Journal of Membrane Science 430 (2013) 4455

Contents lists available at SciVerse ScienceDirect

Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Temperature and pressure dependence of membrane permeance and its

effect on process economics of hollow ber gas separation system
Faizan Ahmad, K.K. Lau n, A.M. Shariff, Yin Fong Yeong
Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Sri Iskandar, Perak 31750, Malaysia

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 20 September 2012
Received in revised form
9 November 2012
Accepted 25 November 2012
Available online 7 December 2012

Conventional hollow ber models in process simulators usually assume constant membrane permeance
i.e., independent of pressure and temperature. In this work, hollow ber membrane model has been
proposed to cater the effects of temperature and pressure on membrane permeance. The proposed model is
incorporated with Aspen HYSYS as a user dened unit operation in order to study the performance of gas
separation system. The simulated model is validated by experimental and published data. The temperature
drop due to Joule Thomson effect and its contribution to the change in membrane permeance has also been
investigated. Similarly, the effect of pressure on membrane permeance has been studied. The inuence of
these effects on the separation performance and process economics has been investigated for the
separation of CO2 from natural gas. The proposed hollow ber membrane model has potential to be
applied for design, optimization and scale up of wide range of gas separation systems.
& 2012 Elsevier B.V. All rights reserved.

Keywords:
Gas separation
Process simulation
Hollow ber membrane
Joule thomson effect
Membrane permeance

1. Introduction
Membrane based gas separation is an important unit operation
in many industrial separations such as pharmaceutical, biotechnology, petrochemical and gas processing [1,2]. Hollow ber
membrane module is attracting wide range of applications due
to its convincing capabilities, e.g., high efciency/volume, lower
energy requirement, chemical-free operation, etc [3].
The modeling of hollow ber membrane separation has been
studied by number of investigators since the development of rst
mathematical model for membrane gas separation by Weller and
Steiner [4]. Thorman et al. [5] incorporated the effect of pressure
drop in a study on the binary mixtures separations employing
silicone rubber capillaries. A model for practical representation of
gas separation using high ux, asymmetric hollow ber membrane has been presented by Pan [6].
A new approach has been presented and analyzed by Thundyil
and Koros [7] in order to solve the mass transfer problem posed
by the permeation process in hollow ber membrane separator.
Rautenbach et al. [8] studied a variation in ber properties that
affects the performance of defect free hollow ber membrane
modules for air separation. Similarly, Lemanski and Lipscomb [9]
presented a theoretical and experimental study of the effects of
variable ber properties on countercurrent hollow ber gas
separation module performance.

Corresponding author. Tel.: 605 3687589; fax: 605 3656176.

E-mail addresses: faizan615@gmail.com (F. Ahmad),
laukokkeong@petronas.com.my (K.K. Lau).
0376-7388/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.memsci.2012.11.070

Zhao et al. [10] developed a mathematical model to describe a

hollow ber membrane separator for binary gases including
water vapors under low feed gas pressure and vacuum. Moreover,
Jin et al. [11] studied the modeling and control of CO2 separation
process with hollow ber membrane modules.
Recently, Katoh et al. [3] proposed a new simulation model that
deals with the dynamic simulation of hollow ber membrane
separation. The relaxation method is applied to solve the governing
ordinary differential equations for transport across the membrane,
mass balance and pressure distributions in a hollow-ber membrane module. Khalilpour et al. [12] analyzed hollow ber separation and proposed a general nite difference method coupled with
GaussSeidel algorithm for the solution of the non-linear membrane
differential algebraic equations.
Model-based process design is a quantitative approach that
includes developing or obtaining a detailed mathematical model for
the process and identifying the most important design variables
which affect the process [13]. Different commercial process simulators are available to evaluate the operating conditions and optimize
the design congurations [14]. Aspen HYSYS is one of the commonly
used process modelling and simulation software. It provides a
component based framework that can easily be customized, updated
and maintained to meet changing user requirements [15]. A built in
model for membrane separation system is not available in the
standard version of Aspen HYSYS but it can be implemented along
with its solution procedure by using Visual Basic (VB) or C
subroutine.
Many studies have been done to propose a exible mathematical
model in process simulator within the last decade. Rautenbach et al.
[16] developed a simple cross ow membrane model in AspenPlus

