =w 0:14 : (14)
However, Cussler [27] and others have pointed out
that Eq. (14) is not valid for very low Reynolds
numbers, presumably due to free convection effects.
In this range the appropriate plot is 1/Ka vs. 1/Q, and
in fact Cooney and Poufos [22] obtained the expected
straight line upon plotting their data in this manner. As
explained above, the intercept of such a plot gives the
membrane resistance.
The organic phase resistance was determined by
performing long runs to allow the solute concentration
on the organic side to become non-zero. The overall
Sh / Re Sc f geometry: (15)
Here Sh, Re and Sc are the Sherwood number, the
Reynolds number and the Schmidt number, respec-
tively, and f is some function of geometry. Several
authors have presented summaries of applicable cor-
relations for both tube and shell side ow
[24,29,53,96,102,122,140]. A summary of equations
presented in this review is given in Table 2.
5.2.1. Tube side flow
The following correlation has been shown by sev-
eral investigators [140,146] to predict tube side mass
transfer coefcients with reasonable accuracy:
Sh 1:62d 2 v=LD1=3 : (16)
This is the well-known Leveque solution, a limiting
case of the more general Graetz solution applicable
when the Graetz number is large [46,47,63,71,
102,139]. Note that Eq. (14) is a variation. Eq. (16)
overestimates experimentally determined mass trans-
fer coefcients at low ows; this can be attributed to
non-uniform ow caused by polydispersity in hollow
ber diameter [140].
 74
Table 2
Summary of equations for predicting individual mass transfer coefficients

Equation no. Equation Comments Reference

Tube side flow

16 Sh1.62(d2v/LD)1/3 In general, predicts tube side mass transfer coefficients with reasonable accuracy for Gz>4 but [71]
overestimates them for Gz<4
17 hShi Sh1 18Sh=Gz 720


Accounts for polydispersity of hollow fiber diameters. hShi is the average Sherwood number; Sh is the [140]
Sherwood number expected for a uniform distribution of fiber radii
Membrane

A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106

12 kmoDioM/[ M(dodi)/2] Assumes unhindered diffusion through organic fluid-filled pores. An analogous expression can be written [93]
for pores filled with aqueous fluid
Shell side flow parallel to the fibers
19 Sh[de(1)/L]Re0.6 Sc0.33  is 5.8 for hydrophobic and 6.1 for hydrophilic fibers; 0<Re<500; 0.04<<0.4 [93]
20 Sh1.25(Re de/L)0.93Sc0.33 0.5<Re<500; 0.03 [146]
21 Sh0.019Gz Gz<60; close-packed fibers [140]
22 Sh8(Re de/L)Sc0.33 Channeling around fibers suspected. Correlation based on diffusion coefficients that were of questionable [29]
accuracy
26 Sh(0.530.58)Re0.53 Sc0.33 Reflects splitting and remixing of fluid elements, which constantly present the membrane surface with [24]
fresh fluid. 21<Re<324; 0.32<<0.76
Shell side flow across the fibers
28a Sh0.15Re0.8 Sc0.33 Developed using a cylindrical tube, a helically wound bundle and a rectangular bed of fibers, with Re>2.5 [140]
28b Sh0.12Re Sc0.33 Same geometries as Eq. (28a) except Re<2.5; results attributed to polydisperse channels between fibers [140]
30a Sh6.0Gz0.35 Crimped flat membrane, Gz>11 [140]
30b Sh1.25Gz Crimped flat membrane, Gz<11 [140]
31 Sh0.9Re0.5 Sc0.33 Proposed for gas absorption with a reactive solvent using a rectangular module; 1<Re<1000, with Re [52]
based on the external fiber diameter; 1<Sc<1000
32a Sh1.38Re0.34 Sc0.33 1<Re<25; 0.70; resembles published heat transfer correlations for single tubes rather than tube banks [146]
32b Sh0.90Re0.40 Sc0.33 1<Re<25; 0.07; resembles published heat transfer correlations for single tubes rather than tube banks [146]
33 Sh0.61Re0.363 Sc0.333 0.6<Re<49; 0.003 [26]
34 Sh1.45Re0.32 Sc0.33 Developed for bubbleless aeration of water using microporous polyethylene hollow fibers [3]
35 Sh0.24(Re de/L)0.59Sc0.33 Developed for bubbleless aeration of water using a sealed hollow fiber bundle unconfined in a jet stream [53]
Hollow fiber fabric
36 Sh0.82Re0.49 Sc0.33 Average of correlations developed using four different configurations, with 0.01<Re<10; individual [141]
correlations were indistinguishable within experimental error
38 Sh0.18Re0.86 Sc0.33 Developed using a rectangular module; similar to Eq. (28a); uneven flow suspected [137]
39 Sh0.46Re0.46 Sc0.33 Developed using a baffled cylindrical module; similar to other correlations obtained with modules having [137]
uniform fiber spacing
40 Sh0.57Re0.31 Sc0.33 Developed using a cylindrical module with liquid flow outside and perpendicular to the fibers [13]
a
Gas/liquid mass transfer with chemical reaction
42 k(kRDAL)1/2 Fast reaction with a low solute concentration in the liquid [70]
43 k0 k(1DBLCB/bDALCAi) Instantaneous reaction with negligible gas phase resistance [70]
a
Analogous equations can be written for liquid/liquid mass transfer.
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
Indeed, Park and Chang [84] showed that tube side
ow distribution is often not uniform. Using high-
speed photography and dye tracer studies, these
researchers determined that the distribution depends
on the inlet manifold type (cylindrical or conical),
manifold height, tube length, ber inner diameter,
shell diameter, ber packing density and Reynolds
number. Nearly uniform ow was achieved for certain
shell and tube geometries with long manifolds at low
Reynolds numbers; however, non-uniform ow was
the rule rather than the exception. Experimental data
75
In general this correlation does not predict available
experimental data on mass transfer in membrane
contactors, probably because of the lack of depen-
dence on geometry [139]. However, variations of this
equation that include geometrical dependence have
been used successfully; examples are cited in the
discussion that follows.
Prasad and Sirkar [93] found that an equation
similar to Eq. (18) correlated their data on liquid/
liquid extraction with various solutes and solvents:
Sh de 1 =LRe0:6 Sc0:33 : (19)
agreed fairly well with model predictions.
Wickramasinghe et al. [140] assumed a Gaussian
distribution of ber radii, then integrated the basic
equation for the mass transfer coefcient over all radii
and obtained the following power series solution for
the average tube side coefcient:
hki k1 9kV=QR0 720


: (17)
Here k is the mass transfer coefcient expected for a
uniform distribution of ber radii, V the average
volume occupied by one ber, R0 the average ber
radius, and 0 is the standard deviation of ber radii
divided by the mean. Eq. (17) was developed for low
ow conditions, i.e., the Graetz number less than four;
at these low ows, the quantity in brackets is less than
one. Since the distribution of ber diameters leads to
low ows in some bers, we see that polydispersity
can lead to a reduction in the mass transfer coefcient.
The hypothesis was veried experimentally upon
stripping oxygen from water into water-saturated
nitrogen using microporous polypropylene hollow
bers. Correlations inferred from the experimental
data agreed with Eq. (16) at high ow rates, but gave
lower mass transfer coefcients at low ows in accor-
dance with Eq. (17).
5.2.2. Shell side flow parallel to the fibers
In contrast to tube side ow, shell side ow is not
clearly understood. A number of correlations like
Eq. (15) have been proposed, but none is applicable
to a wide range of systems in the manner Eq. (16) is
generally applicable to tube side ow.
Knudsen and Katz [63] proposed the following
equation for shell side heat transfer in a shell-and-
tube exchanger:
Sh 0:022Re0:6 Sc0:33 : (18)
Here  is the packing fraction. The constant  was
found to be 5.8 and 6.1 for hydrophobic and hydro-
philic membranes, respectively.
Yang and Cussler [146] obtained the following
correlation in their work with gas absorption and
stripping:
Sh 1:25Re de =L0:93 Sc0:33 : (20)
The authors had no explanation for the unexpect-
edly high Reynolds number dependence vs. available
correlations for heat transfer (e.g., Eq. (18)). How-
ever, in practice Eqs. (19) and (20) give similar
results, even though the latter has a higher Reynolds
number dependence and does not contain the packing
fraction  [139]. Moreover, other studies have also
revealed a linear (or nearly so) dependence on
ow. For example, Wickramasinghe et al. [140]
obtained the following correlation in their work with
gas absorption and stripping using close-packed
bers:
Sh 0:019Gz: (21)
These researchers argued that correlating the Sher-
wood number with the Graetz number instead of the
product of the Reynolds and Schmidt numbers makes
more sense. Their argument assumed that the Sher-
wood number changes little with changes in viscosity,
which they explained is true if the velocity prole is
established quickly.
Dahuron and Cussler [29] correlated their data on
extraction of proteins as follows:
Sh 8Re de =LSc0:33 : (22)
These investigators explained that the deviation
from the expected Reynolds number exponent of
0.6 may have been due to channeling around the
76 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106

