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Ali Rostami (922474003)

Introduction
Separation of CO2 from different gas streams, especially
from biogas and flue gases.

Among many possibilities suggested for CO2 capture,
membrane separation is mentioned frequently, recently
also using ionic liquid membranes.

Selectivity of ionic liquid membranes is strongly
determined by different solubility of separated gases in
ionic liquids.
evaluates the performance of ionic liquid membranes for
permeation of pure gases and separation of their binary
mixtures under different experimental conditions.

Two ionic liquids; 1-ethyl-3-methylimidazolium
bis(trifluormethylsulfonyl) amide [emim][Tf2N] and
1-ethyl-3-methylimidazolium dicyanamide [emim][dca],
supported in porous PVDF were used.

membranes were prepared by immersing porous PVDF
into the chosen liquids under vacuum.
Ionic liquids performance
Similarly to membrane operations employing nonporous
membranes for gas separation, the solution-diffusion
model can be used for the basic description of the gas
transport through ionic liquid membranes (ILM).

Permeation flux intensity through the membrane, Ni, can
be expressed as the following equation:



where:
p
if
: the partial pressure of the component in the feed stream

p
ip
: the partial pressure of the component in the permeate
stream


P
i
: permeability coefficient (defined from the solution-
diffusion model as the product of solubility, S
i
, and
diffusivity ,D
i
)

:


Available models of gas solubilities in ionic liquids are
based on the regular solution theory. It may be simplified
into the following equation:



where and are experimentally determined constants
and V
2
is the molar volume of the ionic liquid.
A different approach to modeling of the solubility of gases
in imidazolium based ionic liquid was introduced by
Shannon et al. based on the fractional free volume of the
ionic liquid :



where D is an asymptotic value of Henrys constant at large
molar volumes and c
*
was explained as a transition point
between cation and anion chain interaction with the gas.
The ratio c
*
/V
2
for calculation of the free volume in ionic
liquids.
Morgan et al. suggested an empirical equation for the
diffusion coefficient based on the viscosity (cm s
-1
) of the
ionic liquid and on the molar volume (cm
3
mol
-1
) of the
solute:

where
2
is the viscosity of the ionic liquid and V
1
is the
molar volume of the solute (diffusing gas) estimated by
the following correlation with the critical volume of the
gas:



Another model was suggested by Hou and Baltus :




An equation for the estimation of CO
2
permeability in ionic
liquids was suggested by Scovazzo . It is based on the
molar volume of the ionic liquid, V
2
:




The permeability of immobilized liquid membranes is a
result of the combination of the properties of the chosen
liquid and those of the used support. For this reason the
characteristics of the support must be taken into account,
namely its porosity and tortuosity.

Tortuosity : ratio of the real length of the pore (C) and the
shortest distance of its ends.The shortest distance of the
ends of the pore is the membrane thickness (l) :


Two different approaches to estimation of tortuosity
described in literature:
The first approach is based on the calculation using Mackie
and Meares correlation :


where is the porosity of the support.

The second approach is based on data reported by Scovazzo
et al.


Where

D
ef
: effective diffusion coefficient

D
0
: the diffusion coefficient of gas in a pure liquid

When assuming the validity of the solution diffusion
model (Eq.(2)), where the solubility of a particular gas in
the chosen liquid is supposed to be constant, the
permeability of the pure liquid (P
i0
) from permeability of
the liquid membrane can be (P
ief
) expressed as follows :

Two different data sets of porosity and tortuosity were
used.(Table 1). Set no. 1 contains the porosity given by the
manufacturer of the support (Millipore Inc.) and the
tortuosity calculated with the Mackie and Meares
correlation. Set no. 2 contains the porosity and tortuosity
estimated by Scovazzo et al.

In this work two ionic liquids [emim][Tf
2
N] and
[emim][dca] with the most convenient properties towards
CH
4
/CO
2
separation were used. Table 2 presents the
available literature data about these ionic liquids.
Model of ionic liquid membrane
A model of mass transport through the membrane in the
permeation cell was developed. The model describes a
mass balance for each involved gas species on both sides of
the membrane and assumes a steady state. The scheme of
the balance is added in Fig. 1.
A radial flow profile is assumed, with emission of the feed
gas at the center and collection of the retentate at the
perimeter. At the downstream side the sweeping gas is
inserted from the center and the permeate is collected at
the perimeter.
There are two equations for each gas species (in this case
CO
2
, CH
4
, N
2
), one for the retentate side and one for the
permeate side of the membrane cell. Thus there are six
equations in total. The balance equations for the gas i (i =
CO
2
, CH
4
or N
2
) have the following form:



where n
i,1
and n
i,2
is the molar flow rate of the gas i in the
gas stream on the retentate (index 1) and on the permeate
side (index 2) of the membrane in a direction parallel to
the membrane surface,n
i
*
is the molar flow rate of i
through the membrane, i.e. perpendicular to the
membrane surface.
Defining K
i
as the mass transfer coefficient of species i
through the membrane, then:


is the mass transfer rate of gas i through an infinitesimal
membrane surface area dA perpendicular to the
membrane surface.
p
i
is a local difference of gas i partial pressures on both
sides of the membrane (driving force for the mass transfer
through the membrane).