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455

without consideration of pressure drop. Tessendorf et al. [17]

implemented a membrane model for gas separations based on
equation oriental approach in external process simulator OPTISM.
Davis [18] also implemented a hollow bre membrane model in
Aspen HYSYS with the assumption of negligible pressure drop
without external custom programming. Chowdhury et al. [14]
presented a numerical solution approach to implement an existing
model by Pan [6] in AspenPlus for co-current and counter current
membrane congurations. In addition, Hussain et al. [19] implemented a one-dimensional isothermal model in Aspen HYSYS for
the feasibility study of CO2 capture ue gas by a facilitated transport
membrane. Peters at al. [20] performed simulation analysis with
Aspen HYSYS for amine absorption and membrane separation.
Recently, we proposed a new method to implement a simple cross
ow model in Aspen HYSYS for CO2 capture from natural gas [21].
Based on the published literature [14,1619,21], it can be
concluded that there is limited membrane model available for
hollow ber membrane module in commercial simulator. All of
the above proposed models do not deal with non ideal effects
such as pressure and temperature dependence of membrane
permeance.
An expansion of the residue gas at higher pressure in a
membrane module to lower pressure gas in the permeate stream
can result in a change of temperature. The common example of
this phenomenon is Joule Thomson (JT) cooling of the gas passing
through adiabatic expansion valve [22]. Membrane permeance is
dependent on temperature and pressure. Thus, pressure drop
across the membrane and temperature drop due to JT effect cause
change in membrane permeance.
A few studies examined temperature change due to Joule
Thomson (JT) effect in membrane based gas separation. Rautenbach
and Dahm [23] investigated temperature change in gas permeation
modules for separating CO2 and CH4. Cornelisson [24] also contributed to study the heat effect on gas permeation. Coker et al. [22]
proposed a model for the JouleThomson effect in CO2/CH4 separation but it has not been applied in process simulators. Scholoz et al.
[25] linked non ideal effects including JT effect in the gas permeation
modeling but has not presented the effect of variable permeance
(due to change in temperature and pressure) on performance and
economics of gas separation system.
In this paper, an experimentally validated hollow ber membrane model considering temperature and pressure dependence of
membrane permeance would be implemented in Aspen HYSYS as
user dened unit operation using nite element method in Visual
Basic (VB) sub routine. The paper demonstrates the case study of
CO2 removal from natural gas by hollow ber membrane. The
comparison of ideal model with constant permeance and non ideal
model with variable permeance (due to temperature and pressure
effects) would be made to evaluate the inuence of this non ideal
effect on the separation efciency and process economics (gas
processing cost) of membrane separation system.

2. Mathematical method
2.1. Mathematical model
The radial cross ow model (shell side feed) for hollow ber
membrane module is schematically represented in Fig. 1. The
bundle of bers is sealed at one end using epoxy The other end of
ber bundle is kept open to allow the ow of gases. The ber
bundle is housed in the middle of shell. Feed gas is introduced in
the system from the shell side that ows radially inward perpendicular to the bers toward the centre. The permeate into the
bers ows axially along to the permeate collector. As a result,

45

Tube side (Fiber Bundle)

Shell side

Feed
Retentate

Permeate

Epoxy Tube Sheet (closed end)

Epoxy Tube Sheet (Open end)

Feed End

j=1

j=M

i=1

i=N

Tube sheet

III

II

IV
Retentate End

Sealed end
sheet

Permeate
End

II

IV

III

Fig. 1. Schematic diagram of Hollow ber membrane separation (shell-side feed).

(a): Types of element in the tube side (ber bundle) of the module [7].

ow rates and compositions vary axially as well as radially

making it two dimensional model [7].
The separation efciency of two components (i, j) is a measured by the ratio of their permability known as selectivity. It is
given by

aij

Pi
Pj

For a binary gas mixture, the local permeation rate at any point
in the stage over a differential membrane area, dAm is as follows
ydV