bers; they also pointed out that their results depended

on the accuracy of the diffusion coefcients of the
proteins they used, and that they had no direct measure
of these coefcients. The work of Dahuron and Cuss-
ler is discussed in more detail in Section 6.6.
Lemanski and Lipscomb [69] looked at the effect of
shell side residence time distribution (RTD) on mass
transfer performance. Plug ow would be obtained
with an ideal contactor, but in real shell side ow the
need to distribute uid across the ber bundle as well
as along it tends to broaden the RTD. Mass transfer is
more efcient for uid elements with a shorter resi-
dence time because the concentration driving force
remains higher than that for elements which spend
more time in the shell. Furthermore, since the mass
transfer coefcient is a function of the local uid
velocity, higher local mass transfer coefcients are
obtained for uid elements in crossow than for those
owing parallel to the bers.
Lemanski and Lipscomb [69] characterized shell
side mass transfer in terms of the ratio of the mass
transfer coefcient for plug ow (at the volume aver-
age velocity) to the actual, intrinsic mass transfer
coefcient. They showed that the ratio depends on
two dimensionless groups: the module geometry
number
MG rr =zz L=R2 (23)
and the mass transfer number
MT ka: (24)
Here  is the Darcy permeability tensor and  is the
space time. By volume averaging the pertinent con-
servation of mass and momentum equations, the ratio
was calculated over a range of values of MT and MG;
results are shown in Fig. 5. At small values of MT,
performance was superior for lower values of MG;
however, as MT increased, the performance decreased
substantially for lower MG values but changed little
for higher ones. The authors concluded that commer-
cial modules should have an MG value of at least 10 to
minimize the effect of MT on performance.
Seibert et al. [109] studied shell side bypassing in
the extraction of acetone from toluene into water using
a hydrophobic hollow ber module. They found from
dye tracer studies that the actual residence time was
less than ideal by a factor of 34, and the extent of
bypassing changed with uid velocity according to the
Fig. 5. Dependence of kE/k on MT for various values of MG.
Diamond: 1; filled circle: 2; triangle: 5; square: 75; open circle: 150
(redrawn from [69]).
following empirical equation:
 expCvs : (25)
Here  is the fraction of uid that bypasses the
hollow bers, C is an empirical constant, and vs is the
shell side uid velocity. The value of C increased with
decreasing ber packing density; the authors reported
values of 0.38, 1.4 and 2.8 s/cm for ber counts of
7500, 3000 and 1500, respectively.
Other investigators have also studied the effect of
ber packing density on shell side mass transfer. For
example, Wickramasinghe et al. [140] looked at the
absorption of oxygen into water with the latter on the
shell side using a module containing 12 000 or 7500
bers. Mass transfer coefcients for the more loosely
packed module were three times higher; the authors
attributed the difference to channeling. Yang and
Cussler [146] also reported that the mass transfer
coefcient was lower for closely vs. loosely packed
bers in the absorption of oxygen into water, and there
was no change in the mass transfer coefcient with
Reynolds number with the former. They attributed
these results to major channeling through the closely
packed bers so that mass transfer was controlled by
diffusion through a stagnant lm between the bers,
hence the lack of Reynolds number dependence.
Costello et al. [24] looked at the effect of ber
packing density on mass transfer upon stripping of
oxygen from water into nitrogen gas, using a hydro-
phobic membrane with water and nitrogen owing on
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
the shell and tube sides, respectively. They pointed out
that most of the published correlations for the shell
side mass transfer coefcient (e.g., Eqs. (19), (20) and
(22)) were developed using contactors with low ber
packing densities (340%). Values of  (Eq. (15)) for
these correlations range from 0.6 to 1.0, characteristic
of turbulent ow. However, these correlations were
developed for shell side Reynolds numbers in the
laminar range; this suggests the presence of local
turbulence as explained below. The correlations did
not predict the experimental data obtained by Costello
et al. at higher packing densities, i.e., 3276%.
Costello et al. [24] proposed the following equation
for the shell side mass transfer coefcient:
Sh 0:53 0:58Re0:53 Sc0:33 : (26)
Their data suggested values of the Re exponent
ranging from 0.50 to 0.57, characteristic of entry
region conditions, over a range of packing densities.
According to the authors, these results were indicative
of splitting and remixing of uid streams, which
constantly presented the membrane surface with fresh
uid. Unlike similar correlations proposed by others
(e.g., Eqs. (19) and (20)), there is no dependence on
d/L in Eq. (26), which implies that the entrance length
is unrelated to the module length; instead it is probably
related to stream splitting and recombining that
occurs repeatedly along the length of the module.
One can solve the differential mass and momentum
balances to obtain a theoretical prediction of the effect
of packing density on the mass transfer coefcient.
According to that prediction, the coefcient increases
steadily with increasing packing density until a max-
imum is reached at a density of 6570%. The sub-
sequent decline is caused by ``dead zones,'' which are
regions where the bers are very close together or
actually touch. For packing densities less than 65%,
experimental coefcients are substantially higher than
expected based on the theory. The reason is that the
theory assumes the bers are packed uniformly, which
is not the case in real systems. This non-uniformity
promotes turbulence, i.e., the stream splitting and
recombining mentioned above, which in turn leads
to mass transfer coefcients that are higher than those
theoretically possible with axial laminar ow [24].
Rogers and Long [104] also attributed at least part
of the difculty in predicting shell side mass transfer
coefcients to incorrect assumptions regarding shell
77
side ow distribution. They explained that most mod-
els divide shell side ow among nite grids whose size
and shape are determined primarily by the geometry of
the ber layout, which is assumed to be (but rarely is)
uniform. Rogers and Long used a technique known as
random sequential addition (RSA) to generate an
ensemble of randomly oriented bers. The maximum
packing density obtained, known as the jamming limit,
was approximately equal to the packing density used
in at least one commercially available module, i.e., the
Liqui-Cel module from CELGARD LLC (Fig. 1).
Interestingly, the placement of 2186 non-overlapping
bers using RSA required 20 953 544 iterations and
80.81 h on a Pentium 100 MHz PC. With the random
placement of bers in this manner, shell side ow was
divided into Voronoi cells or polygons, dened as the
boundary around each tube where the momentum
gradient is zero or the velocity is maximized. These
boundaries were identied using the software known
as Voronoi tessellation code.
Rogers and Long [104] modeled the performance of
hollow ber membrane contactors when used for
extraction accompanied by chemical reaction. Mass
transfer coefcients were calculated using published
correlations, and shell side ow maldistribution was
estimated using RSA and Voronoi polygons as
explained above. Model predictions were compared
to experimental data for the extraction of uranyl nitrate
from a nitric acid solution into tributyl phosphonate
(TBP) in a hydrocarbon diluent. The extraction was
accompanied by the reaction
UO
2 2NO3 2TBP $ UO2 NO3 2
2TBP
(27)
The enhancement of mass transfer by the reaction
was included in the model by the use of a facilitation
factor similar to the Thiele modulus. The authors
concluded that the agreement between experimental
data and model predictions was signicantly better
than the predictions of lumped parameter models that
assume uniform shell side ow. Mass transfer with
chemical reaction is discussed in more detail in
Section 5.3 below.
5.2.3. Alternative hollow fiber geometries
In the early days of hollow ber membrane con-
tactors the controlling resistance was typically the
membrane itself, primarily because membranes were
78 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
thick and permeabilities were low. Since that time, our
knowledge of membrane materials and manufacturing
methods has grown dramatically, and membranes with
much lower mass transfer resistance have been devel-
oped. This progress focused attention on the other
mass transfer resistances encountered in parallel ow
contactors (see Fig. 2), particularly the shell side
boundary layer, hence the work reviewed in the pre-
vious section.
This altered focus has fostered the development of
several alternative geometries that offer higher mass
transfer coefcients than conventional parallel ow.
For example, Wickramasinghe et al. [140] stripped
oxygen from water into nitrogen using four module
congurations, each with water owing outside and
across the microporous polypropylene hollow bers.
The four geometries were a cylindrical tube bundle, a
helically wound bundle, a rectangular bed of bers and
a crimped at membrane. Mass transfer coefcients
for the rst three congurations were described by
Sh 0:15Re0:8 Sc0:33 (28a)
for Re>2.5, and
Sh 0:12Re Sc0:33 (28b)
for Re<2.5. Sherwood numbers obtained at low ow
rates (Eq. (28b)) were lower than those predicted by
the correlation applicable to high ow rates
(Eq. (28a)). The authors attributed this to uneven
ows caused by polydisperse channels between bers;
they presented the following equation to account for
the effect of polydispersity:
hki k1 9kV=QR0 0 1 0 1=2 720


; ow conditions on both sides of the membrane, gas
(29)
where 0 is the void fraction of bers in the module.
This equation is analogous to Eq. (17) and was
derived in a similar manner. Both assume a Gaussian
distribution of ow channel radii; for the tube side this
assumption was supported by measurements of ber
inside diameter, but for the shell side it remained
speculative. Furthermore, on the tube side a larger
ber diameter results in a larger ow through that ber
for the entire module length, but on the shell side the
situation is not so clear. For these reasons the authors
had more condence in the general applicability of
Eq. (17) to tube side ow than in the utility of Eq. (29)
for shell side ow, even though the existence of
polydisperse gaps seemed like a reasonable explana-
tion for inferior module performance at low ows.
Wickramasinghe et al. [140] obtained the following
correlations for the crimped at membranes:
Sh 6:0Gz0:35 (30a)
for Gz>11, and
Sh 1:25Gz (30b)
for Gz<11. The cube root dependence in Eq. (30a) is
consistent with expected results for ow in a slit. The
linear dependence in Eq. (30b) is consistent with
Eq. (28b).
Wickramasinghe et al. [140] compared perfor-
mance of the various module geometries studied in
terms of oxygen removal efciency. When perfor-
mance was compared on the basis of equal ow per
unit membrane area, best results were obtained with
the rectangular bundle, which stripped 98% of the
incoming oxygen. The cylindrical bundle, helical
bundle, and crimped at plate removed 82%, 86%
and 72%, respectively. All of these crossow designs
were substantially more efcient than a parallel ow
cylindrical module, which stripped only 7% of the
oxygen in the incoming water. Findings were similar
when module performance was compared on the basis
of equal ow per unit volume.
For gas absorption applications, Jansen et al. [52]
proposed a rectangular design with gas ow outside
and normal to the bers. According to the authors,
such a design offers a number of advantages, including
high mass transfer, low pressure drop, well-dened
ow unobstructed by ber potting, and ability to stack
modules. A preliminary optimization study suggested
that mass transfer was more efcient with an in-line
rather than a staggered ber arrangement. Best results
were obtained when the transversal pitch was twice
the outside diameter, and the longitudinal pitch
divided by the outside diameter was between 1.1
and 3.0; with this optimal geometry,
Sh 0:9Re0:5 Sc0:33 (31)
for Re and Sc each between 1 and 1000, with Re based
on the external ber diameter.
Yang and Cussler [146] used hydrophobic hollow
bers to study the removal of oxygen or CO2 from
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
water into nitrogen. The water owed outside and
across the bers, which were housed in a conventional
cylindrical shell. The authors obtained the following
correlations for closely and loosely packed bers,
respectively:
Sh 1:38Re0:34 Sc0:33 ; (32a)
Sh 0:90Re0:40 Sc0:33 : (32b)
Both of these equations resemble published heat
transfer correlations for single tubes rather than tube
banks. While this is expected for loosely packed bers
(Eq. (32b)), one would expect correlations for tube
banks to predict data from closely packed bers more
accurately, since the two are more similar geometri-
cally. The authors were unable to explain the result.
Cote et al. [26] obtained a similar correlation for
loosely packed bers in experiments on oxygenation
of water:
Sh 0:61Re0:363 Sc0:333 : (33)
Ahmed and Semmens [3] also developed a similar
correlation in their work on bubbleless aeration of
water using microporous polypropylene hollow bers:
Sh 1:45Re0:32 Sc0:33 : (34)
In related work, Johnson et al. [53] studied bubble-
less aeration of water using a sealed hollow ber
bundle unconned in a jet stream. Their mass transfer
correlation,
Sh 0:24Re de =L0:59 Sc0:33 (35)
was veried using different membrane lengths, jet
orice areas and jet liquid exit velocities. Bubble-free
aeration is discussed in more detail in Section 6.8.
Bafed contactors (e.g., Fig. 1) were developed to
overcome shortcomings of parallel ow such as shell
side bypassing. However, Seibert and Fair [108] found
that bypassing does in fact occur with these modules in
some cases. These researchers proposed a stage ef-
ciency model that was an excellent predictor of mass
transfer coefcients for a shell side-controlled system
(octanol/hexanol/water) and a mixed resistance sys-
tem (butanol/succinic acid/water) at high shell side
ow rates but a poor predictor at low ow rates. They
suggested poor shell side distribution at low ow rates
as a possible explanation for the discrepancy between
expected and observed results. According to the
79
authors, such problems are more severe in larger
modules; little improvement is obtained by decreasing
the ber density because bers tend to part and
provide channels for bypassing.
5.2.4. Hollow fiber fabric
Several of the investigators cited in the above
discussion found that uneven ow distribution led
to a reduction in the mass transfer coefcient. Along
these lines, Cussler [28] pointed out that the inevitable
non-uniform ber spacing in commercial modules
results in non-uniform ow and in turn lower mass
transfer coefcients than those obtained with hand-
built laboratory units, where precise spacing is more
easily achieved. Cussler suggested the use of bers
woven into a fabric to obtain more uniform spacing,
and presented data showing that mass transfer coef-
cients obtained using this approach were nearly as
high as those with hand-built contactors. Wang and
Cussler [137] and Wickramasinghe et al. [141] used
modules employing a woven fabric to strip oxygen or
toluene from water into nitrogen. Similarly, Bhaumik
et al. [13] used hollow ber fabric to absorb CO2 from
pure CO2 and from a CO2/N2 mixture into water. As
explained below, all three groups obtained mass trans-
fer coefcients that were up to an order of magnitude
higher than those achieved with non-woven bers.
Wickramasinghe et al. [141] stripped oxygen from
water using microporous polypropylene hollow bers
arranged in one of the four congurations; in all cases
the gas owed on the tube side. The membrane
modules used in this work were constructed by the
authors, and not manufactured commercially. The rst
conguration (Fig. 6) was an annular bed of hollow
bers wound helically around a central core; liquid
entering the central core was forced radially outward
by a plug so that the ow was perpendicular to the
bers. The second conguration was similar to the rst
except that the shell contained plugs and O-rings to
provide multiple shell side passes. The third cong-
uration (Fig. 7) was similar to the second except that it
was made with knitted hollow ber fabric rather than
individual bers. Finally, in the fourth conguration
(Fig. 8), hollow ber fabric was mounted diagonally
in an open-ended rectangular box, and the liquid
entered through a tubular manifold. The whole box
was towed through the liquid, forcing the liquid to
ow both through and around the box.
80 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106

Fig. 6. A module containing hollow fibers wound helically around a central core. Liquid entering the core is forced radially outward by the
plug so that the flow is perpendicular to the fibers (redrawn from [141]).

Fig. 7. A module containing woven hollow fiber fabric wound helically around a central core. The plugs and O-rings provide multiple shell
passes (redrawn from [141]).

