2502 Ind. Eng. Chem. Res.

2001, 40, 2502-2511

Dendrimer Liquid Membranes: CO2 Separation from Gas Mixtures

A. Sarma Kovvali† and K. K. Sirkar*
Department of Chemical Engineering, Chemistry and Environmental Science,
New Jersey Institute of Technology, Newark, New Jersey 07102

A generation 0 poly(amidoamine) (PAMAM) dendrimer in the immobilized liquid membrane

(ILM) configuration was studied using flat films and hollow fibers for CO2-N2 separation. This
dendrimer as a pure liquid functions as a CO2-selective molecular gate with highly humidified
feed gas (Kovvali et al. J. Am. Chem. Soc. 2000, 122, 7594). The present work broadens the
range of relative humidity of the feed gas stream (RHf) by adding a small amount of glycerol to
the pure dendrimer liquid. A 75% dendrimer-25% glycerol ILM was found to increase the
operating range of RHf substantially while maintaining the CO2 permeance and the selectivity
(RCO2/N2) close to the levels observed with a pure dendrimer ILM. The performances of pure and
75% dendrimer ILMs were found to be superior or comparable to the highest reported RCO2/N2’s.
This behavior is explained in terms of the charged environment in the dendrimer liquid
membrane under humidified feed conditions and facilitated transport of CO2.

1. Introduction
In a recent short paper,1 we had introduced the notion
of a stable liquid membrane based on a pure liquid of
generation 0 poly(amidoamine) (PAMAM) dendrimers
for highly selective separation of CO2 from N2. We had
also provided there a few preliminary results for the
above system for the dendrimer liquid membrane im-
mobilized in a microporous hydrophilized polymeric
substrate. In this paper, we explore this topic in greater
detail to develop a broader perspective on the utility of
dendrimer liquid membranes in the immobilized liquid
membrane (ILM) form for gas transport and separation.
Liquid membranes for gas separation have been
studied by a number of investigators over the years.2-8
Of the various forms of liquid membranes, namely, ILM,
solvent-swollen polymeric membrane,9 contained liquid
membrane (CLM),10 ion-exchange membrane,11-14 and
polyelectrolyte membrane,15-18 ILMs are simple and
attractive if they are stable. They have high species
permeance and generally possess higher selectivities
compared to conventional polymeric membranes. For
example, for CO2-N2 or CO2-CH4 separation, com-
mercialized polymeric membranes generally have se-
lectivities in the range of 15-40; liquid membranes, on
the other hand, can have much higher selectivities, as
much as 4000.19 Liquid membranes, however, are
generally subject to problems of stability. For aqueous
solution-based membranes, the membrane is unstable
unless both feed and sweep streams are humidified
(except in CLM). Further, the facilitating agents incor-
porated in the liquid membrane are often volatile and
therefore are lost with time. This is true even if the
substrate is an ion-exchange membrane.20
Chen et al.21-23 have therefore developed ILMs for
CO2-N2 separation using glycerol as the solvent and
nonvolatile species, such as sodium carbonate and
sodium glycinate, as carriers. Glycerol is essentially a
nonvolatile liquid; as a result, the membranes were
shown to possess remarkable stability in environments
† Current address: Compact Membrane Systems, Wilming-
ton, DE.
* To whom correspondence should be addressed. Tel.: (973)
596-8447. Fax: (973) 642-4854. E-mail: sirkar@adm.njit.edu.
10.1021/ie0010520 CCC: $20.00 © 2001 American Chemical Society
Published on Web 04/26/2001
Figure 1. Schematic of the structure of the EDA core PAMAM
dendrimer of generation 0.
having considerable humidity variations. The hypoth-
esis behind the recent paper by Kovvali et al.1 is as
follows: is it possible to replace the solvent altogether
and use a pure liquid as the liquid membrane medium
as well as the facilitating agent for facilitated CO2
transport over N2? This was prompted by the fact that
pure glycerol has an inherently low selectivity for CO2-
N2, namely, 1.5.
Amine functional groups in a form where the com-
pounds are not volatile could lead to high carbon dioxide
permeances and selectivity with improved stability. One
such class of carriers is dendrimers. Dendrimers are a
novel class of polymers having some unusual properties.
A major class of dendrimers which has been studied in
a wide range of applications is the PAMAM dendrimers.
PAMAM dendrimers of generation 0 having an ethyl-
enediamine (EDA) core were therefore chosen as the
liquid to be immobilized in the pores of hydrophilized
microporous polymeric membranes for selective CO2
separation. This work was focused on a generation 0
dendrimer instead of higher generations because of its
suitable characteristics for the application at hand. As
shown in Figure 1, the generation 0 dendrimer of
molecular weight 518 has four primary amine groups
and two tertiary amine groups; the molar concentration
of primary amines is 9.1 M, and that for tertiary amines
is 4.6 M. It is supposedly nonvolatile and is available