P1 
ph xpl y dAm

1ydV


P2 
ph 1xpl 1y dAm

Dividing Eq. (2) by Eq. (3), we get



ax pl =ph y
y



1y
1x pl =ph 1y

where P1 and P2 are the permeabilities of pure gas components

(CO2 and CH4 in this work), x and y are the feed and permeate
composition at any point along the membrane, d is the membrane
thickness and a is the membrane selectivity [26].
One of the approach used to solve this two dimensional model
is succession of states or nite element method. The main
advantage of nite element method over solution of differential
equations is that it is easy to incorporate non ideal effects in the
former method such as permeate pressure drop in the ber and
tube sheet, Joule Thomson (JT) effect, pressure and temperature
dependence of membrane permeability etc. The method divides
the membrane area into a number of elements having constant
driving force and specied inlet conditions, computing the mass
transfer and this obtaining the outlet conditions [7].
Hollow ber membrane module is mainly characterized by
[7,27,28]
(a) Dimensions of bers bundle (such as ber length, L and radius
of ber bundle, R)
(b) Inner and outer diameter of the bers, di and do
(c) Measure of packing density and porosity: The packing density
of hollow ber membrane module is dened as the

46

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455

fraction of the cross section area of all bers over the cross
section area of the module.
nf

Af
do
nf
Am
dm



15

Q si,j Q si1, j DQ

16

Q T i,j Q T i1, j DQ

17

where nf is the number of bers, Af is the cross section area of

bers and Am is the cross section area of module. Furthermore;
number of bers/cross sectional area of ber (Nf), porosity of ber
bundle (e) and membrane area/bundle volume (A/V) are connected as follows.
1
Nf 

p=4 do 2

 
A
41 e

do
V

The model will consider the specic bundle area, and divide it
up into a predetermined number of elements (index i in the
radial direction and index j in the axial direction). The nite
element is assumed to exist at radius r from the centre of the
bundle having radius of Dr and length of Dz. The membrane
separation area of each nite element is determined by it volume
(2prDrDz) and specic area of membrane bundle (membrane
bundle area/unit volume of membrane bundle) as follows.
A 2pDrDz1=do

In the case of radial cross ow, there are four types of elements
depending upon their radial and axial location in the tube side
(ber bundle) of the module as shown in Fig. 1a The computation
proceeds from the Type 1 to Type 3 elements till the end of
bundle and then starts again from Type 2 elements through the
succession of Type 4 elements [7].
For a binary system, the permeate composition, y1 (faster
permeating component) in the rst and second types (Type
1 and Type 2) of nite elements is given in terms of mole fraction
of the shell side, x1 (faster permeating component) as follows.
y1

DQ 1 P 1 =d ph x1 i1, jpl y1 i,j:A

x1 i,j

Q si1, jx1 i1, j DQ 1 

Q si,j

18

y1 i,j

Q T i1, jy1 i1, j DQ 1 

Q T i,j

19

For elements in contact with feed (Type 3), the sufxes (i 1, 1)
are replaced with feed conditions such as Qf and xf. Solving the
above set of equations, mass transport across the membrane for the
each element can be computed. Using same approach for all the
elements, computation proceeds from the epoxy sealed end of the
hollow ber tubes to the tube-sheet end of these bers [7].
In addition, viscosity of gas mixture is calculated by Wilkes
method while viscosity of pure components and their temperature dependence are determined using Lucas method [29]. The
assumptions that follow the suggested model making it applicable only for ideal conditions are:
1. It holds only for the binary gas mixture. Even though it is an
ideal assumption, yet it is a rst step to understand realistic
modeling and simulation of many important separations
[6,7,10,11,19,21,30,31] such as CO2-methane separation in
the current work.
2. The shell side pressure variations are negligible (due to
constant bulk ow in an axial direction) while the permeate
side pressure drop is determined by HagenPoiseuille
[6,7,10,17,19,21].
3. The system operates at isothermal conditions [6,7,10,14,17,
19,21,31]
4. Membrane permeability is assumed to be independent of the
temperature and pressure [3,6,7,10,11,14,19,21,30]

a1bx1 1 ba1bx1 1 b2 4abx1 a10:5 

2a1

9
where a is the selectivity of membrane and b is the pressure ratio
of higher pressure side to lower pressure side. The ow rate into
the nite element of the permeate side is given by




DQ P 1 =d ph x1 i1, 1pl y1 i,1 P2 =d ph: x2 i1,1
pl y2 i,1:A

10

where x2 1  x1 and y2 1 y1 (Binary component gas mixture)