Higher mass transfer coefcients were obtained
with the axially wound individual bers (i.e., the rst
two congurations described above) than with mod-
ules manufactured commercially, especially at low
ows [140]. However, coefcients for the axially
wound modules were not as high as those obtained
with modules built one ber at a time [146]. These
results support the argument that better mass transfer
is achieved with more uniform ber spacing, since
uniformity is usually best with hand-built and worst
with commercially manufactured contactors; unfortu-
nately, the benets of hand-built modules are probably

Fig. 8. A module containing woven hollow fiber fabric mounted diagonally in an open-ended box (redrawn from [141]).
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106 81

not justied by the higher manufacturing cost. Sur-

prisingly, the mass transfer coefcients for the
unbafed (Fig. 6) and bafed (the second congura-
tion described above) axially wound modules were
about the same.
Mass transfer coefcients for the axially wound
fabric (Fig. 7) were slightly higher than those obtained
with the axially wound individual bers, yet still lower
than those achieved with hand-built modules. When
compared to performance of commercial modules
[140], coefcients were an order of magnitude higher
with the fabric at low ows, while at high ows the
improvement was not as dramatic. The authors attrib-
uted the superior performance of modules containing
the fabric to higher uniformity of ber spacing com-
pared to individual bers. The fabric is also easier to Fig. 9. A rectangular module containing two baffles (redrawn from
assemble than commercial modules, so that better [137]).
mass transfer is achieved at a lower manufacturing
cost. The mass transfer coefcients for the rectangular
module (Fig. 8) were similar to those obtained with modules built from individual bers. The three
hand-built modules [146], i.e., they were the highest of module congurations they used are shown in
the four congurations studied. However, the com- Figs. 2, 9 and Fig. 10. The rst (Fig. 2) was a
plexity of these modules may outweigh their perfor- conventional parallel ow module containing
mance advantage. individual bers; liquid and gas were placed on the
Wickramasinghe et al. [141] presented mass trans- tube and shell sides, respectively. The second and
fer correlations for hand-built modules [146], the third congurations (Figs. 9 and 10) used the woven
axially wound individual bers, the axially wound fabric instead of individual bers, with shell side
fabric, and the rectangular modules. The four correla- uid ow primarily across rather than parallel to
tions were indistinguishable within experimental the bers. The module depicted in Fig. 9 was rectan-
error, so the following average correlation was gular with two bafes; liquid and gas owed through
proposed: the shell and bers, respectively. The third congura-
tion (Fig. 10) was a fully bafed cylindrical module;
Sh 0:82Re0:49 Sc0:33 : (36) again liquid and gas were placed on the shell and tube
sides.
Wang and Cussler [137] also compared gas strip- By performing a mass balance around a differential
ping with hollow ber contactors containing a woven module segment, the authors showed that the mass
fabric of microporous polypropylene bers to transfer coefcient for removal of oxygen from water

Fig. 10. A fully baffled cylindrical module (redrawn from [137]).

82 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
into nitrogen can be described by
k Q=A lnC1 =C0 : (37)
Here Q is the liquid ow rate, A is the membrane
area, and C1 and C0 are the liquid outlet and inlet
concentrations, respectively. The authors measured C1
and C0, and then used this equation to determine the
mass transfer coefcient for a given ow rate and
module geometry.
The Sherwood number correlation obtained for the
rectangular module (Eq. (38)) was similar to the one
reported by Wickramasinghe et al. [140] for commer-
cial oxygenators (Eq. (28a)):
Sh 0:18Re0:86 Sc0:33 : (38)
Since commercial oxygenators are often compro-
mised by uneven ow as discussed above, the authors
surmised that the problem also existed in their rec-
tangular module. Mass transfer coefcients for the
cylindrical modules were higher, possibly because the
rectangular module contained stagnant liquid zones
between adjacent bers in each layer of fabric. Coef-
cients for the cylindrical modules were closer to the
results obtained by others using either hand-built,
carefully made axially wound, or other cylindrically
wound bafed fabric module designs [141,146]. This
indicates that the authors were successful in achieving
uniform ow in the cylindrical modules by using the
woven fabric, and the proposed Sherwood number
correlation is in fact similar to other correlations
obtained with modules having good ber spacing
(e.g., Eq. (36)):
Sh 0:46Re0:46 Sc0:33 : (39)
Bhaumik et al. [13] measured mass transfer coef-
cients obtained upon absorption of CO2 from pure
CO2 and from a CO2/N2 mixture into water using a
fabric made from microporous polypropylene hollow
bers. The fabric was wound helically around a central
core similar to the conguration depicted in Fig. 6.
Gas owed on the tube side, while liquid entering the
central core was forced radially outward (perpendi-
cular to the bers) by the plug. The number of ber
wraps around the central core was kept small so that
the liquid supercial velocity was clearly dened. This
in turn was expected to give the correct mass transfer
correlation rather than the module average value one
would expect with many wraps. Modules with two or
seven wraps were studied using Reynolds numbers
ranging from 0.02 to 1.01. The similarity of data
obtained with pure CO2 and mixed gas plus the
observed effect of changes in liquid ow rate led
the authors to conclude that gas phase resistances
were negligible. Data obtained from both modules
using pure CO2 or mixed gas were tted reasonably
well by the following correlation:
Sh 0:57Re0:31 Sc0:33 : (40)
The authors compared their data to the predictions
of other correlations developed for low Reynolds
numbers. There was a good t with the correlation
of Wickramasinghe et al. [141], who stripped oxygen
from water using a similar module and ow pattern
(Eq. (36)).
5.3. Mass transfer with chemical reaction
As in any mass transfer device, chemical reaction
can have a major effect on the rate of mass transfer in
membrane contactors. Consider gas/liquid mass trans-
fer: in the absence of chemical reaction, the gas phase
resistances are usually negligible and the liquid
boundary layer resistance controls. However, if a
chemical reaction occurs between the absorbed spe-
cies and the solvent, the liquid side resistance is
reduced and the gas phase resistance may actually
control.
Suppose we have the following reaction:
A from gas bB liquid ! products liquid
(41)
For a fast reaction and low solute concentration in
the liquid, CB is essentially constant and the mass
transfer coefcient is given by
k kR DAL 1=2 ; (42)
where kR is the rst order reaction rate constant. Here
the reaction is fast but not so fast that the reactants
cannot coexist; an example is the mass transfer of
chlorine into water, where the two react to form
hypochlorous and hydrochloric acids [70,102].
For an instantaneous reaction with negligible gas
phase resistance,
k0 k1 DBL CB =bDAL CAi ; (43)
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
where k0 and k are the mass transfer coefcients with
and without chemical reaction, respectively, and i
refers to the uid/uid interface. Here the reaction
is so fast that the reactants cannot coexist, e.g., the
absorption of hydrogen sulde in aqueous sodium
hydroxide to produce sodium bisulde [70,102]. Com-
parable equations can be written for liquid/liquid mass
transfer with reaction.
Reports dealing with chemical reactions in liquid/
liquid systems include Refs. [8,10,50,72,78,104,148
151]. Gas/liquid reacting systems have been discussed
by Qi and Cussler [97,98], Cooney and Jackson [21],
Semmens et al. [112], Karoor and Sirkar [56], and
Kreulen et al. [65]. Examples of reacting systems are
given in Section 6.
5.4. Additional considerations in contactor design
and operation
5.4.1. Design objective
In mass transfer with membrane contactors the
design objective depends on the application. For
example, with blood oxygenators the objective is to
maximize the amount of oxygen transferred per unit
volume. This minimizes the contactor volume
required, which in turn minimizes the volume of blood
outside the body. On the other hand, for industrial
applications the objective is clearly to minimize the
cost per amount of mass transferred, which does not
necessarily coincide with the maximum solute trans-
ferred per unit volume [139].
5.4.2. Design approach
Module length is a key design specication because
it is directly related to the number of transfer units (see
Eq. (7)). However, the higher efciency offered by
longer modules comes at the cost of increased pressure
drop. If the module is too long, the pressure of the non-
wetting uid may fall below that of the wetting uid,
allowing bulk ow of the wetting into the non-wetting
uid (see Section 3.2). There may be some recourse in
increasing the inlet pressure, but that pressure is
limited by the breakthrough pressure.
A number of design features must be considered to
obtain the required capacity and number of transfer
units while meeting these pressure constraints, i.e.,
tube diameter, wall thickness, porosity, tortuosity,
packing factor, ow rates, inlet concentrations, dis-
83
tribution coefcient, and uid physical properties.
Prasad and Sirkar [96] suggested a design procedure
that considers these factors and gives the required
number of bers, module diameter and length for a
given design problem. For cases where single module
designs are not practical, Prasad and Sirkar suggested
the use of series/parallel cascades. Reed et al. [102]
gave several design examples.
5.4.3. Optimum fiber diameter
Wickramasinghe et al. [139] looked at the cost of
stripping gas from water into nitrogen using a hollow
ber contactor with the water owing through the
tubes. Both a highly volatile and a less volatile solute
were studied; with oxygen, the volatile solute, the tube
side boundary layer resistance controlled, while with
bromoform, the less volatile solute, the shell side
resistance was important. Cost per unit mass trans-
ferred was plotted vs. ber diameter, with either
membrane cost per unit area (for a xed module
length) or module length (for a xed membrane cost)
as a parameter. The cost was taken as the sum of the
membrane and pumping costs; the amount of mass
transferred was calculated using shell and tube side
mass transfer coefcients obtained from Eqs. (20) and
(16), respectively. Results are shown in Figs. 1114.
In nearly all cases there was an optimum ber
diameter which corresponded to a minimum cost.
That is, pumping cost decreased with increasing ber
diameter, but membrane cost increased due to the
increase in membrane area. This means that pumping
costs dominated at small diameters while membrane
costs dominated at large ones, hence the existence of
an optimum. The cost varied as d4 at low diameters
and linearly with d at large diameters.
Not surprisingly, an increase in membrane cost
decreased the optimum ber diameter. Furthermore,
the optimum diameter increased with increasing
length; this was explained by the increase in pumping
cost resulting from the increase in length, which in
turn required a larger diameter before the membrane
cost began to dominate. It is interesting that in most
cases the optimum diameter was around a few hundred
microns, which coincides with the diameters of com-
mercially available bers.
While the trends were the same with oxygen and
bromoform, the costs were about half for bromoform
under comparable conditions. This resulted from the
84 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106

Fig. 11. Cost per unit mass transferred for stripping oxygen from Fig. 13. Cost per unit mass transferred for bromoform stripping.
water into nitrogen using a module 1 m in length. The parameter is Again the module is 1 m in length, and the parameter is membrane
membrane cost in $/m2 year (redrawn from [139]). cost in $/m2 year (redrawn from [139]).

difference in controlling resistance. That is, since the shell side ow rate. The increase in mass transfer rate
tube side resistance controlled for the oxygen but not more than compensated for the increase in pumping
for the bromoform, a higher mass transfer coefcient cost corresponding to the higher ow rate, hence the
could be achieved with the latter by increasing the decrease in cost per unit mass transferred. However,

Fig. 12. Cost per unit mass transferred for oxygen stripping. This Fig. 14. Cost per unit mass transferred for bromoform stripping.
figure shows the effect of module length for a fixed membrane cost This figure shows the effect of module length for a fixed membrane
of $10/m2 year (redrawn from [139]). cost of $10/m2 year (redrawn from [139]).
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
the calculations for bromoform were the least reliable
because shell side ow is not as well understood as the
tube side ow and the available correlations for the
mass transfer coefcient are not as good, as discussed
above.
5.4.4. Flow direction
Wang and Cussler [137] explained that conven-
tional parallel ow modules offer true countercurrent
ow and are preferred when the membrane or the tube
side boundary layer resistance controls. However,
with these modules mass transfer coefcients can
be reduced and/or ows can become uneven if the
shell side resistance is signicant; in this case a
crossow design is preferred. Flow normal rather than
parallel to the bers leads to higher mass transfer
coefcients, but the price is loss of efciency com-
pared to countercurrent designs. Some efciency is
regained by the use of bafed modules, which provide
elements of both countercurrent and crossow; ef-
ciency increases as the number of bafes increases,
but pressure drop increases as well, and the modules
become more difcult to build.
Wang and Cussler [137] looked at the effect of the
number of bafes on mass transfer performance. They
measured the fraction of toluene stripped from water
into nitrogen using a rectangular module (Fig. 9)
equipped with one, two or four bafes, operated in
either cocurrent or countercurrent mode with the
liquid on the tube side. Toluene removal was higher
for countercurrent ow as expected. Interestingly,
oscillations in the fraction of toluene removed vs.
number of bafes were observed for cocurrent but
not countercurrent ow. The authors explained that in
cocurrent ow, exit liquid contacts less saturated gas if
there is an even number of bafes and more saturated
gas if there is an odd number. Consequently, more
toluene is removed with an even number and less with
an odd number, hence the oscillations. No oscillations
were observed with countercurrent ow since exiting
liquid always contacts the entering gas.
The effect of bafing on oxygen stripping from
water into nitrogen using cylindrical modules was
assessed with a predictive model. Performance was
examined as a function of the absorption factor GH/Q
for several different congurations, including cross-
ow, countercurrent and cocurrent ow, all with the
gas ow inside the bers. The latter two contained
85
zero, two or ve bafes; no bafes were used in the
crossow case. The highest oxygen removal was
achieved using countercurrent ow with ve bafes,
although performance with two bafes was almost as
good. Crossow with no bafes was superior to
cocurrent ow with two.
6. Applications
A summary of applications is presented in Table 3.
6.1. Liquid/liquid extraction
The versatility of membrane contactors is clear
from the abundance of published reports on liquid/
liquid extraction applications, and several of these
have already been cited. Results from two compre-
hensive studies [91,93] are summarized in Table 4.
These works illustrate the utility of the technology for
chemical systems covering a broad range of mi values
using different membrane geometries, materials and
ow congurations.
In liquid/liquid extraction using hollow ber mod-
ules, several considerations govern which uid is
placed on the shell side and which one is selected
for ow through the bers. Because the shell side uid
is subject to bypassing and channeling as discussed
above, a high degree of extraction is often difcult to
obtain with the solute-containing feed on the shell
side. However, if the feed contains particulates that are
not at least one order of magnitude smaller than the
inside diameter of the bers, then tube side ow is not
advisable. On the other hand, large particulates are
more likely to settle out in dead spots on the shell side,
which suggests particle size reduction (e.g., with a
homogenizer or grinder) or removal by ltration to
allow tube side ow. Another consideration is the
integrity of the bond between the bers and the
tubesheet; if leakage is a concern, the lower pressure
uid (i.e., the one which wets the pores) preferably
ows on the tube side [22,96].
In most liquid/liquid extraction applications the
lowest membrane mass transfer resistance is obtained
if the pores are lled with the uid in which the solute
is most soluble. This suggests the use of a hydrophilic
or hydrophobic membrane for a low or high mi solute,
respectively (see Eqs. (2)(5)). That is, a low mi solute