in a 20% methanol solution, from which methanol could
be removed by vacuum to yield a pure dendrimer liquid.
PAMAM dendrimers are considered nontoxic up to
generation 5.24
The PAMAM dendrimer of generation 0 is hygroscopic
but has a finite solubility in water. Similarly, glycerol
is strongly hygroscopic but completely miscible with
water. When dendrimer-based ILMs are exposed to
humidified feed gas, they pick up a significant amount
of water from the feed. Some of the water will be
transported across the membrane because the sweep gas
used in our experiments was always dry helium. The
water content in the liquid membrane is likely to have
a significant influence on the performance of the den-
drimer-based ILMs.
Kovvali et al.1 employed experimental conditions in
which the feed gas had 100% relative humidity (RH),
whereas the sweep gas stream was dry. These condi-
tions were similar to those employed by Chen et al.21-23
It is important to know the effect of feed gas humidity
variation on the dendrimer membrane performance
because it has been pointed out1 that when the feed gas
is completely dry, the pure dendrimer membrane has a
CO2-N2 selectivity of only 5 and a very high N2
permeance. However, addition of a significant amount
of glycerol to the dendrimer liquid may potentially
decrease the N2 permeance under dry feed gas condi-
tions. Because glycerol-based ILMs containing nonvola-
tile carriers such as glycine-Na and Na2CO3 were found
to be quite effective even when the feed gas had rather
low RHs,21-23 we have studied specifically ILMs con-
taining small amounts of glycerol in the dendrimer
generation 0 liquid. The objective of the addition of
glycerol to the pure dendrimer liquid was to see if the
operating RH range of the feed gas stream can be
broadened substantially without compromising the high
selectivities associated with pure dendrimer liquids.
The sorption of moisture in the dendrimer liquid is
obviously important for the CO2 facilitation reactions.
However, the data on water uptake by pure dendrimers
is not available in the literature. Chen et al.21 reported
preliminary data on water uptake by glycerol at differ-
ent ambient RHs. Therefore, the extent of sorption of
moisture in the pure dendrimer liquid has also been
determined at various known RHs and compared with
that in glycerol. An important observation in Kovvali
et al.1 was that the permeability of N2 through the
PAMAM generation 0 dendrimer liquid membrane was
extraordinarily low when the feed gas was humidified.
This was ascribed to the very highly charged environ-
ment in the presence of moisture due to a very high
concentration of reactive functional groups in the pure
dendrimer liquid. Whether such a behavior is retained
in the presence of small amounts of glycerol in the ILM
is also of interest. We have also briefly studied the CO2-
O2 system to the same end. Because hollow fibers are
often the substrate of choice for gas separation, we have
explored here pure dendrimer liquid membranes in two
types of hollow fiber substrates.
2. Reaction Mechanisms for Carbon Dioxide
Facilitation Reactions with Amines
In general, amines as carriers perform better than
carbonate/bicarbonate solutions for carbon dioxide sepa-
ration. Among various amines, sterically hindered ones
have higher capacities for CO2 than unhindered primary
and secondary amines.25
Ind. Eng. Chem. Res., Vol. 40, No. 11, 2001 2503
In systems where amines are used as carriers, the
reactions can occur with primary, secondary, or tertiary
amines. A primary amine reacts with carbon dioxide
according to
CO2 + 2RNH2 S RHNCOO- + RNH3+ (1)
The overall reaction between CO2 and a secondary
amine is
CO2 + 2R2NH S R2NCOO- + R2NH2+ (2)
Although the tertiary amine is not supposed to react
directly with CO2 like a primary or a secondary amine
because they lack the proton needed in the deprotona-
tion step, tertiary amines show considerable reactivity
toward CO2; further, water is essential for this reaction.
The reaction of CO2 with tertiary amines can be
described satisfactorily with the base-catalysis reaction
mechanism26,27
CO2 + R3N + H2O S HCO3- + R3NH+ (3)
3. Experimental Details
Dendrimer liquids used in the current work are
hydrophilic. Hydrophilic or hydrophilized membrane
substrates were therefore used in the present study to
immobilize the liquid membranes. The dendrimer liquid
does not wet hydrophobic substrates spontaneously, but
it does wet hydrophilic substrates without any special
effort. All of the ILMs formed completely filled the pores
of the substrate membrane, resulting in the ILM thick-
ness being equivalent to that of the substrate. Both flat
and hollow fiber membranes were employed. The flat
membranes used were hydrophilized poly(vinylidene
fluoride) (PVDF) membranes (Millipore, Bedford, MA)
and hydrophilized Celgard 2500 membranes (Celgard
LLC, Charlotte, NC). The hydrophilized Celgard 2500
membranes prepared from hydrophobic polypropylene
microporous substrates are not yet commercially avail-
able. The developmental hydrophilized Celgard mem-
branes studied here were prepared by an approach quite
different from the surfactant-based approach used for
the commercially available hydrophilized Celgard 2500
films. Two types of hollow fiber membranes were also
used: hydrophilized poly(acrylonitrile) (PAN; Sepracor,
Marlborough, MA) and polysulfone (PS; Minntech, Min-
neapolis, MN). It should be pointed out that the PAN
fibers used are of the ultrafiltration type whereas the
PS fibers are of the microfiltration type. Hollow fiber
modules were fabricated by placing the fibers in a
transparent polyethylene shell casing and separating
the tube side and shell side with appropriate potting.
The details of the substrate membranes and membrane
modules fabricated are provided in Table 1.
Starburst PAMAM dendrimers of generation 0 in
methanol were obtained from Sigma (St. Louis, MO).
Starburst PAMAM dendrimers of generation 0 are
henceforth identified as “dendrimers”. Methanol from
the dendrimer solution was removed by subjecting the
solution to vacuum for several hours to several days;
the resulting pure dendrimer solutions were stored in
a desiccator until used. Dendrimer solutions of 44% (1M)
and 75% in glycerol were also prepared for particular
experiments. All mixtures of CO2 and N2 containing
between 0.5% and 25% CO2 were obtained from Mathe-
son (East Rutherford, NJ). Higher CO2 concentrations
2504 Ind. Eng. Chem. Res., Vol. 40, No. 11, 2001

Table 1. Details of Substrates and Modules Used

membrane supplier material porosity tortuosity thickness, µm pore diameter, µm
Flat Membrane Substrates
Millipore Durapore (hydrophilized PVDF) 0.7a 2.58b 100a 0.1a
Celgard hydrophilized Celgard 2500 0.45c 2.54c 25c 0.08c
Hollow Fiber Substrates
Sepracor poly(acrylonitrile) (PAN) N/Ad N/A 50e 70000 MWCO
Minntech polysulfone (PS) 0.3-0.4 N/A 40f 0.1
a From the manufacturer’s catalog (Millipore). b From ref 21. c From ref 28. d N/A: not available. e Fiber i.d. 200 µm and o.d. 300 µm;

logarithmic total membrane area of 116.4 cm2. f Fiber i.d. 280 µm and o.d. 360 µm; logarithmic total membrane area of 35.96 cm2.