Similarly, the shell side ow rate, Qs (i, 1) and permeate side
ow rates, QT (i, 1) contacting the next element are given by
Q si,1 Q si1, 1 DQ

11

Q T i,1 DQ

12

The shell side composition x1 (i, 1) of respective element is

given by
x1 i,1 Q si1, 1x1 i1, 1 Q T i,1y1 i, 1=Q si,1

13

For elements in contact with feed (Type 1), the sufxes (i1, 1)
are replaced with feed conditions such as Qf and xf. These elements
will not have any preceding elements in the radial direction [7].
For Type 3 and Type 4 elements, shell and tube ow rates and
compositions are known and mass transport is measured by
solving the following equations




DQ P1 =d ph x1 i1, jpl y1 i,j P2 =d ph: x2 i1,jpl y2 i,j:A
14

2.2. Temperature and pressure dependence of membrane permeance

One of the limitations in the proposed mathematical model is
the assumption (discussed in previous Section 2.1) that system
operates at isothermal conditions. Experiments [32] clearly indicate that, in a number of separations problems, deviations from
isothermal conditions occur which cannot be neglected. The main
reason for temperature change is Joule Thomson effect which
occurs when non-ideal gases are expanded [23].
In the separation of CO2 from natural gas, the permeate
temperature decreases as a direct consequence of the Joule
Thomson effect. The observed temperature decrease on the high
pressure side is an indirect consequence of the JT effect since heat
is transported across the membrane along with enthalpy due to
the permeation of mass through the membrane. Both lead to a
decrease of the membrane temperature along the module [23].
Thus the module temperature may change and affect its separation performance in case of non-ideal mixtures. This is especially
true for cases involving high membrane permeance values such as
CO2/CH4 separation [27].

The JT coefcient mJT must be calculated in order to study
the JT expansion effect on the gas passing through the membrane.
The calculation procedure is elaborated by Maric [33,34]. The
general equations are provided as follows
 
R T 2 jZ
mJT g
20
rC m,p jT p

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455



0
C PI  Rg T T00 2
Cp

C m,p
M
M

21

where Rg is univeral gas constant, Cm,p is molar heat capacity, CPI is

the ideal heat molar capacity, M is molar mass, 0 and 00 are the
rst and second derivatives of the gas fugacity coefcient. The
rst derivative of the compression factor with respect to temperature is
 0

P
n0 n
RTZ2 58
n 13 C n Dn pZ TZ 0 Z 1
Z
22
R TZ2 pTZ 1
where
cnr

Dnn bn cn kn rr kn rr bn e
18
X

Z 1 Brm rr

C nn

n 13

Z 0 BK 3

18
X

k
r n

58
X

23
C nn bn cn kn rr kn rr bn ecnrr kn

24

n 13

C nn

Z 00 B0  K 3

58
X

C nn0

26

C nn K 3 bn cn kn 2bn kn cn kn rr kn rr kn  rr bn 1 ecn rkr n

n 13

27
where, rm is gas mixture molar density, rr is reduced density, B is
second virial coefcient, kn and bn are equation of state parameters and Cnn is temperaturecomposition dependent coefcient. Therefore, the nal analytical equation for JouleThomson
coefcient is given by

mJT

RT 2

M


CPI RT T00 20
 0

P
n n
RTZ2 58
n 13 C n Dn rZ TZ0  Z 1

r


where a, b, c, d and e are model constants, Rg is universal gas

constant, p is pressure and T is temperature at which permeance
has to be calculated. The above equation shows good agreement
both with theory and experimental data [39].
The current study used Eqs. (20)(29) to calcualte the temperature drop due to JT effect and Eq. (32) to calculate the
inlfuence of temperature and pressure on membrane permeance.
These equations are then included with ideal hollow ber
membrane model, explained in the previous section.
2.3. Process simulation and economics

n 13

Z1 Z0

where Po is the pre-exponential factor independent of temperature and Ep is the activation energy for permeation.
Safari et al. [39] examined different forms of equations based
on partial immobilization and Arrhenius models and presented
the following form that includes pressure and temperature effect
simultaneously.