Table 3
Summary of applications
Application
Liquid/liquid extraction
Gas absorption and stripping
Dense gas extraction
Chiral separations
Fermentation and enzymatic
transformation
Protein extraction
Pharmaceutical applications
Wastewater treatment
Metal ion extraction
Semiconductors
Osmotic distillation
86
Comments Selected references
Membrane contactors have been employed in a variety of chemical systems covering a broad range [8,10,22,34,59,91,93,96,101,109]
of mi values. A number of membrane geometries, materials of construction and flow configurations
have been investigated. Results from two comprehensive studies are given in Table 4
A variety of solute/solvent systems have been studied, some including chemical reactions. [12,52,56,64,65,88,97100,118,
A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
Solutes investigated in recent work include CO2, SO2, NOx, Br2, H2S, I2, N2, NH3, (NH4)2S, acetic 122,125,134,140,146]
acid, HCl, lactic acid, ethane, ethylene and VOCs. Commercial applications include carbonation
of beverages, treatment of boiler feedwater, stripping of CO2 from anion exchange feed streams
(to extend bed life), nitrogenation of beer to provide a dense foam head, and deoxygenation of beer
to preserve flavor. Wastewater treatment and semiconductor applications are discussed separately
Membrane contactors offer a low-cost alternative for production of otherwise expensive [103,121]
supercritical extracts, particularly those of interest to the food and flavor industry
Selective extraction of d-leucine from a racemic mixture in water using a 1-octanol solution of [35,72]
N-n-dodecyl-l-hydroxyproline has been demonstrated. A membrane reactor has been employed to
selectively remove the undesirable stereoisomer from a racemic mixture of enantiomers encountered
in the production of a drug used to treat hypertension and angina.
Several investigators have shown that productivity of ethanol and other metabolic products can be [19,40,41,50,54,55,74,78,79,
increased by in situ extraction using membrane contactors. Enzymatic hydrolysis of triglycerides 119,136]
with simultaneous separation of the resulting glycerol and fatty acids has also been demonstrated
Various proteins have been investigated, including cytochrome-c, myoglobin, a-chymotrypsin, [29,33]
catalase, urease, and a-amylase
Several important compounds (e.g., 4-methylthiazole, 4-cyanothiazole and mevinolinic acid) have [94,95]
been extracted from actual industrial steams using membrane contactors
Recovery of a number of troublesome pollutants from aqueous streams has been demonstrated, [1,2,25,26,75,83,91,93,96,
including 2-chlorophenol, benzene, nitrobenzene, trichloromethane, tetrachloromethane and 111,113115,152,153]
acrylonitrile. Bubble-free aeration offers several advantages over conventional approaches,
including no venting of VOCs and 100% oxygen transfer efficiency at low power input
The efficacy of the technology has been demonstrated for recovery of a variety of ions from [20,57,96,148,150,151]
aqueous wastewaters. Some authors have reported the use of dual contactors operated in chelating
and stripping mode, respectively. Numerous applications using chemical reaction to facilitate ion
removal have been described
Membrane contactors are used in semiconductor manufacturing operations for the production of [23,31,45,143]
ultrapure water and for ozonation of cleaning water
In this process, one or more volatile components of a liquid feed are transferred through a [37,49,68,87]
non-wetted microporous membrane into another liquid. Applications include fruit and vegetable
juice concentration and production of low alcohol wine
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106 87

Table 4
Liquid/liquid extraction using membrane contactorsa

Feed solvent Solute Extraction solvent Partition coefficient Membrane configuration Membrane material
b
n-Heptane Toluene NMP 1.03 Flat Hydrophobic
Water Acetic acid MIBK 0.52 Flat Hydrophilic
Water Acetic acid MIBK 0.52 Flat Compositec
Water Acetic acid MIBK 0.52 Hollow fiber Hydrophobic
Water Acetic acid MIBK 0.52 Hollow fiber Hydrophilic
Water Acetic acid Xylene 0.0125d Hollow fiber Hydrophobic
Water Acetic acid Xylene 0.0125d Hollow fiber Hydrophilic
Water Succinic acid n-Butanol 1.49 Hollow fiber Hydrophobic
Water Succinic acid n-Butanol 1.49 Hollow fiber Hydrophilic
Watere Phenol MIBK 119 Hollow fiber Hydrophobic
Watere Phenol MIBK 119 Hollow fiber Hydrophilic
a
Refs. [91,93].
b
A polar organic solvent.
c
A hydrophobic sheet placed on the top of a hydrophilic sheet.
d
Prasad and Sirkar [93] gave a range of 0.01250.039 corresponding to aqueous concentrations of 0.274.75 mol/cm3.
e
pH 6.8.