in the feed gas mixture were obtained by mixing pure
CO2 and N2 gas streams using Matheson electronic
mass flow controllers (model 8272-0412) in required
ratios.
3.1. Preparation of ILMs. The ILMs were prepared
by the immersion technique.21 ILMs prepared by this
technique normally have thicknesses comparable to
those of the substrates. After immersing in the den-
drimer solution (either pure or in a solvent), the
substrate was removed from the liquid, and the excess
liquid from the surfaces was carefully wiped with
kimwipes. In some instances, any moisture absorbed by
the liquid was removed by applying a vacuum during
the wetting process. The procedure was similar if a 44%
or 75% solution of dendrimer in glycerol was used as
the liquid.
Pure dendrimer ILMs were immobilized in the hollow
fibers by filling the entire void fraction of the fibers. The
lumen side of the fibers was filled with the 20% solution
of dendrimer in methanol for a minute with the other
end closed. Nitrogen was passed at a low flow rate on
the shell side to evaporate the methanol. The procedure
was repeated from the other tube end. In the case of
polysulfone fibers, because of their pore size and poros-
ity, methanol was seen coming out on the shell side. No
attempt was made to evaporate methanol from the shell
side during immobilization because it could hinder the
ILM preparation. After the ILM was immobilized in the
pores, nitrogen at high flow rates (∼50 cm3/min) was
passed from the tube side for a few minutes to clear the
lumen side of any possible blockage. This was verified
by making sure all fibers were open. To remove any
remaining methanol from the pores, a house vacuum
(∼45.7 cmHg) was applied from the shell side with a
3.3. Experimental Setup and Procedure. The
experimental setup and procedure were similar to those
used in our earlier studies.1,21-23 The flat membrane of
approximately 10 cm2 area was placed between half-
cells and was supported by a porous stainless steel
screen (Pall Trinity Micro, Cortland, NY) in the bottom
cell well. The gas space on the top of the membrane was
sealed by a Viton O-ring on the top half of the cell. The
CO2/N2 permeation performance through the ILMs was
measured by the sweep gas technique.4 The experimen-
tal setup for the hollow fiber modules was the same as
the one used for flat membranes. The feed for all hollow
fiber ILMs was introduced through the lumen side of
the membrane with the sweep gas flowing on the shell
side. Experiments with the hollow fiber ILMs were
performed in both cocurrent and countercurrent modes.
The humidities of the gas streams were measured by
humidity probes. In all experiments, the sweep gas was
always dry helium. All experiments were conducted at
room temperature, 23 ( 2 °C.
3.4. Calculation Procedure for Gas Permeances
and the Separation Factor. On the basis of the
calibration in the gas chromatograph (GC) and the peak
areas obtained, the mole fractions of the species in the
sweep gas stream can be obtained. When these mole
fractions are multiplied by the sweep side gas volumet-
ric flow rate, one obtains the volumetric permeation rate
of the species through the membrane.
The effective permeance of a species through the
membrane was calculated by
()
Qi
tm eff
)
Vi
At∆pi
(4)

small flow of nitrogen from the tube side overnight. The

immobilization procedure was repeated for both sets of where Vi is the volumetric permeation rate of species i,
fibers to produce leak-free hollow fiber modules. Im- ∆pi is the partial pressure difference of species i across
mobilization using the pure dendrimer liquid is poten- the membrane, and At is the total membrane area. The
tially much simpler. true permeance of the species (Qi/tm)true is obtained from

() ()
3.2. Measurement of the Equilibrium Water
Concentration in Dendrimer and Glycerol. Be- Qi Qi τm
cause of its hygroscopic nature, fresh dendrimer liquid ) (5)
tm true tm eff m
absorbs water from ambient air when exposed to it. If
the contact time between the dendrimer liquid and The permeability Qi of a particular gas species through
ambient air is sufficient, it can be assumed that an the ILM is obtained by multiplying its true permeance
equilibrium distribution of water has been reached through the ILM and the membrane thickness:
between the dendrimer and ambient air. The change of

()
weight of the dendrimer + water under different RHs
Qi
was recorded using an electronic balance (model PB 303, Qi ) tm (6)
Mettler-Toledo). The humidity in the balance environ- tm true
ment was monitored by a humidity probe (model HMP
32UT, Vaisala, Woburn, MA). The measurements showed The separation factor of species i with respect to species
that this technique can give reasonably reproducible j, Ri/j, is defined by
results. For comparison, the water uptake by glycerol
was also measured. These measurements were done Qi (Qi/tm)eff (Qi/tm)true
independently of the data reported earlier21 and covered Ri/j ) ) ) (7)
a wider range of RH conditions. Qj (Qj/tm)eff (Qj/tm)true