Combining (13) and (14) and writing them in 1D cylindrical
coordinates (axial symmetry), we obtain:


The (2rdr) term is the membrane surface area dA between
radial coordinate r and r + dr. The d
ni,1
, d
ni,2
(mol/s) are the
molar flow rate changes of the compound i on the
retentate (1) and permeate (2) side of the membrane in the
radial direction over the membrane surface area (2rdr).


Note: dn
i,1
= dn
i,2

The local partial pressure difference p
i
is defined as:



where p
1tot
is a total pressure on the retentate side and p
2tot
on
the permeate side of the membrane.
The mass transfer coefficient K
i
is proportional to the ith gas
diffusivity in the membrane (m
2
/s), solubility (molm
-3
Pa
-1
)
and membrane porosity (), and inversely proportional to
the membrane thickness (l) and tortuosity ():


Note that the mass transfer coefficient K
i
is related to the
previously defined liquid membrane permeability P
ief
(12)
simply as:


Rearranging Eqs. (16) and (17) and using (18) the final form
of the model is obtained (i = CO
2
, CH
4
and N
2
):


That is the model consists of a set of six (3 compounds 2
membrane sides) 1st order ordinary differential equations
in total.
The n
i,1
and n
i,2
are dependent variables, r is independent
variable and p
1tot
, p
2tot
and K
i
are the parameters of the
model.
The initial conditions are given by the molar flow rates of
each species at the gas inlets on the retentate and permeate
side of the membrane (feed and sweeping gas).
The feed usually consists of mixture of methane and carbon
dioxide, the sweeping gas is pure nitrogen. Also the model
parameters p
1tot
, p
2tot
and K
i
must be specified.
The main assumptions used in deriving the model for the membrane
cell include:
(a) Perfect mixing in axial direction (perpendicular to the membrane
surface) in both retentate (1) and permeate (2) chamber/gap.
(b) Steady state.
(c) Ideal gases.
(d) Isothermal process.
(e) Constant pressure in retentate and permeate chamber (p
1tot
,p
2tot
).
(f ) Mass transfer through the membrane is only due to diffusion
and only in the axial direction (no diffusion in radial direction in the
membrane).
(g) Dissolved gas concentration on the membrane surface is in
equilibrium with the partial pressure of the gas flowing along the
membrane surface.
(h) Spatially and temporally constant membrane properties (, , l).
The set of model equations (six equation total) was solved
using ode45 solver in Matlab R2011a. Model parameters
are summarized in Table 3 for [emim][Tf
2
N]and in Table 4
for [emim][dca].

Experimental
Experimental apparatus :
The apparatus designed for testing of liquid membranes is
schematically displayed in Fig. 2.

Support selection and membrane
preparation
In order to achieve the optimal membrane performance,
two careful selection steps a support selection and an
ionic liquid selection were done. The tested ionic liquids
were purchased from Sigma Aldrich and they are
summarized in Table 5.

The samples of the different porous polymeric materials
were tested for wettability with chosen ionic liquids:

PVDF and PTFE with the best chemical stability were
chosen to be the most convenient materials for membrane
preparation.

A hydrophobic PTFE membrane was used as the second
membrane support because it was non-wettable by ionic
liquid so it could protect the membrane from leakage of
the ionic liquid into the porous stainless steel.

Preparation of ionic liquid
membranes
The porous support was completely immersed into the
selected ionic liquid on a Petri dish.
The dish was then placed inside a desiccator and was
evacuated until no bubbles were observed.
the membrane sample was removed from the liquid and
the excess liquid was wiped away gently.
The membrane was put on a porous hydrophobic Teflon


filter to avoid the direct contact between the porous
stainless steel and the ionic liquid.
The membrane was placed inside the permeation cell and
it was not removed until all the measurements were
completed.
Permeability and selectivity
measurements
The experiments with the ionic liquid membrane consisted
of the following steps:
pure gas permeation measurements at different pressures
mixed gas permeation measurements at one pressure and
different compositions of the gaseous mixture.
Permeability of pure gases (CO
2
and CH
4
) and their binary
mixtures were measured at 25

C.
The feed flow rate of the measured sample gas(ses) was 20
ml min
-1
.
The sweeping gas flow rate 15 ml/min
The effective membrane area was124.6 cm2.
Results and discussion
Results of ionic liquid membrane experiments:
Fig. 3 shows that the CO
2
permeability increases linearly
with pressure while the CH
4
permeability is constant.
The mixed gas permeability and selectivity are depicted
in Fig. 4. Both figures present dependence of
permeability on partial pressure difference of the
particular gas.
The membranes should be operated at the absolute feed
pressure from 150 to 350 kPa since the membrane at
higher pressures loses the selectivity properties and
both gases from feed start to permeate the membrane.
The concentration ratio of gases in the permeate is then
equal to that in the feed.
The permeability of pure CO
2
and the CO
2
/CH
4
selectivity
increase in both membranes with an increasing partial
pressure difference in an almost linear trend.
The trends of mixed gas permeability in both ionic liquids
are similar to the trends observed in pure gas permeability.
The permeability of CO
2
increases with an increasing
partial pressure in both cases.
Its values are in both cases lower than the values of pure
gas permeability.
The mixed gas permeability of the CH
4
was slightly higher
than the permeability of pure CH
4
, indicating that the
mixture components influence the permeability of each
other slightly, which is called the coupling effect.
The CH4 may be dragged through the membrane by the
permeation of CO2 molecules.