is more soluble in a polar solvent than in a non-polar
one, and the polar solvent will wet the pores of a
hydrophilic membrane; the situation is analogous for a
high mi solute and a hydrophobic membrane. How-
ever, with proper membrane pretreatment, a polar
solvent will wet a hydrophobic membrane, so that
low membrane resistance can still be achieved with a
low mi solute; similarly, hydrophilic membrane pores
can be lled with a non-polar solvent [90].
For example, Prasad et al. [90] obtained a at
Cuprophan 150PM membrane (regenerated cellulose,
ENKA) from the manufacturer with the pores lled
with a low-volatility organic; the wetting character-
istics of the membrane were set by the method used to
remove this organic. That is, operation with water-
lled pores was achieved by rst washing the mem-
brane with isopropyl alcohol then air-drying; conver-
sely, operation with a non-polar organic in the pores
was accomplished by rst washing with xylene. Simi-
lar results were obtained with other hydrophilic mem-
branes including nylon (polyamide, at, ENKA),
ceramic (alumina, tubular, ALCOA), and glass (tub-
ular, ASAHI). A hydrophobic membrane (Celgard
2400, polypropylene, tubular, CELGARD LLC) was
also operated with either a non-polar (n-heptane) or
polar (n-methyl pyrrolidone) solvent in the pores by
soaking in the respective solvent before use.
This unconventional approach allows one to obtain
the lowest possible mass transfer resistance with
fewer restrictions on membrane material. However,
a penalty is paid in breakthrough pressure, which is
signicantly lower for hydrophilic and hydrophobic
membranes lled with non-polar and polar uids,
respectively [90].
Reed et al. [101] performed pilot scale extractions
of chlorinated and aromatic compounds from indus-
trial wastewaters in Holland. Some 75 l/h of waste-
water were treated using three Liqui-Cel modules
(Fig. 1), each with an interfacial area of 23 m2.
Treatment was performed successfully for periods
up to three months, with individual contaminant levels
reduced to less than 10 mg/l, and process economics
were competitive with other approaches.
Basu and Sirkar [8] looked at liquid/liquid extrac-
tion facilitated by chemical reaction. These investi-
gators used a hydrophobic at sheet (i.e., organic-
lled pores) to study the extraction of phenol from
MIBK into aqueous sodium hydroxide, which is
facilitated by the following instantaneous reaction:
C6 H5 OH NaOH ! C6 H5 ONa H2 O (44)
For sodium hydroxide concentrations below some
critical value, the reaction front resided within the
aqueous boundary layer; the front moved closer to the
liquid/liquid interface as the NaOH concentration
increased, nally reaching the interface when some
critical concentration was exceeded. Basu and Sirkar
presented the entire set of resistance-in-series equa-
88 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
tions for mass transfer with instantaneous reaction in
the aqueous boundary layer. Cases considered
involved hydrophobic, hydrophilic and composite
membranes, each with aqueous reactant concentra-
tions above and below the critical value.
In a related study, Basu and Sirkar [10] used
hydrophobic hollow ber modules to investigate the
extraction of citric acid from water into trioctyl amine/
MIBK followed by back-extraction into sodium
hydroxide. The formation of the citric acid/trioctyl
amine complex followed the fast reversible reaction
C6 H8 O7 aq 3R3 N org
$ R3 NH3 C6 H5 O7 org (45)
The effects of aqueous phase ow rate, organic
phase ow rate and trioctyl amine concentration were
studied. Experiments were performed with the aqu-
eous phase ow on the tube side as well as the shell
side, and a mathematical model was proposed that
successfully predicted the effect of the chemical reac-
tion on the mass transfer rate. Under most conditions,
the aqueous boundary layer controlled as expected for
a hydrophobic membrane and a high mi solute (see
Eq. (3)), i.e., the citric acid/amine complex. However,
in some cases, the size of the complex rendered the
membrane resistance signicant. Interestingly, the
back-extraction into NaOH was much slower than
the forward extraction into the organic phase.
Keurentjes et al. [59] employed a membrane con-
tactor to extract a series of fatty acids from soybean oil
into 1,2-butanediol using cellulosic hollow bers with
the oil owing on the tube side. The fatty acids were
recovered by combining the extract with water, separ-
ating the resulting dispersion into pure fatty acids and
a fatty acid-free 1,2-butanediol/water mixture, then
dewatering the mixture to recover 1,2-butanediol for
reuse. The chain length of the fatty acids studied
ranged from 6 (caproic) to 22 (erucic). In most cases
the major resistance to mass transfer was diffusion
through the membrane pores, which were wetted by
the 1,2-butanediol. Because of the low interfacial
tension with this system, small pores were necessary
to avoid breakthrough (see Eq. (6a)).
The authors found that the mass transfer coefcient
increased and the equilibrium distribution shifted
more towards the 1,2-butanediol with decreasing
chain length. That is, there were two mechanisms
acting in the same direction to obtain enhanced selec-
tivity, which suggests the use of a membrane contactor
for fractionation of fatty acids. The authors explained
that higher purities can be obtained in less time with
this approach than with traditional crystallization
methods.
Two other examples of liquid/liquid extraction
applications were cited by Sirkar [125]:
 Matsumura [73] used a hydrophilic membrane to
study the extraction of ethanol, isopropanol and n-
butanol.
 Brose [15] extracted onion oil and other flavors
from fruit and vegetable processing waste streams.
Small membrane contactors have been tested by a
number of industrial organizations for a variety of
liquid/liquid extraction applications. However, large
systems are not yet ready for use, primarily because of
a lack of suitable materials of construction [125,126].
6.2. Gas absorption and stripping
Even though the large density difference between
liquid and gas leads to faster countercurrent ows and
somewhat alleviates the problems of ooding and
unloading in conventional equipment, the advantages
of membrane contactors cited above are still important
[28]. Indeed, gas/liquid contacting applications are
enjoying numerous commercial successes; several
of these are discussed below.
Two modes of operation are possible in gas/liquid
contactors: wetted mode and dry (or non-wetted)
mode. Wetted mode occurs when the pores are lled
with liquid, e.g., if the liquid phase is aqueous and a
hydrophilic membrane is used. Conversely, a hydro-
phobic membrane would operate in dry mode in this
case because the pores would be lled with gas. Dry
mode is usually preferred to take advantage of the
higher diffusivity in the gas; however, wetted mode
may be preferred if there is a fast or instantaneous
liquid phase reaction and as a result the gas phase
resistance controls [56].
Karoor and Sirkar [56] studied the absorption of
pure CO2, pure SO2, CO2 from CO2/N2 mixtures, and
SO2 from SO2/air mixtures into water. They used a
parallel ow module employing microporous poly-
propylene bers, usually with the water on the tube
side. These researchers also modeled the system by
writing the differential mass balance, substituting the
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
appropriate velocity proles and reaction kinetics,
then solving using a nite difference scheme [30].
A parabolic velocity prole was assumed for the tube
side, while the shell side velocity prole was predicted
using Happel's free surface model [48]. Both wetted
and dry modes were investigated. Absorption of SO2
was facilitated by the following chemical reaction:
SO2 2H2 O $ H3 O HSO
3; KE 0:014 M
(46)
Further disassociation of HSO 3 was avoided by
proper selection of pH. The reaction of CO2 with water
was neglected because of the low value of the equili-
brium constant.
As expected, CO2 absorption was limited by the
liquid phase resistance, and best results were obtained
in the dry mode. Experimentally determined mass
transfer coefcients agreed well with those predicted
by the model when the aqueous phase owed through
the tubes, and the Leveque [71] solution was also in
good agreement with the data. The mass transfer
coefcients were as much as ve times those typically
obtained for conventional packed towers. Mass trans-
fer coefcients obtained with SO2 absorption also
agreed well with predicted values for liquid ow
through the tubes, and those values were 10 times
higher than those usually obtained in packed towers.
In spite of the chemical reaction (Eq. (46)), resistance
was somewhat higher in the wetted vs. dry operating
mode with SO2 absorption.
On the other hand, Yang and Cussler [146] did in
fact show a shift in controlling resistance that was
attributable to chemical reaction. That is, when oxy-
gen on the shell side of a microporous polypropylene
hollow ber module was absorbed into water on the
tube side while operating in dry mode, the aqueous
phase boundary layer resistance controlled as
expected. However, with CO2 absorption into dilute
sodium hydroxide, the chemical reaction reduced the
tube side mass transfer resistance so that it no longer
controlled. Qi and Cussler [97,98] also reported on
absorption of CO2 into aqueous sodium hydroxide
using hydrophobic hollow bers, including character-
ization of the mass transfer behavior.
Jansen et al. [52] employed microporous hydro-
phobic hollow bers (diameter: 0.6 mm; length:
25 cm) to absorb SO2 from (a) a model gas of SO2
in nitrogen, and (b) real ue gas from a coal-red
89
boiler; the reactive absorbent was Na2SO3. Over 99%
recovery was obtained with the model gas, and the
results agreed well with theoretical predictions. Simi-
lar recoveries were maintained with the real ue gas
over a period of 500 h, and there were no problems
with dust, particles, condensation, or other ue gas
components (e.g., NOx, CO2, HCl). Encouraged by
this success, a pilot plant was built in Krim, Holland,
as a collaborative effort between the TNO Institute of
Environmental and Energy Technology, Hoogovens
Technical Services, Bronswerk Heat Transfer and
AVEBE. The plant was tested for two six-month
seasons; SO2 recovery exceeded 95%, there were no
fouling problems and in general the plant was easy to
operate.
Bhaumik et al. [12] investigated the use of a micro-
porous polypropylene membrane contactor operated
with a pressure swing cycle, a technique known as
rapid pressure swing absorption, to recover CO2 from
nitrogen. In this work the absorbent (20% aqueous
diethanolamine, or DEA) was stationary on the shell
side. Feed gas (10% CO2 in nitrogen) was passed
through the bers, CO2 was absorbed and the puried
gas was obtained at the ber outlet. At the end of the
absorption period (1025 s), absorbed gas was
removed from the absorbent by pulling a vacuum
on the shell side for 1520 s, then the cycle was
repeated. This technique offers a number of advan-
tages over conventional pressure swing absorption in
addition to those already cited for membrane contac-
tors in general:
 Purification ability is extraordinary. The exit gas
contained less than 50 ppmv (the detection limit
for the analytical method used) at a flow rate of
5055 cm3/min, or 1.11.2 cm3/min per cm3 of
module volume.
 The capacity and selectivity of liquid absorbents,
especially reactive ones, are much higher than for
most solid adsorbents.
 The absorber and stripper used in conventional
processes are replaced with one vessel.
 High rates of absorption/desorption are possible
by using short cycle times.
The authors pointed out that the same approach is
applicable to a variety of gas purication problems,
including removal of CO2 from ue gas, CO and CO2
from post-shift reactor synthesis gas, H2S from
streams containing H2S and CO2, and VOCs from air.
90 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
Qi and Cussler [99,100] studied the transport of
nine volatile solutes from aqueous solution on the tube
side through a hydrophobic gas-lled membrane and
into a second aqueous solution on the shell side. In this
manner stripping and absorption were carried out in a
single device. The nine solutes were Br2, H2S, I2, SO2,
NH3, (NH4)2S, acetic acid, HCl, and lactic acid; mass
transfer coefcients ranged from about 0 for HCl and
lactic acid to 0.00041 cm/s for Br2. Although the ux
depended both on the volatility of the solute and its
solubility in water, the latter was more important. In
some cases the absorption step was facilitated by
reaction with the stripping solution, e.g., 0.5 N
H2SO4 was used to strip NH3; the relative resistance,
of the shell side boundary layer diminished accord-
ingly. The authors explained that ionization of
solute can have a dramatic effect on mass transfer
resistance so that the overall resistance is no longer
simply the sum of the boundary layer and membrane
resistances.
Kreulen et al. [64] studied the absorption of CO2
into water/glycerol using polypropylene or polysul-
fone hollow bers. Interestingly, when the liquid
owed through the bers, agreement between theore-
tical and experimental values of the mass transfer
coefcients was obtained when the active mass trans-
fer area was taken as the entire area of the bers, not
just the area of the pores themselves. This was true
regardless of the porosity of the bers, which was 0.7
and <0.03 for the polypropylene and polysulfone,
respectively (pore sizes were 1107 and
5109 m). The authors explained that the distance
between adjacent pores was much less than the dis-
tance from the ber wall to the center of the ber. This
meant that diffusion parallel to the ber led to a
boundary layer that was in effect homogeneous and
saturated, hence the importance of the entire mem-
brane area rather than just the pore area.
Other ndings from this work were as follows:
 For liquid flow through the tubes, mass transfer
coefficients followed the GraetzLeveque solution
for heat transfer [46,47,71] (see Eq. (16)).
 For liquid flowing around regularly packed fibers,
mass transfer was described reasonably well by the
correlation of Miyatake and Iwashita [77], which
was derived for a similar heat transfer problem.
 Correlating mass transfer results obtained with
liquid flowing around irregularly packed fibers
was difficult because of the unknown dimensions
of the channels between the fibers.
Yang and Cussler [147] demonstrated the efcacy
of two types of microporous polypropylene membrane
modules (parallel ow and crossow) as articial gills.
Water was pumped through the tubes of the module,
while gas was pumped in a closed loop between the
module shell and a small box. Transfer of oxygen from
the water to the gas and CO2 from the gas to the water
was actually sufcient to sustain a small animal placed
in the box. When a hamster was put in the air-lled
box, the oxygen and CO2 concentrations in the box
reached a steady state (corresponding to the hamster's
metabolic rate) in about 2 h. A white rat remained
healthy in the box for three days. To accommodate the
larger size and higher metabolic rate of a dog, a larger
box was used and 40 modules were connected in
parallel; the dog, a 4.9 kg West Highland terrier,
survived quite nicely. The articial gill was even
demonstrated on a 57 kg human (the rst author of
the paper); for that experiment the pump and box were
replaced by a SCUBA mouthpiece, hoses and a rubber
bladder.
The authors presented equations that successfully
predicted the oxygen and CO2 concentrations in the
box over time as well as the mass transfer coefcients.
They concluded that articial gills could be designed
which would keep small animals alive. Such gills
could also keep resting humans alive if water were
pumped rapidly through the gill, but the task would be
more challenging if the human moved through the
water.
Jansen et al. [52] proposed the use of membrane
contactors to remove harmful components of environ-
mental tobacco smoke (ETS) from the air, e.g., in a
home or ofce where smokers are present. These
investigators used a smoke generator to produce
ETS, then passed the contaminated air through a
laboratory membrane module with water owing on
the opposite side. Percent removal efciencies were as
follows: acetone 97, styrene 15, formaldehyde 98,
nicotine 99, and ammonia 95. The poor recovery
for styrene is not surprising considering its poor
solubility in water.
Tsou et al. [134] investigated the use of membrane
contactors for separation of olens from petrochem-
ical feedstocks, using silver as a complexing agent to
improve the ux and selectivity [43,106]. They fed a
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
mixture of 74/26 ethylene/ethane to the shell side of a
hydrophilic hollow ber membrane module with a
silver nitrate solution (0.55 N) on the tube side. Shell
and tube side pressures of 0200 psig were possible
using back pressure regulators. The exit liquid stream
owed to a ash pot aided by a helium sweep to
release the absorbed gas, and the regenerated absor-
bent was returned to the module. Throughput and
separation efciency were high enough to support
commercial implementation of the technology not
only to separate ethylene from ethane but for purica-
tion of other olens as well. The authors have used the
technology to reliably produce puried propylene
from renery grade propylene at pilot scale, i.e.,
one half barrel per day.
Poddar et al. [88] looked at absorption of volatile
organic compounds (VOCs) from N2/air into silicone
oil or mineral oil. Two types of hollow ber modules
were used: one containing a porous hydrophobic
membrane, and one containing a highly VOC-perme-
able non-porous silicone skin over a porous mem-
brane; in both the cases the absorbent owed through
the shell side. Spent absorbent was regenerated under
vacuum in a separate module then recycled.
Efcient VOC removal from the gas stream was
achieved; the highest efciency was obtained with
toluene, followed by methylene chloride, acetone and
methanol. Efciency was higher with silicone vs.
mineral oil because of the higher diffusivities and
mi values with the former, but mineral oil provided
better long term stability. The absorbent-lled porous
membrane was responsible for 8095% of the mass
transfer resistance, while for the skinned membrane
most of the resistance was found in the skin and the
liquid boundary layer outside of it. Plots of dimen-
sionless concentration vs. the inverse of the tube side
Graetz number agreed well with theoretical predic-
tions. Mass transfer coefcients were substantially
higher than those typically obtained with packed
towers. The authors suggested that their regenerative
membrane-based absorption process could eventually
replace carbon adsorption in VOC removal applica-
tions.
Similarly, Jansen et al. [52] discussed the use of a
hydrophobic membrane coated with cross-linked
polydimethylsiloxane (PDMS) for VOC recovery
from air into non-polar hydrocarbon or silicone oil.
This approach (known as selective membrane absorp-
91
tion) has been successfully demonstrated with the feed
gas having a VOC content of only 0.6 mg/m3.
Gas absorption/stripping with membrane contactors
was recently reviewed by Sirkar [122]; additional
information can be found there. Gas/liquid contacting
in wastewater treatment and semiconductor manufac-
turing are discussed in Sections 6.8 and 6.10, respec-
tively.
6.2.1. Commercial applications
A number of gas/liquid applications have been
commercialized successfully. For example, a Pepsi
bottling plant in West Virginia has operated a bubble-
free membrane-based carbonation line since Decem-
ber 1993. The plant processes 112 gal/min of beverage
with 10 4 in.28 in. Liqui-Cel Extra Flow modules
(see Section 2 and Fig. 1) having a total interfacial
area of 193 m2. Advantages over conventional carbo-
nation methods include reduced foaming, improved
yield, lower CO2 pressures, and minimal drop in ller
speed when lling at elevated temperatures
[51,86,125].
Liqui-Cel contactors are also used in beer produc-
tion. Several plants are using the technology for CO2
removal followed by nitrogenation to obtain a dense
foam head, and others are employing membranes to
remove oxygen from beer to preserve avor. Some
breweries are using Liqui-Cel equipment to strip
oxygen from water, then using the deoxygenated
water to dilute beer that contains 910% alcohol.
The high alcohol content is obtained from high gravity
brewing, a process that offers the brewer increased
capacity [86].
Other commercial applications include treatment of
boiler feedwater, stripping of CO2 from anion ex-
change feed streams to extend bed life, and production
of ultrapure water for semiconductor manufacturing
(see Section 6.10) [5,118,126]. Sengupta et al. [118]
reviewed three operating modes for stripping of vola-
tile gases from water for these applications: vacuum,
inert sweep or purge gas, and a combination of the two;