In the case of hollow fiber modules, the partial
pressure differences of the species and the membrane
area for transport are based on logarithmic mean
averages. The logarithmic values of the total membrane
area and partial pressure difference are calculated
according to
Ain - Aout
Alm ) (8)
ln(Ain/Aout)
∆pi,in - ∆pi,out
∆pi,lm ) (9)
ln(∆pi,in/∆pi,out)
Here Ain and Aout are the total membrane areas based
on the inside and outside diameters of the fiber; ∆pi,in
and ∆pi,out refer to the partial pressure difference of
species i at the inlet and outlet of the module, respec-
tively, for the calculation of the logarithmic partial
pressure difference. The subsequent reported values of
permeances are denoted with subscript lm to highlight
this aspect of the calculation.
Gas permeances are reported in units of cm3(STP)/
cm2‚s‚cmHg. Wherever convenient, gas permeances are
reported in units of GPU, which is equivalent to 10-6
cm3(STP)/cm2‚s‚cmHg. Gas permeabilities are reported
in units of barrer, which is 10-10 cm3(STP)‚cm/cm2‚s‚
cmHg.
4. Results and Discussion
Dendrimer-based liquid membranes are unique in
terms of their preparation and behavior. The generation
0 PAMAM dendrimer was often used in its pure form
without any additional solvent as a facilitated transport
liquid membrane. For convenience, whenever a genera-
tion 0 dendrimer is used in its pure form without any
solvent as the ILM, the ILM is referred to as a pure
dendrimer ILM.
4.1. Effect of Glycerol on the Performance of
Dendrimer-Based Liquid Membranes. Kovvali et
al.1 observed that pure dendrimer liquid membranes
tend to lose their ability to function as CO2-selective
molecular gate vis-à-vis N2 when the feed side inlet RH
was reduced. However, when a significant amount of
glycerol was added to dendrimer, the liquid membrane
tended to be stable and essentially leak-free even under
dry feed gas conditions. They postulated that glycerol
present in the intramolecular and intermolecular spaces
prevented the leakage of N2 in the absence of water in
the gas streams. However, the addition of glycerol has
other implications on the ILM performance. They ob-
served that glycerol in a 44% (1 M) dendrimer mem-
brane did not have much contribution to CO2 perme-
ation. However, the selectivity of the ILM for CO2 over
N2 decreased drastically from over 18000 to less than
5000. This was expected. A nonselective, nonfacilitating
liquid like glycerol will reduce the highly charged ionic
environment that a pure dendrimer liquid provides,
resulting in much higher N2 transport. Is it, therefore,
possible that a minimum amount of glycerol added to
the pure dendrimer liquid could retain the molecular
gating behavior of pure dendrimers while increasing its
effective operating range of feed RH? This idea was
explored by adding 25% glycerol to the dendrimer liquid.
Figure 2 illustrates the results for an ILM containing
75% generation 0 dendrimer in a glycerol solution in
Ind. Eng. Chem. Res., Vol. 40, No. 11, 2001 2505
Figure 2. Variation of permeance of carbon dioxide and separa-
tion factor with partial pressure difference of carbon dioxide in
hydrophilic PVDF substrates for different dendrimer concentra-
tions in the ILM.
the hydrophilized PVDF substrate exposed to a feed gas
having 100% RH. For comparison, the behaviors of pure
dendrimer and 44% dendrimer in glycerol ILMs1 are
also plotted. The substrate membranes were soaked in
the dendrimer solutions for 8 h, and a vacuum was
applied for about 5 h to remove any absorbed moisture.
The removal of absorbed moisture proved to be impor-
tant for successful operation of the ILM under dry or
partially humid feed conditions. The ILM formed
with a 44% (1 M) dendrimer solution in glycerol without
removing any absorbed moisture tended to perform
poorly under dry feed gas conditions with a high N2
permeability of 1260 barrer. However, the N2 perme-
ability dropped significantly even under dry feed gas
conditions to about 8 barrer when the ILM was formed
by vacuuming the solution for about 5 h. The highest
CO2 permeability observed was about 5400 barrer for a
0.5% CO2 feed gas.
The sorbed water by glycerol, when left unremoved,
would be essentially a third component in the ILM.
Under dry feed gas conditions, this water would pre-
sumably evaporate, providing channels for excessive N2
transport. Hence, removal of sorbed water is considered
critical for preventing excess N2 transport. However,
once feed-side humidification was started, N2 perme-
ability dropped to about 1 barrer because of the salting
out effect and creation of a highly ionic environment in
the ILM. Because of humidification of the feed side, CO2
facilitation occurs and CO2 permeability increased
drastically.
The 75% dendrimer ILM achieved a separation per-
formance much closer to the pure dendrimer ILM than
44% dendrimer ILM. The highest selectivity obtained
for a 0.76% CO2-N2 gas mixture (∆pCO2 of 0.82 cmHg)
was about 16 300 (compare 18000 for a pure dendrimer
at a lower ∆pCO2 of 0.27 cmHg). The corresponding CO2
and N2 permeabilities were 3200 and 0.19 barrer,
2506 Ind. Eng. Chem. Res., Vol. 40, No. 11, 2001
Table 2. Performance of Dendrimer Membranesa at Low CO2 Concentrations (Feed CO2 Concentration: ∼0.5%)
CO2 effective permeance,
carrier GPU
75% dendrimer-balance glycerol 8.58
PAMAM pure dendrimer, generation 0 9.8
44% dendrimer-balance glycerol 10.2
2.25 M glycine sodium salt-glycerol 27.5
1 M Na2CO3-glycerol 8.4
plasma-grafted AA with EDA 100
a Substrate: hydrophilized PVDF.
respectively. The increase in nitrogen permeability from
an average value of 0.17 barrer for pure dendrimer ILM
to 0.19 barrer is not very significant. This indicates that
the addition of small amounts of glycerol did not affect
the CO2-selective molecular-gating behavior of PAMAM