cexp d=Rg T
b


P aexp

32
Rg T
1 e=T p

25

n 13
18
X

47

RTZ2 rTZ 1

28

The temperature drop due to JT effect can thus be calculated as

follows


DT T h T l mJT ph  pl
29
Membrane permeance is dependent on temperature and
pressure described by Arrhenius and partial immobilization
models [35,36]. Paul and Koros [37] presented the rst partialimmobilization model based on the concentration gradient. The
modications to the Ficks law for diffusion were done by
introducing a new diffusion coefcient DH for the mobility of
the Langmuir mode species. A simplied permeance expression is
derived as [38,39]


30
P K D DD 1 FK=1 bp 
where F DD/DH and KCHb/Kd. DD the Henrys diffusion coefcient and DH is the Langmuir diffusion coefcient. The parameter
b is explained conceptually as the afnity of the gas molecules to
get absorbed in the holes, CH is the total concentration of these
holes in that polymer, and KD is the Henrys law dissolution
constant.
Generally, the gas transport process through polymer membranes can be considered as an activated process which indicates
that we can represent the temperature dependence of permeability by an Arrhenius-type equation [35, 39]


Ep
P P o exp
31
Rg T

The membrane units are most likely to be part of a complex

process ow sheet along with other unit operations. Thus, it is
advantageous to introduce the membrane unit into commercial
process simulator which will then provide a tool to simulate,
design and optimize the overall process rather than an isolated
membrane module.
In this work, hollow ber membrane model (Fig. 1) has been
interfaced with Process simulation programme, ASPEN HYSYS in
order to calculate permeate and retentate of the system with
any number of modules, allowing complex process simulations.
The programme has the possibility to use ASPEN HYSYS capabilities to calculate mass and energy balances and combine in the
process model.
The equation of state was solved to calculate Joule Thompson
coefcient at certain temperature using Visual Basic coding as a
part of complete hollow ber membrane model. The model is
then interfaced as a user dened unit operation (extension) in
Aspen HYSYS employing Visual basic subroutine in order to
calculate permeate and product compositions, ow rates and
membrane area required for the separation. These parameters,
along with methane losses, stage cut and compressor power,
dene the gas processing cost (GPC) for the membrane system. In
order to get the optimal design, it must be minimized keeping
operating conditions under consideration.
Usually, upgraded natural gas is sold on the basis of product
volume rather than of feed volume [40]. Therefore, processing
cost per MSCF of product is used in the present study. It should
also be noted that retentate containing high methane is considered as product in the current study.
The procedure to calculate the gas processing cost (GPC) is
given in Table 1. It includes the capital related cost (CRC), the
variable operating and maintenance cost (VOM) and the cost of
CH4 lost in the permeate stream (CH4LS) [19,40]. The cost of
cooling system is included in the compressor cost (CC) as it usually
comes along with compressors. A payout time is considered to be
5 years in order to calculate the capital cost whereas project
contingency, that covers the unpredictable elements of the project,
is assumed to be 20% of the base plant cost [40]. Gas processing
cost (GPC) must be minimum subject to operating conditions,
material and energy balances, and individual permeator mathematical model [31].
One of the approaches to design of a membrane separation
process is to select a small number of design congurations and
optimize the operating conditions of each conguration. The nal

48

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455

optimum design is chosen to be the system with most favourable

economics [31,4143]. In the previous paper [21], we have shown
that double stage with permeate recycle system (shown in Fig. 2)
gives the optimum design conguration due to minimum process
gas cost involved with it. In this work, non ideal effects have been
introduced in the model and the optimum design conguration is
explored further to see the inuence of non ideal effects on the
performance and economics of the separation system.