they also discussed performance data, mass transfer
correlations and cost/performance characteristics.
6.3. Dense gas extraction
Like liquids, dense gases offer a high solubility of
many solutes of interest, yet they also offer the high
92 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
mass transfer rate and low pressure drop enjoyed with
gases. Furthermore, solubility (or distribution coef-
cient) is usually a strong function of density so that the
dense gas is easily separated from the solutes simply
by reducing the pressure [14,129]. This is particularly
attractive in food and avor applications where sol-
vent residues (e.g., in the production of spice oleo-
resins using hexane extraction) are coming under
increased scrutiny by the FDA and other regulatory
organizations. Dense CO2 is a particularly good
choice for applications like these [80], not only
because it leaves no residue but also because it is
non-toxic, non-ammable and inexpensive. The lack
of toxicity offers an important environmental advan-
tage in today's stringent regulatory climate as well as
increased ease of handling.
The strong dependence of solubility on density
allows one to selectively extract solutes of interest
or to fractionate them. For example, one may be
interested in the avor but not the fat contained in
an essential oil such as peanut oil for use in a low-fat
food application. In this case a CO2 density can be
selected (via the temperature and pressure) so that the
avor is largely extracted yet the fat is largely
excluded, since the latter is less soluble at a given
density. Alternatively, both the fat and avor fractions
may be of interest but for different applications. In this
case one would operate at a high density so that both
the fat and avor are extracted, then collect separate
fat and avor fractions by letting the pressure down in
stages (i.e., collect the fat at an intermediate pressure
and the avor at a low pressure).
Although CO2 is often the solvent of choice in
dense gas extraction, other solvents are also used.
For example, in many cases propane offers a more
complete extraction than one would obtain with CO2.
CF Foods (Arvada, CO) has developed a process to
remove nearly 100% of the oil from food products like
peanut and cocoa using dense propane, obtaining both
our and oil as valuable products [85]. Of course, the
ammability of propane is a serious disadvantage.
More generally, however, the disadvantage of hand-
ling CO2 and other uids in the near critical or super-
critical range is the high pressure required. For
example, the critical pressures for CO2 and propane
are 73.8 and 42.5 bar, respectively, as given by Smith
and Van Ness [128] and other textbooks on thermo-
dynamics. Operating at these pressures is expensive.
That is, capital cost is high because the equipment
must be designed to withstand high pressure; operat-
ing cost is also high because the capital cost leads to a
sizeable depreciation charge, and the compression of
the gas incurs substantial charges for power and
maintenance.
Fortunately, the issue of cost can be addressed by
using a membrane contactor for dense gas extraction, a
patented approach given the name PorocritTM by the
inventors [103,121]. A key aspect of the invention is
the ability to operate at high pressure using hollow
bers having a burst strength of <100 psig. This is
accomplished by a novel design that equalizes the
pressure on either side of the membrane so that even
though the system pressure is quite high, the pressure
drop across the membrane is nearly zero. The inven-
tors pointed out that the lower viscosity of CO2 results
in better shell side distribution and less bypassing than
one would obtain with more traditional liquid sol-
vents. The advantages of membrane contactors cited
above, particularly the high efciency (low HTU)
afforded by the plentiful interfacial area, allow a given
supercritical extraction task to be performed in con-
siderably smaller (hence less expensive) equipment
than would be required using a traditional contacting
column.
Apparently, little work has been reported on deter-
mination of mass transfer coefcients for liquid/dense
gas systems in membrane contactors. Brunner [16]
cited the work of Zehnder and Trepp [154], who
measured mass transfer with a-tocopherol and dense
CO2 in laminar ow through tubes, but he stated that in
general there were not enough data for development of
generally applicable correlations. Such correlations
are needed for design if the technology is to realize
its full commercial potential; unfortunately, the unique
characteristics of dense gases render equations like
Eq. (15) unsuitable.
One such characteristic is the kinematic viscosity,
which tends to be rather low for dense gases. For
example, the kinematic viscosity of CO2 at 310 K and
150 bar is one and three orders of magnitude lower
than that of water and air, respectively, at 298 K and
1 bar. Since the magnitude of buoyant forces is inver-
sely proportional to the kinematic viscosity, natural
convection becomes important near the critical point
of a uid [16,32,131]. However, correlations of the
type given in Eq. (15) were developed using systems
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
where natural convection was not important. To render
such correlations valid for dense gases, the Grashof
number Gr must be included [11,32]. Gr, the ratio of
viscous forces to momentum, arises in similarity
solutions to the differential equations that describe
mass transfer with natural convection [42].
6.4. Chiral separations
Ding et al. [35] demonstrated the selective extrac-
tion of d-leucine from a racemic mixture in water
using a 1-octanol solution of N-n-dodecyl-l-hydroxy-
proline. These investigators were able to obtain nearly
complete separation of the two enantiomers, and a plot
of the fraction of d-leucine extracted vs. the Graetz
number agreed closely with the results predicted by
theory [36].
A second example of a chiral separation [72] is
given in the following section.
6.5. Fermentation and enzymatic transformation
As mentioned earlier, membrane contactors offer a
means of in situ extraction of chemical or biochemical
reaction products, which can improve productivity by
shifting equilibrium to the right. This feature is parti-
cularly well suited to fermentation processes because
membrane contactors can be operated aseptically.
Frank and Sirkar [40,41] studied the fermentation of
glucose to ethanol in a membrane contactor. An
aqueous solution of glucose and other nutrients was
pumped through the shell side, which housed yeast
cells immobilized on wooden chips, while dibutyl
phthalate was passed through the tubes to extract
ethanol as it was formed. Frank and Sirkar [41] found
that ethanol productivity increased substantially with
increased tube side ow rate, e.g., productivity
improved by 28% (from 8.65 to 11.08 g/l h) when
solvent ow rate was increased from 0.5 to 0.7
ml/min. These workers also demonstrated the utility
of the membrane contactor for gas exchange, i.e.,
supply of oxygen and removal of carbon dioxide.
Several other studies of extractive fermentation
have also been reported. These include ethanol fer-
mentation with oleyl alcohol [54,55], sec-octanol
[136] or tributyl phosphate [19,74] as the extracting
solvent, acetonebutanolethanol fermentation with
2-ethyl-1-hexanol as the extractant [119], and lactic
93
acid with tri-(n-octyl)phosphine oxide (TOPO, diluted
in kerosene) as the solvent [7,105]. Naser and Fournier
[79] presented an economic analysis of ethanol
production using extractive fermentation.
Other investigators have studied membrane reactors
using single enzymes rather than whole cells. For
example, Lopez and Matson [72] used a microporous
hollow ber membrane reactor to selectively remove
the undesirable stereoisomer from a racemic mixture
of enantiomers encountered in the production of dil-
tiazem. This drug, sold in the US as Cardizem1, is
used to treat hypertension and angina. The precursors
of interest are the methyl esters of ()-trans-4-meth-
oxy-3-phenylglycidic acid (MMPG); the (2R-3S)
form yields the diltiazem stereoisomer with highest
activity. The racemic mixture can be puried by using
a stereoselective lipase to convert the undesirable (2S-
3R)-trans enantiomer to (2S-3R)-methoxyphenylgly-
cidic acid and methanol. This unstable acid rapidly
decarboxylates to form p-methoxyphenylacetalde-
hyde, a strong inhibitor of the enzyme, but this
decomposition can be arrested by the reversible
formation of an adduct with sodium bisulte.
Lopez and Matson [72] used a hydrophilic hollow
ber membrane contactor to carry out this enzymatic
transformation. Their module contained bers made
from a polyacrylonitrile-based copolymer with good
solvent resistance potted in epoxy and housed in
stainless steel. The interior surface of the hollow bers
was covered by an ultraltration-type skin having a
nominal molecular weight cutoff of about 30K, too
small for the enzyme to pass, while the outer surface
was open and readily permeated by the enzyme. The
water-soluble enzyme was immobilized inside of
these asymmetric, aqueous-lled pores, retained by
the 30K skin on the inner surface and the aqueous/
organic interface at the outer one. A solution of the
()-trans-MMPG in toluene owed through the shell,
while an aqueous solution of sodium bisulte passed
through the tubes. The (2S-3R)-methoxyphenylglyci-
dic acid resulting from the enzymatic conversion was
extracted into the aqueous phase, where it was imme-
diately stabilized by the sodium bisulte.
Lopez and Matson [72] explained that their
approach easily accommodates the inevitable loss of
enzyme activity. Periodically, the enzyme can be
removed by backushing water from the tube to the
shell side, then reloaded by ultraltering enzyme-
94 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
containing solution in the opposite direction. Unlike
covalent immobilization schemes, this approach per-
mits easy replacement of the enzyme without the need
to replace the more expensive membrane, and it does
not require development of specic coupling chemis-
tries. As a result of this work, a commercial scale
membrane reactor system in Japan is currently produ-
cing over 75 metric tons per year of 99% (2R-3S)-
trans-MMPG, which accounts for over half of US
Cardizem sales. The plant uses two banks of 12
modules for a total interfacial area of 1440 m2, and
achieves a productivity of over 75 kg/year m2.
Hoq et al. [50] also employed a membrane con-
tactor to carry out a lipase-mediated reaction, i.e.,
hydrolysis of triglycerides. These researchers passed
olive oil and an aqueous solution of lipase and glycerol
(included to stabilize the lipase) on opposite sides of a
microporous polypropylene at sheet membrane with
oil in the pores. The enzyme was adsorbed onto the
membrane surface, and the reaction took place there.
Reaction products, glycerol and fatty acids, parti-
tioned into the aqueous and oil phases, respectively,
so that the reaction and separation were accomplished
in a single step. The extent of hydrolysis was measured
by the amount of glycerol in the exit aqueous stream.
At an oil phase residence time of about 3.6 h, the
extent of hydrolysis was found to increase linearly
with interfacial enzyme concentration at low enzyme
concentrations. However, at higher enzyme concen-
trations the extent of hydrolysis was unaffected by
changes in enzyme concentration, even though the
extent of hydrolysis was much less than 100%. The
authors explained that the process was limited by
reaction at low enzyme levels and diffusion at high
levels. Extent of hydrolysis increased with increased
oil phase residence time, approaching 100% at resi-
dence times of about 8 and 13 h for countercurrent and
cocurrent ow, respectively. Hoq et al. [50] suggested
that a membrane bioreactor for fat hydrolysis would
offer numerous advantages over conventional emul-
sion systems. They also suggested that a hollow ber
conguration might be preferred for industrial imple-
mentation because the interfacial area is higher than
that of the at plate geometry they used.
Similar work was reported by Molinari et al. [78],
who used a 50K polyamide-based ultraltration mem-
brane reactor with olive oil and water owing in
cocurrent mode on the shell and tube sides, respec-
tively. Candida cylindracea lipase was immobilized
onto the membrane by passing an aqueous solution
from the outside sponge surface to the inside skin
layer of the ber; best results were obtained when a
cross-linking agent (gluteraldehyde) was used. As
with the work described above [50], diffusion through
the membrane was the major resistance to mass
transfer.
Molinari et al. [78] compared the results from this
two-uid reactor to those obtained with a 10K mem-
brane reactor operated as a crossow lter with olive
oil/water emulsion fed to the tube side. The specic
enzyme activity was over three times higher for the
two-uid reactor (0.529 vs. 0.170 mmol/mg h). As
with Hoq et al. [50], the two-uid arrangement
allowed simultaneous reaction and product removal,
relieving product inhibition and improving productiv-
ity. Furthermore, the membrane reactor is less energy
intensive than traditional fat-splitting processes,
which typically use an inorganic catalyst operated
at temperatures of 1502608C and pressures of 1.2
5.0 MPa.
Several industrially important organic acids pro-
duced by fermentation have been subjects of mem-
brane contactor studies, including acetic [29,34,61,89,
9193], lactic [20], succinic [9193,108] and citric
acid [9]. For example, Coelhoso et al. demonstrated
the extraction of lactate from a 60% aqueous solution
of sodium lactate using a quaternary ammonium salt
carrier, Aliquat 336 (Fluka, Germany). These
researchers found that the membrane resistance con-
trolled, and resistance could be reduced by lowering
the viscosity of the organic uid via an increase in
temperature or reduction in concentration. Simulta-
neous extraction and stripping of lactate (the latter
with 1 M sodium chloride) was achieved by using two
hollow ber modules in series, with the organic uid
circulating from one to the other and back.
The use of membrane contactors in biological waste
treatment is discussed in Section 6.8.
6.6. Protein extraction
This topic has received increased attention in recent
years with advances in genetic engineering, protein
engineering and related technologies. With progress in
these areas the development of economical means of
protein purication has become the focus of many
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
investigations. Challenges include low concentration,
abundance of molecules similar to the desired one, and
sensitivity to heat, extremes of pH, and organic sol-
vents. Proposed solutions include two-phase aqueous
extraction [67] and reversed micelles formed from an
alkane solution of oil-soluble detergent [44].
Dahuron and Cussler [29] studied protein extraction
in membrane contactors using both of these
approaches. Solutions of cytochrome-c, myoglobin,
a-chymotrypsin, catalase, and urease in phosphate
buffer were extracted using an immiscible aqueous
phase, PEG. Additionally, cytochrome-c was
extracted from phosphate buffer by forming reversed
micelles in aerosol OT dissolved in octane. For each
experiment, uids were circulated from their respec-
tive reservoirs through the membrane contactor and
back to the reservoirs, and the reservoir concentrations
were monitored as a function of time.
Equations were presented which predicted that
ln(
C/
Co) would change linearly with time, and
the experimental data supported that prediction. The
mass transfer coefcients were calculated from the
slopes of ln(
C/
Co) vs. time plots, and values
ranged from 103 to 106 cm/s. This is the range
commonly observed for small solutes [27,133], which
implies the absence of any special mechanism for
protein transport. In particular:
 There was no ultrafiltration effect. If there were,
one would expect the lowest mass transfer coeffi-
cient for urease since it was the largest molecule
studied (MW250 000), yet it exhibited the lar-
gest coefficient.
 There was no interfacial resistance with the
inverted micelle system, an observation that can
be explained by considering the mechanism of
extraction using reversed micelles. The protein
diffuses through the water to the fluid/fluid inter-
face, reacts to form the reversed micelle, then the
micelle diffuses through the membrane pore. The
mass transfer coefficient would be reduced (vs.
what is typically observed for small solutes) if the
formation of the micelle were slower than diffu-
sion through the pore, yet no such reduction was
observed.
Some of the challenges encountered in this work
were as follows:
 With the inverted micelle system the surfactant
was adsorbed onto the membrane surface, which
95
lowered the interfacial tension and led to emulsion
problems. Emulsions were also encountered with
the two-phase aqueous system as a result of the
low interfacial tension between the fluids. These
problems were addressed by careful control of the
static pressure difference across the membrane.
 Protein denaturation (and consequent precipita-
tion) occurred with the inverted micelle system,
an issue that was addressed by taking care to
remove trapped air beforehand.
 In correlating the measured mass transfer coeffi-
cients to the usual dimensionless groups (i.e., Re,
Gz and Sc), diffusion coefficients of proteins were
difficult to obtain. Best results were obtained when
diffusion coefficients in water were used.
Dekker et al. [33] also studied protein extraction
using a membrane contactor. Specically, they
employed microporous polypropylene hollow bers
to investigate extraction of a-amylase using reversed
micelles composed of iso-octane and surfactants.
These investigators found that the system was stable
over only a small range of differential pressure (8
20 cm H2O), which could present difculties upon
scale-up.
6.7. Pharmaceutical applications
Prasad and Sirkar [95] characterized the simulta-
neous extraction of MT and CNT from an actual
process stream provided by Merck (see Section 4)
using a hydrophobic membrane and either toluene
or benzene as the extraction solvent. Solute recoveries
varied with uid ow rates as expected, and values
>99% were reported. As mentioned earlier, surpris-
ingly small HTU values (i.e., 315 cm) were obtained,
and those values decreased with decreasing ber
diameter. The tube side mass transfer coefcient
was predicted with reasonable accuracy using the
Graetz equation [46,47]. No deterioration in mem-
brane contactor performance was observed after 64
days of continuous operation. Contacting schemes
using seriesparallel arrangements of multiple mod-
ules were also discussed.
Prasad and Sirkar [94] studied the purication of
mevinolinic acid also using an actual commercial
stream provided by Merck. Mevinolinic acid, also
known as MK-819, is the precursor to the hypocho-
lesteremic agent mevinolin [4]. MK-819 is produced
96 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
by fermentation of Aspergillus terreus; the product is
easily extracted into isopropyl acetate, which in turn is
extracted at high pH into water, and then back-
extracted into isopropyl acetate at low pH. Prasad
and Sirkar demonstrated the efcacy of hydrophobic
at sheet and hollow ber membrane contactors for
the latter two extractions; their work included inves-
tigation of pressure drop, breakthrough pressure, mass
transfer behavior, gel formation, and cost. Several
aspects of the work are noteworthy:
 Pressure drop through the hollow fiber module was
negligible under the conditions studied, i.e., fiber
diameter 240 mm, fiber length 15 cm, and tube
side velocities as high as 1 cm/s.
 Acidification prior to the low pH extraction would
have led to the formation of a troublesome gel
phase. This was avoided by controlled addition of
acid while the aqueous phase was within the
hollow fibers in contact with the extractant.
 The high and low pH extractions represented low
and high mi systems, respectively. This means that
the organic phase resistance was higher than that
of the aqueous phase with the former, so a hydro-
philic membrane (wetted by the aqueous phase)
would have been preferred. Unfortunately, this
was not feasible due to the formation of an
unstable precipitate which would have blocked
the aqueous phase-filled pores.
 Contrary to Eq. (6a), when 3% isopropanol was
added to the aqueous phase prior to the high pH
extraction, the breakthrough pressure increased
(from 34 to 7 psi at pH 12) even though the
interfacial tension dropped. The authors explained
these and other results in terms of the membrane
pore size, the change in charge of MK-819 with
pH, and the surfactant properties of MK-819.
6.8. Wastewater treatment
Recovery of troublesome pollutants from aqueous
solution by liquid/liquid extraction has been investi-
gated extensively. The list of pollutants studied
includes phenol, toluene, 2-chlorophenol, benzene,