dendrimers. It is conceivable that glycerol present in
small amounts (25%) in the ILM was able to occupy
intermolecular and intramolecular spaces of dendrimer.
However, the amount of glycerol added (25%) was not
in excess to disrupt the highly charged environment that
was created by the pure dendrimer liquid. This es-
sentially ensures that the N2-blocking ability of the pure
dendrimer liquid is retained. Note that the 44% den-
drimer liquid has a QN2 of 0.94 barrer (pure glycerol QN2
is 2.85 barrer, while pure dendrimer QN2 is 0.17 barrer).
It should be mentioned that nitrogen was detected by
the GC in only a few experiments for 75% dendrimer
ILM even though three test cells were used in series
for the experiments.
4.2. Comparison of the Performance of Den-
drimer Membranes. It would be useful to compare the
performances of the dendrimer-based ILMs in PVDF
substrates with some of the promising membranes in
the literature at both low and high carbon dioxide
partial pressures. The carbon dioxide permeances for
pure dendrimer ILMs were lower compared to those
obtained by glycine sodium salt in glycerol ILMs22 in
PVDF substrates. The selectivities, however, were about
4-5 times those obtained for glycine sodium salt-
glycerol ILM. This could be due to a lower mobility of
dendrimer-carbon dioxide complexes. The molecular
weight of dendrimer of generation 0 is 518, whereas the
molecular weights of glycine salt and glycerol are about
100. Hence, it can be expected that the diffusivities of
dendrimer and the dendrimer-CO2 complex could be
much less than those in the glycine salt-glycerol
system. Another major reason for reduced carbon diox-
ide permeances in pure dendrimer ILMs is due to
reduced solubilities of all gas species due to the salting
out effect. There are no direct data available for
solubilities of carbon dioxide and other gases in pure
dendrimer solutions of different generations. However,
it can be inferred from aqueous amine solutions that
increased amine concentrations lower carbon dioxide
loading per mole of amine at the same carbon dioxide
partial pressure. For example, at a carbon dioxide
partial pressure of 1 kPa (0.75 cmHg), a 0.5 M trietha-
nolamine (TEA; corresponding to 7.37 wt %) aqueous
solution can be loaded up to about 0.8 mol of CO2/mol
of TEA. As the TEA concentration increases, the CO2
loading decreases. At 5 M TEA concentration (corre-
sponding to 67 wt %), the CO2 loading is reduced to
about 0.1 mol of CO2/mol of TEA.29,30
Table 2 compares the performances of dendrimer-
based membranes at a low CO2 feed gas concentration
of around 0.5%. At such low carbon dioxide partial
pressures, the pure dendrimer membranes are highly
CO2 permeability,
barrer RCO2/N2 ref
3200 16300 current work
3600 ∼18000 1
3800 3000 1
10100 g4000 22
3100 1400 21
∼4000 4000 14
selective for CO2 over N2. The pure dendrimer mem-
branes offer about the same effective permeance of CO2
as 1 M sodium carbonate-glycerol ILM but are about
13 times more selective for CO2. Similarly, glycine
sodium salt-glycerol membranes offer the tradeoff of
higher effective permeance for CO2 and about one-fourth
of the pure dendrimer membrane selectivity for carbon
dioxide. The presence of a small amount of glycerol in
the dendrimer (25%) liquid does not affect either the
permeances or RCO2/N2 very much. However, a further
increase in the glycerol content in the ILM reduces the
selectivity of the ILM for carbon dioxide without offering
any significant advantages in terms of carbon dioxide
permeance.
The plasma-grafted thin membrane soaked with
EDA19 offers by far the highest effective permeance for
carbon dioxide of 100 GPUs and a selectivity that is
comparable to or somewhat less than that of glycine
sodium salt-glycerol ILM. It should be stressed that
these thin membranes were tested under humidified
conditions on both the feed and sweep sides of the
membranes. There was no study performed on the loss
of EDA with time. EDA is a volatile and toxic amine,
and it could lead to process stream contamination.
However, dendrimer membranes have permeabilities for
carbon dioxide similar to those of the above membrane
at these CO2 concentrations. This confirms that the
dendrimer membranes facilitate carbon dioxide on par
with other facilitated transport membranes, whereas
the high selectivities are mainly due to the high density
of charged functional groups present under humidified
feed conditions.
At higher partial pressures of carbon dioxide, the
selectivity of dendrimer membranes is comparable to
the highest levels of selectivity reported in the literature
by polyelectrolyte salt membranes.17 Table 3 sum-
marizes the comparison of dendrimer-based ILMs with
various membranes studied in the literature at higher
feed CO2 concentrations. The selectivity and permeances
offered by the polyelectrolyte membranes were achiev-
able within a narrow range of the feed and sweep RHs.
It should also be mentioned that making a pinhole-free
membrane from these salts is difficult.18
A poly(ethylene oxide)-containing and crosslinked
polymer film31 could provide from a dry gas a CO2
permeability as high as 250 barrer and a RCO2/N2 of 60
based, however, on pure gas permeabilities. Poly(eth-
yleneimine)/poly(vinyl alcohol) blend membranes20 pro-
vide about 5 times higher permeance than dendrimer
membranes, but the selectivity of the blend membranes
for CO2 was an order of magnitude lower than that of
dendrimer membranes. This indicates that the den-
drimer membranes are in the right direction for com-
mercialization of membrane processes for CO2 removal
from flue gases, because Haraya et al.32 indicated that
a RCO2/N2 of more than 210 is required to recover CO2
efficiently by a single-stage permeator. On the other