The mixed gas selectivity of the [emim][Tf2N] is slightly
lower than the ideal selectivity.

The trend of mixed gas selectivity in [emim][dca] differs
from the ideal selectivity.

The CO
2
/CH
4
mixed gas selectivity is close to 20, which is
less than the highest value achieved for the ideal
selectivity. However, the effect of the pressure on mixed gas
selectivity is not definite.

Summarizing

the permeability of [emim][dca] is lower than that of
[emim][Tf
2
N].
Thus, under the same conditions the [emim][dca]
membrane yields a smaller amount of a permeate with a
higher purity compared to [emim][Tf
2
N].
Comparison of measured and theoretical calculated data:

The experimental data were compared with our
mathematical model of the membrane cell. The mass
transfer coefficient K
i
can be calculated as:
Knowing all the terms on the right hand side of Eq. (18),
allows us to perform the simulations designated as sets 1,
2 and 3.
For the remaining simulation sets 4, 5, 6, and 7 the
coefficients K
CO2
and K
CH4
were obtained by fitting the
simulation results to our experimental results for pure
gases and then they were used for the simulation of the
CO2/CH4 mixture separation.
K
N2
was estimated as 0.5 K
CH4
([emim][Tf2N]) and 0.4 K
CH4
([emim][dca]), based on the ideal membrane selectivities
measured by Scovazzo.
It appears from the pure gas experiments that K
CH4
can be
approximately considered to be constant. On the other hand,
the K
CO2
was not constant and it was rising with the CO
2

pressure. We suspect that this is caused by the deviation of the
CO
2
solubility from linearity. Therefore, in the simulation set 6,
we estimated K
CO2
as:


where K
0
is the infinite dilution mass transfer coefficient, K
1
is
the constant describing how fast the mass transfer coefficient
increases with the dissolved carbon dioxide concentration (and
thus with CO
2
partial pressure)


and


is the average partial pressure of CO2 on both sides of the
membrane.
In our model K
0
= 6.86110
-10
mol/(m
2
sPa) and
K
1
= 2.247 10
-6
Pa
-1
for [emim][Tf2N] and K
0
= 6.6810
-10

mol/(m
2
s Pa) and K1 = 1.1710
-6
Pa
-1
for
[emim][dca]membrane simulations.

The highest deviation was found for simulation set 2, which
uses the Hou and Baltus calculation of the diffusion
coefficient (7). Simulations sets 1 and 3 are close to each
other because they differ only in values of porosity and
tortuosity of the porous support.
In the next step the coefficients calculated for pure gases
were applied to the permeation fluxes measured with the
binary mixture(Fig. 7).

Because the simulation sets 1, 2 and 3 gave poor results for
pure gases, they were not applied on the binary mixture.
Only simulation sets 4, 5, 6
Experimental mass transfer coefficients are very well
applicable to the binary mixture in case of [emim][Tf
2
N].
and 7 were used.
In case of [emim][dca] the mass transfer coefficients of pure
CO
2
do not describe well the behavior of CO
2
in the binary
mixture.
Permeability vs. selectivity trade-off
The correlation diagram known as the Robeson plot is
frequently used to compare the permeability and
selectivity of a new membrane with the already reported
data.
Fig. 8 combines the Robeson upper bound data with the
determined results and the data of pure ionic liquids
reported by Scovazzo.

Fig. 8 shows that the permeability and selectivity of pure
ionic liquids are well comparable to the permeability and
selectivity of the best polymeric membranes.

The same results were achieved in this work. The data
obtained for the supported ionic liquids membrane
(SILM) are situated between the Robeson upper bound of
1991 and 2008.

Conclusion
The main problem seems to be the lack of data of the
diffusion coefficients of gases in ionic liquids and,
consequently, there are no correlations available between
the transport properties and the molecular properties of
the gas and of the IL.

The data available in literature are measured and
calculated for pure ionic liquids only but there is no
reasonable way how to apply them to the supported ionic
liquid membranes.

The reasons why the theoretical models overpredict the
real values of permeation fluxes may be summarized
below:

The mass transfer resistance of the support is not
negligible, as often assumed.
Some pores of the support are not opened for permeation.
The structure of the support obstructs the maximal
saturation of the liquid with the gas or in other words the
initial concentration of the gas in the liquid does not reach
the expected equilibrium value.
None of these reasons should be totally excluded

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