chloroform, 1,1,2-trichloroethane, trichloroethylene,
carbon tetrachloride, tetrachloroethylene, nitroben-
zene, trichloromethane, tetrachloromethane and acrylo-
nitrile, with MIBK, hexane, isopropyl acetate,
kerosene, silicone oil and sunower oil as extraction
solvents [6,91,93,96,152,153].
Air stripping of VOCs has also been demonstrated.
Semmens et al. [115] used microporous polypropy-
lene hollow bers to strip chloroform, tetrachloroethy-
lene, carbon tetrachloride, 1,1,2-trichloroethane and
trichloroethylene from aqueous solution, with the
water and organic-free air owing countercurrently
on the tube and the shell sides, respectively. Not
surprisingly, the liquid lm resistance controlled,
and in general the experimentally determined mass
transfer coefcient agreed reasonably well with the
value predicted by Eq. (16). Semmens and Gantzer
[114] discussed both the theoretical and practical
aspects of VOC removal by gas stripping.
Several studies have been done on the use of
membrane contactors for bubble free aeration in waste-
water treatment. Such an approach offers several
advantages over conventional methods including
absence of foaming and higher aeration rates
[25,26]; additional advantages are discussed below.
Cote et al. [26] studied the problem using a bundle of
silicone rubber hollow bers immersed in a chamber
containing water that had been treated with sodium
sulte to remove the oxygen. The temperature-con-
trolled water was circulated across the bundle while
gas (oxygen or air) owed through the bers, and the
oxygen concentration in the water was measured over
time.
Data were collected for a variety of conditions, and
the corresponding mass transfer coefcients were
calculated; results were predicted by a model that
considered two resistances in series, i.e., the mem-
brane and the liquid lm (see Eq. (33)). The authors
compared operation in ow-through vs. dead end
mode on the gas side, and reported a 45% lower
oxygen transfer rate with the latter. They attributed
this to the fact that in dead end mode the oxygen had to
diffuse through water vapor, while with ow-through
operation the water vapor was swept away.
Ahmed and Semmens [1] also looked at bubbleless
aeration with bers operated in the dead end mode.
These workers sealed one set of ends of a microporous
polypropylene ber bundle, then placed the bundle
inside a PVC pipe. The bers were connected to an
oxygen supply, while water was circulated through the
pipe from a reservoir, causing the bers to uidize.
The oxygen concentration in the reservoir was mea-
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
sured vs. time, and from those data the overall mass
transfer coefcient was calculated. The authors con-
cluded that liquid lm mass transfer coefcients were
as high as any previously reported for parallel ow
modules, primarily because of the high Reynolds
numbers achievable with the module design
employed. The mass transfer coefcient increased
with increasing pressure, but this turned out to be
an artifact caused by back diffusion of nitrogen from
the water into the bers [2]. The results indicate that
one can realize the advantages of dead end operation
without sacricing mass transfer efciency. These
advantages include no loss of VOCs to the gas stream
and 100% oxygen transfer efciency at low power
input. Low power input is important in aquaculture
because trout, salmon and other sh that require high
levels of dissolved oxygen are troubled by the high
power inputs associated with conventional aeration
equipment [111].
In related work, Johnson et al. [53] studied bubble-
free aeration using a sealed hollow ber bundle in a jet
stream. That is, the bundle was unencumbered by a
shell or similar enclosure, which allowed the bundle to
become uidized by the turbulent ow of the jet.
Johnson et al. pointed out two important advantages
of this conguration: reduced head loss, and ability to
process solids-laden streams without clogging. The
authors showed that these advantages are available
with no reduction in mass transfer rate compared to
conventional designs (see Eq. (35)).
Semmens et al. [111] described eld studies used to
test a microporous polypropylene membrane contac-
tor operated in dead end mode. Short bers (less than
0.7 m) performed better than long (3 m) ones because
the former moved more freely and were less likely to
trap occulent solids. Uncoated bers performed well
in the aeration of secondary efuent, but they fouled
easily upon treatment of lake water. However, a gas
permeable coating allowed the bers to run for over
300 h with no decrease in oxygen transfer efciency.
Related reports were given by Semmens and Gantzer
[113], Pankhania et al. [83], and Semmens and Gant-
zer [114].
McGrath and Ergas [75] demonstrated the removal
of toluene from air and subsequent biological destruc-
tion using a microporous polypropylene hollow ber
module. An aqueous solution containing a mineral
media inoculated with a culture of Pseudomonas
97
putida was circulated through the shell side, and a
syringe pump was used to continuously add toluene to
the air that owed on the tube side of the bers. Over
98% toluene removal was achieved at an inlet con-
centration of 100 ppm and an overall residence time of
less than 1 min.
Aziz et al. [6] studied the biodegradation of tri-
chloroethylene in a microporous polypropylene hol-
low ber contactor. They passed contaminated water
(containing up to 709 mg/l trichloroethylene) through
the tube side of the bers while circulating Methylo-
sinus trichosporium OB3b, a methanotrophic bacter-
ium, through the shell side. Some 78.399.9% of the
trichloroethylene was removed from the bers at
hydraulic residence times of 315 min; biodegrada-
tion rate constants ranged from 0.16 to 0.9 l (mg
TSS)1 day1, where TSS is total suspended solid.
The authors concluded that the hollow ber membrane
bioreactor is a promising technology for degradation
of chlorinated solvents.
6.9. Metal ion extraction
There is a growing need for cost-effective technol-
ogies for recovery of metals from industrial process
streams, not only because the metals are valuable, but
also to meet increasingly stringent regulatory require-
ments. Several examples of metal recovery using
membrane contactors have been reported. Yang et
al. [148] described the use of membrane contactors
for simultaneous extraction of cations (e.g., Cu, Zn,
Ni) and anions (e.g., Cr(VI), Hg, Cd) from metal-
contaminated wastewaters. These investigators used a
hollow ber contactor with two sets of bers contain-
ing a liquid ion exchanger and a tertiary amine solvent,
respectively; details were described by Carroll et al.
[18]. The wastewater stream owed on the shell side of
the module, and each extractant owed through one of
the ber sets.
Taking a divalent cation as an example, the extrac-
tion proceeded according to the following reaction:
A2 aq 2RH org $ R2 A org 2H aq
(47)
In this reaction the proton release caused an un-
desirable shift in the partition coefcient towards
the wastewater. However, a synergy was created by
simultaneously extracting of an anion, a process that
98 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
consumed protons:
HX aq H aq 2R3 N org taking into account the velocity distributions on both
$ R3 NH2 X org (48)
A similar approach was used for enhanced ef-
ciency in the simultaneous recovery of two cations,
e.g., Cu2 and Zn2. These cations are typically
recovered using extractants like LIX 84 (Henkel,
Tuscon, AZ) and bis(2-ethylhexyl)-phosphoric acid
(D2EHPA; Sigma, St. Louis, MO), but selectivity is
usually poor when the cations are extracted simulta-
neously. A signicant improvement in selectivity was
obtained from the synergy offered by the geometry
described here, with the wastewater on the shell side,
LIX 84 owing through one set of bers and D2EHPA
owing through the other set.
Yun et al. [151] also studied extraction of copper
and chromium(VI) from water using a hollow ber
membrane contactor, with water and extracting sol-
vent on the tube and shell side, respectively. Copper
was extracted using LIX 84 in accordance with
Eq. (47), while chromium(VI), present as HCrO 4,
was extracted using tri-n-octylamine as described
by Eq. (48). Metal concentrations were reduced to
1 mg/l from 500 and 100 mg/l for copper and chro-
mium(VI), respectively. The authors presented a
mathematical model that predicted the experimental
data well. They concluded that the extraction of
copper was controlled by interfacial kinetics; the
equilibrium constant for the interfacial reaction
(Eq. (47)) is 1.7, and the forward reaction rate con-
stant is 9.0106 cm/s.
Yoshizuka et al. [150] characterized the extraction
of palladium(II) from aqueous chloride media into
3,3-diethylthietane (DETE) using a hollow ber mod-
ule. They pointed out that reactions accompanying
extraction of metals (e.g., Eqs. (47) and (48)) take
place either at the aqueous/organic interface or on the
aqueous side close to the interface. The latter occurs
when the extractant has signicant solubility in water,
such as with chelating agents like diphenylthiocarba-
zone and benzoylacetone, while the reaction is con-
ned to the interface with extractants such as
tributylphosphate due to their long hydrophobic tails.
Yoshizuka et al. showed that DETE, which is highly
soluble in water, does not show interfacial activity.
Equilibrium and kinetic studies allowed extraction
rates to be explained by both a diffusion model and
homogeneous reaction kinetics in the aqueous phase
the shell and tube sides.
Kathios et al. [57] investigated the feasibility of
microporous polypropylene hollow ber membrane
contactors for processing radioactive wastes. They
chose neodymium as a model solute; this element is
not radioactive but behaves similarly to trivalent
americium, a long-lived actinide. The organic extracts
DHDECMP (dihexyl-N,N-diethylcarbamoylmethyl-
phosphonate) and CMPO (n-octyl(phenyl)-N,N-diiso-
butylcarbamoylmethylphosphine oxide) were chosen
as organic extractants because of their selectivity for
actinides over ssion products and their afnity for
trivalent actinides at moderate acid concentrations;
diisopropylbenzene (DIPB) was used as a diluent. The
extraction proceeded in the presence of 2 M nitric acid
via the formation of a neodymium complex:
Nd3 3NO
3 3CMPO $ NdNO3 3
3CMPO
(49)
(Note that Eq. (49) is similar to Eq. (27).) The reverse
reaction describes the subsequent recovery of neody-
mium from the organic phase by back-extraction into
dilute (0.01 M) nitric acid. Aqueous and organic
phases owed on the tube and shell side, respectively,
in countercurrent mode.
High organic and low aqueous ow rates gave best
results for the forward extraction, while low organic
and high aqueous ow rates were best for the back
extraction. In each case the low ow rate of the solute-
rich stream provided a long residence time for mass
transfer, while the high ow rate of the extracting uid
maintained the maximum driving force by keeping the
solute concentration low. In accordance with Eq. (3), a
higher extent of neodymium removal was obtained
with a system having a higher value of the distribution
coefcient mi. That is, the forward reaction was
increasingly efcient for 0.25 M DHDECMP,
0.81 M DHDECMP and 0.25 M CMPO; respective
mi values were 0.25, 3.6 and 8.8.
Neodymium recovery was better in the back-extrac-
tion with a low mi system, where the higher mass
transfer resistance (see Eq. (3)) is more than compen-
sated by the greater equilibrium concentration driving
force. The authors suggested that a hydrophilic mem-
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
brane might be more appropriate in this application. In
that case the pores would be wetted by the aqueous
rather than the organic phase; this would lead to a
lower mass transfer resistance because the neody-
mium would travel in its compact ionic form rather
than as a bulky complex.
Additional examples of metal ion extraction were
provided by Prasad and Sirkar [96].
6.10. Semiconductors
Membrane contactors are used in the production of
ultrapure water for semiconductor manufacturing,
where remarkably low levels of contaminating gases
are required. For example, oxygen concentration must
be reduced to the ppb range to avoid uncontrolled
native silica oxide growth in wafer-immersion sys-
tems. Unlike conventional deoxygenation approaches
like such as nitrogen bubbling and vacuum degasica-
tion, membrane contactors provide a uniform water
dispersion and they are insensitive to changes in ow
rate. Nitrogen bubbling has another disadvantage, i.e.,
even though it removes oxygen, it saturates the water
with another troublesome gas, nitrogen. Membrane
contactors are also used to add CO2 to water to
increase the aggressiveness of a rinse step [31].
As mentioned in the above discussion of commer-
cially available modules (Section 2), membrane con-
tactors are used commercially for ozonation of water
in silicon wafer cleaning applications. Specic uses
include removal of organic and metal contamination,
control of native oxide growth, and photoresist strip-
ping. Unlike conventional approaches, this method of
ozonation is bubble-free, an important feature in the
semiconductor industry because bubbles attract par-
ticles that later form troublesome deposits on wafer
surfaces. Membrane contactors also allow manufac-
turers to enjoy the advantages of ozone in lieu of
conventional cleaning chemicals like sulfuric acid and
peroxides. That is, ozone is milder, more environmen-
tally friendly, reduces water usage, and requires less
oor space to handle. Membrane contactors have
become the technology of choice for ozonation in
Japan [17,142144].
Wikol et al. [143] investigated the ozonation of tap
water using a microporous PTFE hollow ber module
(DISSO3LVE, W.L. Gore & Associates, Elkton, MD;
see Section 2) with water and gas on the tube and shell
99
sides, respectively. Inlet gas ozone concentrations as
high as 235 g/m3 were obtained by feeding two stan-
dard liters per minute of oxygen and 10 standard
cm3/min of nitrogen to an ozone generator.
The authors found that the dissolved ozone con-
centration in the liquid leaving the membrane con-
tactor increased linearly with inlet gas ozone
concentration and with pressure in accordance with
Henry's law. They also found that ozone concentration
decreased with increasing ow rate of water; this
indicates that increased residence time for mass trans-
fer was more important than decreased tube side
boundary layer resistance or increased concentration
driving force (see Eq. (9)). When operated at a total
pressure of 1.0 kg/cm2, temperature of 258C and feed
gas ozone concentration of 235 g/m3, target dissolved
ozone concentration of 210 ppm (suitable for most
wafer cleaning applications) was obtained at water
ow rates as high as 15 l/min. Similar results were
reported by Gottschalk et al. [45].
In related work, Cornelissen et al. [23] studied
ozonation of degasied, deionized water using W.L.
Gore's DISSO3LVE PTFE membrane contactor, again
with liquid and gas on the tube and shell sides,
respectively. Lower oxygen ow rates led to higher
ozone concentrations in the gas exiting the ozone
generator; the corresponding increase in mass transfer
driving force led to higher dissolved ozone concentra-
tions in the water leaving the membrane module. The
extent of ozonation also increased with decreasing
water pH, where base-catalyzed decomposition is less
important, and with decreasing temperature, where the
equilibrium ozone concentration is higher. Dissolved
ozone levels increased with decreasing water ow rate
in agreement with the ndings of Wikol et al. [143]
discussed above; again target ozone concentrations
were obtained at a water ow rate of 15 l/min, suitable
for most commercial applications.
6.11. Osmotic distillation
Osmotic distillation (OD) is a process where one or
more volatile components of a liquid feed are trans-
ferred through a non-wetted microporous membrane
into another liquid capable of absorbing those com-
ponents. The driving force is the difference in vapor
pressures of the volatile component(s) over the respec-
tive liquid solutions. The process proceeds at ambient
100 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
temperature, which is particularly attractive for heat
sensitive products such as those found in the food and
pharmaceutical industries. For many applications of
practical interest, the feed is a dilute aqueous solution
of non-volatile solutes such as sugars, polysacchar-
ides, amino acids, proteins, or carboxylic acid salts,
and the objective is to concentrate the solution by
removing the solvent water. A concentrated aqueous
salt solution (brine) is employed on the opposite side
of the membrane to provide the vapor pressure driving
force; the diluted salt solution leaving the membrane
contactor is concentrated then reused. A number of
salts are suitable, but potassium salts of ortho- and
pyrophosphoric acid offer several advantages, includ-
ing low equivalent weight, high water solubility, steep
positive temperature coefcients of solubility, and safe
use in foods and pharmaceuticals [49,125,126].
Osmotic distillation can also be used to concentrate
aqueous solutions of volatiles by selective removal of
water, a feature of interest to the avor and fragrance
industry. Flavor and fragrance compounds can be
concentrated in this manner because (1) at the low
operating temperatures typically used, the vapor pres-
sure of these compounds is depressed relative to that
of water, (2) many avor/fragrance volatiles are
hydrophobic, rendering them poorly soluble in con-
centrated saline solutions, and (3) the molecular
weights of these compounds are substantially higher
than that of water, so that their diffusive permeability
through the membrane is much lower [49].
Fruit and vegetable juice concentrations have been
successfully demonstrated at pilot facilities in Mel-
bourne and Mildura, Australia. The Melbourne plant
contains two 19.2 m2 Liqui-Cel modules (see Fig. 1),
along with ultraltration and reverse osmosis equip-
ment (for feed pretreatment) and a brine evaporator.
The plant can concentrate 50 l/h of juice to 6570%
solid by weight. The Mildura plant is operated by
Vineland Concentrates (a subsidiary of the Wingara
Wine Group) and CELGARD LLC. This plant
contains 22 4 in.28 in. Liqui-Cel modules (total
interfacial area: 425 m2) operated at 30358C and
two atmospheres. Color, avor and aroma retention
are good, but module cleaning is an issue
[49,86,125,126].
Varietal grape juice concentrates used for produc-
tion of high-quality wines are of particular interest.
These concentrates are stable upon long periods of
storage; as a result, they can be used as needed to
adjust the sugar content of fresh grapes so that varia-
tions in the alcohol content of a particular wine are
minimized. Furthermore, such concentrates can be
shipped over long distances to allow production of
high-priced wines in regions where the required
grapes are not available or too expensive [49]. Tomato
juice concentration has also been studied in recent
work (e.g., [37,87]).
The growing emphasis on health and tness in
recent years has led to a demand for beer and wine
with reduced alcohol content. Such products can be
prepared by osmotic distillation if water is used as the
stripping liquid instead of saline solution. This leads to
selective removal of ethanol without signicant deple-
tion of water or the components that give beer and
wine their characteristic taste, aroma and mouthfeel.
Similarly, OD can be used to reduce the alcohol
content of ``hot'' wines, i.e., wines whose alcohol
content is too high because they are produced from
grapes with high sugar. J. Lohr Winery (San Jose, CA)
is currently using four 4 in.28 in. Liqui-Cel modules
to produce Ariel, a wine that contains less than 0.5%
alcohol [49,76,86].
In the pharmaceutical area, OD can be used to
concentrate miscible solvent extracts of intracellular
products from fermentation broths. Similarly, solvent
can be selectively removed from chromatography
column eluants to concentrate antibiotics, vaccines,
hormones and other heat-sensitive biologicals [49].
Osmotic distillation has been recently reviewed by
Kunz et al. [68] and Hogan et al. [49].
7. Concluding remarks
Membrane contactors embody an exciting new
approach to uid/uid contacting that offers numerous
advantages, including substantially higher efciencies
(i.e., lower HTU values) than those achievable in
traditional dispersed phase devices. Membrane con-
tactors have been demonstrated in a diverse range of
gas/liquid and liquid/liquid applications; even though
several of these have been commercialized, the num-
ber of commercial applications has not yet reached the
full potential of the technology, particularly with
liquid/liquid contacting. To facilitate further commer-
cialization, challenges that need to be addressed
 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106 101