Table 3. Performance of Dendrimer Membranesa at High Concentrations of CO2 in the Feed Gas
CO2 effective permeance,
carrier ∆pCO2
75% dendrimer-balance glycerol 26
PAMAM dendrimer, generation 0 30
44% dendrimer-balance glycerol 32
2.25 M glycine sodium salt-glycerol 30
1 M Na2CO3-glycerol 59
polyelectrolyte membrane 36
PEO-containing polymer c 250
PEI/PVA blend membrane 30
a Substrate: hydrophilized PVDF. b The range based on the range for thickness of 10-20 µm. Membrane tortuosity and porosity are
not accounted for in the calculation. c Pure gas permeability.
Figure 3. Effect of the feed side average RH on dendrimer ILM
performance. Feed CO2 concentration: 0.27-1.03 cmHg.
hand, the pure dendrimer membranes spanning the full
thickness of the thick PVDF substrates offer signifi-
cantly lower effective permeance for carbon dioxide. At
high feed CO2 concentrations, both 75% dendrimer and
44% dendrimer solutions in glycerol behave in a manner
similar to that for low CO2 feed concentrations.
4.3. Effect of the Feed Gas RH on the ILM
Performance. The facilitation reactions of amines and
carbonates with CO2 require the presence of water. Most
studies in the literature on the carbon dioxide reaction
with the amines were carried out in an aqueous me-
dium. However, glycerol-based ILMs21-23 employed
glycerol as the solvent for the carrier instead of water.
It was found that an absence of water vapor in the feed
stream resulted in a complete loss of facilitation and
drastically reduced the permeabilities for both nitrogen
and carbon dioxide. In the case of pure dendrimer
membranes, water is also required for creating a
charged environment for effective rejection of nitrogen
for achieving high CO2-N2 selectivities in addition to
implementing the CO2 facilitation reactions.
Figure 3 shows the effect of a variation of the average
feed side RH, RHf,avg (average of feed inlet and feed
outlet values), on the separation behavior of dendrimer-
based ILMs in a PVDF substrate on a semilog scale.
The feed inlet RH was adjusted by mixing a completely
humidified feed stream with a dry feed stream before
it entered the cell. For a pure dendrimer ILM, a
reduction in the RH of the feed stream increased
nitrogen permeation tremendously, resulting in a loss
of selectivity by the ILM for carbon dioxide over
nitrogen. It appears that, below a critical RHf,avg value
Ind. Eng. Chem. Res., Vol. 40, No. 11, 2001 2507
CO2 permeability,
GPU barrer RCO2/N2 ref
0.8 300 760 current work
0.4 150 720 1
0.64 240 250 1
1.1 400 200 22
2.5 100 21
9.0 90-180b 835 17
60 31
2.0 ∼440 70 20
of around 81%, the CO2-selective gating ability of the
pure dendrimer ILM is reduced substantially. However,
the selectivity was regained as the feed was completely
humidified. It should be stressed that, in all of these
experiments, dry helium was used as the sweep gas. To
observe the effect of an absence of humidity in the feed
stream on the ILM performance, the humidification of
the feed gas stream was stopped in between. The
nitrogen permeance of the ILM increased drastically,
resulting in a CO2/N2 separation factor of around 5.
However, as the feed gas humidification was started
again, the performance of the ILM returned to its
original values of high CO2-N2 selectivity and very low
N2 permeability. For a completely humidified feed inlet
stream, the feed exit RH is usually around 70%.
However, it depends on the gas flow rate.
As shown in Figure 3, the addition of a small amount
of glycerol to the pure dendrimer liquid (75% den-
drimer-25% glycerol) improves the ability of the liquid
membrane to withstand lower feed inlet RH (and hence
lower average feed side RH) before a significant increase
in N2 transport occurs. Up to about a RHf,avg of 50%,
the 75% dendrimer membrane blocks N2 transport very
effectively. For example, for RHf,avg of ∼50-55%, no N2
could be measured in the GC. (However, the CO2
permeance values at these higher RHf,avg’s for these
membranes are somewhat lower.) Glycerol sorbs more
water than pure dendrimer at a given RH (as will be
discussed later). Hence, addition of 25% glycerol to
dendrimer liquid maintained a higher level of water
content in the liquid membrane compared to that in the
pure dendrimer liquid. This maintains the charged
environment even at lower RHf,avg values. Thus, as far
as CO2 selectivity is concerned, the 75% dendrimer
membrane behaves essentially the same as the pure
dendrimer membrane over a larger RHf,avg.
Table 4 summarizes the performances of dendrimer-
based ILMs under dry and completely humid feed gas
conditions. Data obtained for pure glycerol ILM under
similar conditions21 are also presented for comparison.
It should be stressed that, in all of these experiments,
the sweep gas was dry helium. Pure glycerol ILM has a
CO2 permeability of 5.62 barrer under dry feed gas
conditions with a RCO2/N2 of 1.5. When 100% RH feed
gas was introduced, CO2 transport is facilitated 20
times, resulting in a RCO2/N2 of around 39, which is close
to that of water. For pure dendrimer membranes, under
completely humidified feed conditions, the CO2 perme-
ability was 3600 barrer with a RCO2/N2 of 18000 for a
∆pCO2 of 0.27 cmHg. However, the significant feature
of the pure dendrimer ILM was that its N2 permeability
was about 0.17 barrer. This value was almost 15 times
lower than that of pure glycerol ILM; the pure den-
2508 Ind. Eng. Chem. Res., Vol. 40, No. 11, 2001

Table 4. Performance of Dendrimer-Based ILMsa under Dry and 100% Humid Feed Gas Conditions
dry feed gas 100% RH feed gas
QCO2, QN2, QCO2, QN2,
ILM barrer barrer RCO2/N2 barrer barrer RCO2/N2
pure glycerolb 5.62 3.79 1.48 111 2.85 39
44% (1 M) dendrimer (generation 0) in glycerolc 17.0 7.54 2.25 900 0.94 900
75% dendrimer in glycerold 5800 860 6.7 3200 0.19 16300
pure dendrimer (generation 0)e 4700 930 5.05 3600 0.17 ∼18000
a Substrate: hydrophilized PVDF. b Reference 21. c Feed 5.2% CO -balance N mixture at 7 psig of feed pressure. d Feed 0.76% CO2-
2 2
balance N2 mixture at 12 psig of feed pressure. e Feed 0.5% CO2-balance N2 mixture at 3 psig of feed pressure.

drimer ILM functions as a CO2-selective molecular gate

in blocking the nitrogen transport.
Under completely dry feed gas conditions, the per-
meabilities of 75% dendrimer membrane for CO2 and
N2 were 5800 and 860 barrer, respectively. These values
were close to those obtained with pure dendrimer
membranes under dry feed gas conditions. This was
expected. It appears that the amount of glycerol added
was not sufficient to penetrate into all of the intermo-
lecular and intramolecular spaces of the dendrimer
liquid; therefore, the CO2 as well as N2 permeances were
very high under dry feed gas conditions. The 44%
dendrimer-balance glycerol ILM under completely dry
feed gas conditions has CO2 and N2 permeabilities of
17 and 7.54 barrer, respectively, with a very low
selectivity for carbon dioxide over nitrogen. Addition of
a significant amount of glycerol to the pure dendrimer
has therefore the effect of preventing the membrane
from having very high nitrogen permeability under dry
feed conditions. In the presence of humidified feed gas,
carbon dioxide transport was facilitated about 52 times,
while the nitrogen permeation rates were reduced by 8
times for the 44% dendrimer membrane. It should be
mentioned that the data presented in the table were Figure 4. Pure dendrimer ILM performance in hydrophilized
obtained using a 5.2% CO2-balance N2, where the Celgard 2500 substrate.
effects of carrier saturation were evident in the low
carbon dioxide permeabilities. CO2 effective permeances were higher at 1.68 GPU (at
ILMs with thicknesses lower than that of the PVDF 4.95 cmHg) and 0.96 GPU (at 9.87 cmHg) with hydro-
substrate would increase CO2 permeances at the ex- philized Celgard substrates compared to 0.97 GPU (at
pense of a simultaneous decrease in RCO2/N2 as in any 4.48 cmHg) and 0.82 GPU (at 8.95 cmHg) with PVDF
facilitated transport membrane. However, because the substrates. This is encouraging because the porosity of
present ILMs possess exceptionally high selectivities for the Celgard substrate is only about 65% that of the
CO2, a tradeoff between increased CO2 permeances with PVDF substrate. However, the N2 permeabilities were
thinner ILMs and the resulting lower RCO2/N2 is expected 3-4 times larger; therefore, only one test cell was
to be a viable approach. Because of the lower per- needed in these experiments to detect N2 in the sweep
meances for carbon dioxide observed in pure dendrimer gas. The increased nitrogen permeabilities are due to
liquid membranes, there is a need to improve the CO2 inherent or residual hydrophobicity of the developmen-
permeances while retaining the high selectivities from tal Celgard polypropylene substrate. This was also
pure dendrimer solutions. One way to achieve this observed by Chen et al.22 The highest separation factor
objective is to use thinner substrate membranes. Hy- obtained for a feed gas mixture of 0.5% CO2-balance
drophilized Celgard 2500 may be a suitable substrate N2 was close to 3900, and carbon dioxide permeability
having a thickness of 25 µm compared to the 100 µm was 1000 barrer.
thick PVDF substrate. However, Celgard 2500 has a 4.5. Equilibrium Water Uptake by the Den-
lower porosity, which reduces the effective permeances. drimer Liquid. It is necessary to compare the equi-
4.4. Hydrophilized Celgard 2500 Substrate. Fig- librium water uptake by the dendrimer liquid and
ure 4 shows the variation of carbon dioxide effective glycerol. Chen et al.21 measured the equilibrium water
permeance and separation factor for a hydrophilized concentration in glycerol in the ambient RH range of
Celgard 2500 membrane containing pure dendrimer 48-85%. The equilibrium water uptake by a generation
liquid. The data were obtained using a single cell having 0 dendrimer liquid was measured here in the ambient
a membrane area of 12.56 cm2. The feed gas was RH range of 17-75%. The water uptake by glycerol
completely humidified; the sweep gas was dry helium. liquid was also measured in this RH range; they were
CO2 effective permeances observed as a function of found to be consistent with the reported data.21 Figure
∆pCO2 are close to those observed in the PVDF substrate. 5 shows the variation of the water content in both
For example, the CO2 effective permeance for a ∆pCO2 dendrimer and glycerol as a function of the ambient RH.
of 1.86 cmHg was 4.27 GPU compared to 2.29 GPU in The measurements of the water uptake did not show
the PVDF substrate at ∆pCO2 of 1.7 cmHg. Similarly, any signs of hysteresis with the direction of RH change.