include (1) better understanding of shell side ow Sc Schmidt number, /D

leading to more reliable scale-up procedures, (2) Sh Sherwood number, kd/D
higher comfort level with the technology among hShi average Sherwood number, hkid/D
potential users, and (3) improved materials of con- v velocity (cm/s)
struction that offer a wide range of solvent compat- V average volume occupied by one fiber (cm3)
ibility. Undoubtedly, the advantages of membrane
contactors will render the technology pervasive as Subscript
progress is made in these areas.
A component A
b bulk
8. Nomenclature B component B
E effective; equilibrium (Eq. (46))
a interfacial area (cm2/cm3) e equivalent
A membrane area in module (cm2) f feed
C concentration (g mol/l); constant in Eq. (25) G gas
Cp heat capacity at constant pressure (J/s K) i component i
d diameter (cm) (mm in Figs. 1114) i inside; at the interface
de equivalent diameter (cm) in module inlet
D diffusivity (cm2/s) L liquid
f function of geometry in Eq. (15) lm log mean
G gas flow rate (cm3/s) M membrane
Gz Graetz number, d2v/DL Nb number of baffles
h heat transfer coefficient (J/s cm2 K) o organic phase; outside; initial condition
H Henry's law constant out module outlet
HTU height of a transfer unit (cm) r radial
k individual mass transfer coefficient (cm/s); s shell side
thermal conductivity (J/s cm K) t tube side
k0 mass transfer coefficient with instantaneous w aqueous phase; wall
reaction (cm/s) z axial
hki average mass transfer coefficient (cm/s) 1 end of module where organic phase exits
K overall mass transfer coefficient (cm/s) 0 end of module where organic phase enters
KE equilibrium constant (g mol/l)
kR reaction rate constant (s1) Greek letters
L length (cm)
LTU length of a transfer unit (cm)  exponent for Reynolds number in Eq. (15);
m partition coefficient: ratio of equilibrium extent of shell side bypassing
concentration in organic phase to that in  exponent for Schmidt number in Eq. (15);
aqueous phase constant in Eq. (19)
MG module geometry number (rr/zz)(L/R)2  membrane porosity
MT mass transfer number, kA 0 void fraction of fibers
NTU number of transfer units 0 standard deviation divided by the mean
Nu Nusselt number, hd/k (Eqs. (17) and (29))
Pr Prandtl number, Cp/k
interfacial tension (dynes/cm)
Q flow rate (cm3/s)  fiber packing fraction
r radius (cm)  Darcy's permeability tensor
R0 average radius (cm)  viscosity (g/cm s)
Re Reynolds number, dv/  contact angle
S cross-sectional area (cm2)  density (g/cm3)
102 A. Gabelman, S.-T. Hwang / Journal of Membrane Science 159 (1999) 61106
 surface tension (dynes/cm)
 space time (s); tortuosity
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