Figure 5. Equilibrium sorption of water by dendrimer and
glycerol.
Figure 6. Performance of pure dendrimer ILMs in poly(acryloni-
trile) PAN fiber substrate.
For all RH levels studied here, glycerol holds much more
sorbed water than the pure dendrimer liquid. This
phenomenon explains the nitrogen rejection behavior
of the pure dendrimer liquids at high feed inlet RHs
and poor selectivities observed at low feed side RHs.
While pure dendrimer liquids under highly humidified
feed gas conditions can presumably sorb enough water
to create a highly charged environment, lower feed side
humidity conditions will not be able to do so effectively.
This also explains why the performance of a 75%
dendrimer membrane decreases with a decrease in the
feed RH much more slowly than that of a pure den-
drimer membrane (Figure 3).
4.6. Performance of Dendrimer Membranes in
Hollow Fiber Substrates. A generation 0 PAMAM
dendrimer was immobilized in two types of hydrophilic
hollow fibers potted in a module. Completely humidified
feed gas was introduced in all experiments from the
lumen side while the sweep gas (dry helium) was passed
on the shell side. Figures 6 and 7 show the effective CO2
permeance and the RCO2/N2 for the PAN and polysulfone
fiber modules, respectively. Logarithmic mean average
values for the membrane areas and the partial pressure
differences across the ILM were employed for calculat-
ing the permeances of both species.
The experiments with a PAN fiber module were done
in both cocurrent and countercurrent modes for trans-
membrane pressure differences up to 139 cmHg (1.8
Ind. Eng. Chem. Res., Vol. 40, No. 11, 2001 2509
Figure 7. Performance of pure dendrimer ILMs in polysulfone
fibers.
atm) on the feed side. Higher permeances for both
carbon dioxide and nitrogen and separation factors were
observed in the countercurrent mode. However, higher
water fluxes (not reported here) were observed in the
countercurrent mode of operation, resulting in lower
feed side exit RHs. The highest CO2 effective permeance
obtained with PAN fibers was about 1.3 × 10-5 cm3/
cm2‚s‚cmHg, resulting in a separation factor of 1300 for
a ∆pCO2 of 0.28 cmHg when the feed and sweep gases
were flowing countercurrently. The experiments with
polysulfone fiber modules were conducted only in the
cocurrent mode. The effective permeances and water
fluxes observed were higher compared to those observed
in the PAN fiber module at comparable ∆pCO2 values.
This is expected because the PAN fibers, used for
ultrafiltration, have a lower porosity whereas polysul-
fone fibers, used for microfiltration, have a significantly
higher porosity. The highest effective permeance for the
polysulfone fibers was about 9.7 × 10-6 cm3/cm2‚s‚cmHg
for a feed CO2 partial pressure of 0.45 cmHg.
Even though the effective permeances for carbon
dioxide in these hollow fiber modules were comparable
to those obtained in flat membrane ILMs, the effective
permeances for nitrogen are, in general, higher in the
case of both hollow fiber modules. The effective per-
meance of nitrogen through the PAN module was
between 6.8 and 9.3 × 10-9 cm3/cm2‚s‚cmHg. These
permeances for pure dendrimer membranes were 2-3
times higher than those obtained with sodium carbon-
ate-glycerol ILMs in the PAN fibers.23 Similarly, the
pure dendrimer ILMs in polysulfone hollow fibers have
a nitrogen effective permeance in the range of (3.9-9)
× 10-9 cm3/cm2‚s‚cmHg. These values are comparable
to those obtained in polysulfone fibers with sodium
carbonate-glycerol ILMs.23
The discrepancy in N2 permeation rates between
ILMs in hollow fibers and flat membranes is expected
because of the differences in the procedure for forming
the dendrimer ILMs in flat membranes and hollow
fibers and the very nature of dendrimer liquids. The
dendrimer liquid was introduced as a solution in
methanol into the hollow fibers, and methanol was
subsequently evaporated by applying a mild vacuum
(12.7-38.1 cmHg) from the shell side, leaving pure
dendrimer behind in the pores of the hollow fibers. The
dendrimer in a methanol solution was applied at
atmospheric pressure from the lumen side because
application of higher pressures may result in a loss of
2510 Ind. Eng. Chem. Res., Vol. 40, No. 11, 2001
Figure 8. Effect of the transmembrane pressure difference on
QCO2 in pure dendrimer ILMs.
the dendrimer to the shell side. It is possible that some
of the fine pores of the hollow fibers may not be filled
with dendrimer but will permeate some nitrogen, re-
sulting in a loss of selectivity for carbon dioxide vis-à-
vis N2. The reason could also be the inherent hydro-
phobic nature of the substrates. This is particularly true
in the case of PAN fibers which were hydrophilized,
because poly(acrylonitrile) is inherently hydrophobic.
Better techniques of hydrophilization of hydrophobic
fibers to ensure uniform and permanent hydrophiliza-
tion could improve this situation. Better approaches for
immobilization of the dendrimer in the pores should
result in higher separation factors by hollow fiber
membrane ILMs. An additional reason for higher N2
permeance is the somewhat lower exit gas RH on the
feed side compared to that for flat membranes which
will increase the N2 permeance.
4.7. Effect of the Transmembrane Pressure Dif-
ference. ILMs consist of liquids immobilized in the
pores of the substrates. The maximum transmembrane
pressure difference (TMP) for an ILM varies inversely
with the pore size of the substrate and directly with the
surface tension of the ILM liquid. For any practical
application, the ILM should be able to withstand the
transmembrane pressure difference. The PVDF film
used here has a water bubble point pressure of 4.8 atm
(360 cmHg).21 Figure 8 shows the variation of carbon
dioxide permeability for different transmembrane pres-
sures for both hydrophilic PVDF and hydrophilized
Celgard 2500 based pure dendrimer ILMs. The PVDF
membranes were not tested for TMPs higher than 0.68
atm (51.7 cmHg). The hydrophilized Celgard 2500
membranes were tested up to a TMP of 1.7 atm (120
cmHg). It should also be noted that the PVDF membrane-
based ILM was tested with a 0.5% CO2-N2 feed gas
mixture. The steep behavior of the ILM performance
with transmembrane pressure is due to the strong
dependence of the carbon dioxide permeability on CO2
partial pressure differences at low CO2 concentrations
in the feed gas mixtures. This trend can be seen in
Figure 8. Data for Celgard 2500 membrane were
obtained using a 5.2% CO2-N2 feed gas mixture where
the effect of facilitation will not be very evident at the
relatively higher ∆pCO2’s.
4.8. Dendrimer Liquid Membranes for Separa-
tion of CO2/O2 Mixtures. Table 5 presents a limited
amount of data on the performance of the generation 0
dendrimer-based liquid membranes for separation of
carbon dioxide/oxygen mixtures using relatively low
Table 5. Gas Transport of Dendrimer-Based ILMs for
CO2-O2 Mixtures
ILM ∆pCO2 (QCO2/tm)eff (QO2/tm)eff QCO2 QO2 RCO2/O2
pure generation 0 0.74 5.34 2.35 × 10-32000 0.87 2300
75% generation 0 0.56 11.8 1.16 × 10-2 4400 4.28 1000
44% generation 0 0.99 7.59 8.41 × 10-3 2800 3.10 920
∆pCO2’s of up to 0.99 cmHg. At a ∆pCO2 of 0.74 cmHg,
the pure dendrimer ILM has a QCO2 of 2000 barrer and
a RCO2/O2 of 2300. The carbon dioxide permeability was
comparable to that obtained using a humidified CO2-
N2 gas mixture under similar CO2 partial pressures. The
permeability of oxygen through the pure dendrimer ILM
was about 0.87 barrer compared to the nitrogen perme-
ability of 0.17 barrer. This could be partly because of a
significantly higher solubility of oxygen in water com-
pared to nitrogen. However, the fivefold difference in
O2 and N2 permeabilities cannot be due to higher
solubility of oxygen in water alone. Additional experi-
ments are needed to clarify this aspect. Because the feed
gas stream was completely humidified, water sorbed by
the dendrimer liquid yielded higher transport rates for
oxygen than for nitrogen. The addition of glycerol to a
generation 0 dendrimer increases the permeabilities of
both carbon dioxide and oxygen with a reduction in the
selectivity of the ILM for carbon dioxide over oxygen to
about 1000. This trend was seen with both 75% den-
drimer and 44% dendrimer ILMs. The presence of
glycerol in the liquid membrane increases the effective
permeance of oxygen more than the increase in the
effective permeance of carbon dioxide for similar carbon
dioxide partial pressures. As a result, the CO2/O2
separation factors are lower for dendrimer-glycerol
mixture ILMs than for pure dendrimer liquid mem-
branes.
5. Conclusions
From the above discussion, the following conclusions
can be drawn:
(1) The CO2-selective molecular gating ability of pure
dendrimer liquid membranes was preserved over a wide
range of feed gas RHs by adding 25% glycerol to the
dendrimer liquid. The addition of small amounts of
glycerol does not seem to affect the CO2 permeances for
the CO2 partial pressure range studied.
(2) The dendrimer-based liquid membrane provides
the highest selectivities for CO2-N2 separation both at
low and high ∆pCO2’s. There is a need to improve the
CO2 permeances, particularly at high CO2 partial pres-
sures.
(3) Hydrophilized Celgard membranes having a thick-
ness lower than that of PVDF substrates marginally
improved the CO2 effective permeances. This is encour-
aging because the porosity of the developmental hydro-
philized Celgard substrate is only about 65% of that of
the PVDF substrate.
(4) The dendrimer liquid membranes were able to
withstand TMPs of up to 52 cmHg in a 0.1 µm PVDF
substrate and 120 cmHg in a 0.08 µm hydrophilized
Celgard substrate. Studies were not made at higher
TMP values.
(5) The water uptake of pure dendrimer liquids was
experimentally determined and compared with pure
glycerol liquid at different ambient RHs. Dendrimer
liquid absorbs less water than glycerol at comparable
ambient RH values.

(6) The use of hollow fiber substrates for containing
the ILMs was explored with two types of hollow fibers.
Their performances were consistent with the observa-
tions made with glycerol-based ILMs conducted sepa-
rately.
Acknowledgment
We acknowledge the support from the Membrane
Separations and Biotechnology Program at NJIT. We
thank Celgard LLC, Charlotte, NC, for providing their
developmental hydrophilized Celgard 2500 films. A.S.K.
appreciates the support of Dr. Hua Chen on various
aspects during the present work.
Nomenclature
A ) membrane area
pi ) partial pressure of species i
P ) pressure
Qi ) permeability coefficient
RH ) relative humidity
RHf,avg ) average of feed inlet and outlet RHs
tm ) membrane thickness
Vi ) volumetric permeation rate of species i
Subscripts/Superscripts/Greek Letters
eff ) effective
i, j ) species
in ) inlet condition
lm ) logarithmic mean
out ) outlet condition
t ) total
true ) true
Ri/j ) separation factor of species i over j
m ) porosity of the substrate
τm ) tortuosity of the substrate
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Received for review December 5, 2000
Revised manuscript received March 14, 2001
Accepted March 15, 2001
IE0010520