2.4. Simulation conditions

Feed conditions for natural gas treatment plant depend mainly on
the source; therefore composition, ow rates, pressures and temperature of crude natural gas typical for medium sized natural gas
treatment plant for removing CO2 gas are selected. As a result, the
feed ow rate of feed gas is maintained at 50000 SCFH (1.3 MMSCF).
Feed temperature is 323 K. On the other hand, feed pressure and
permeate pressures are maintained at 59.6 bar and 1.8 bar,
Table 1
Economics parameters for gas processing cost [19].
Total plant investment (TPI):

TPI TFI SC

Membrane module cost (MC)

Installed compressor cost (CC)
Fixed cost (FC)
Base plant cost (BPC)
Project contingency (PC)
Total facilities investment (TFI)
Start up cost (SC)

$ 5/ft3
$ 8650 *(Wcp/Zcp)0.82
MC CC
1.12 * FC
0.20 * BPC
BPCPC
0.10 * VOM

Annual variable operating and

maintenance Cost (VOM):
Contract and material maintenance
cost
(CMC)
Local taxes and insurance (LTI)
Direct Labor cost (DL)
Labor overhead cost (LOC)
Membrane replacement costs (MRC)
Utility cost (UC)

VOMCMC LTI DL LOC MRC UC

Annual cost of CH4 lost in

permeate (CH4LS):
Annual natural gas lost (NGLS)

0.05 * TFI
0.015 * TFI
$ 15/h
1.15 * DL
$ 3/ft2 of membrane
$ 0.07/kw h
CH4LS NGLS * NHV * NWP
NGLS 365 * OSF * Lf * yP(CH4) * xf (CH4)

GPC (CRC CH4LS VOM)/[365 * OSF *

Lf * (1SCE) * 1000
Annual capital related cost (CRC)
0.2 * TPI
Membrane life (t)
4 years
Wellhead price of crude natural gas $ 2/MMBTU
Heating value of natural gas
1066.8 MMBTU/MMSCF
On stream factor (OSF)
96%
Compressor efciency (Zcp)
0.8
Gas processing cost (GPC)

respectively, unless specied otherwise [7,22]. The permeance values

used for the simulation (22 GPU for CO2 and 0.7 for CH4 at 50 1C)
correspond to membrane material of polyimide for the effective
separation layer thickness of 0.1 mm [22,44].
Modules parameters are typical for hollow ber membrane
separations used for natural gas treatment applications. Unless
specied otherwise, the simulations are run at the ber bundle
radius of 10 cm. Similarly, hollow ber module is composed of
bers having outer diameter of 0.040 cm and packing density of
50%. Lower packing density may cause ow channelling outside
the hollow bers. In contrast, higher packing density may lead to
a reduction of the ow space for shell-side feeding, which may
cause higher pressure drop [27].
Natural gas contains different amounts of CO2 ranging from
sweet (CO2-free) gas in Siberia to very high CO2 content of 90% in
the Platong and Erawa elds in Thailand [45]. The natural gas eld
in the Greater Sarawak Basin (Indonesia), with estimated 46
trillion cubic feet recoverable reserves, remains undeveloped
due to high CO2 contents of 71% [45,46]. In Malaysia, 13 trillion
cubic feet natural gas reserves are undeveloped due to high CO2
content that varies from 28% to 87% [46,47]. Therefore, three
cases have been investigated including lower concentration feed
(10% CO2), medium concentration feed (40%) and higher CO2
concentration feed (70% CO2).

3. Experimental method
Mathematical models have to be supported by experimental
data. Thus, the proposed model is veried by experimental
method through comparison of the simulated and experiments
results. The experimental set up mainly consists of hollow ber
membrane module and the gas separation testing unit in which
the module is installed to facilitate the separation mechanism.
3.1. Hollow ber membrane module
Hollow ber modules may have different congurations to
meet the needs of different applications. The current work used
cross ow (shell-side feeding) hollow ber module as shown in
Fig. 1. In this conguration, two tube sheets hold the ber ends in
place and separate the retentate from the permeate ow. One is a
plug-sealed tube sheet in which the openings of ber ends are
blocked by the epoxy resin; the other is an open-end tube sheet in
which the bores of hollow bers are exposed [27].
The hollow bers used for the experimental work are commercial (Alpha Membrane Hi-Tech Pte. Ltd, Singapore). The
material of membrane used is polyimide having the permeance
of 22 GPU for CO2 and 0.7 GPU for CH4 at 50 1C. The bers have
outer diameter of 400 mm and inner diameter of 180 mm. The

Fig. 2. Process ow diagram (PFD) of double stage system with permeate recycle in Aspen HYSYS.

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455

49

gas cylinders, mass ow controllers, compressor, and infrared

analyser. Natural gas (with impurities) and pure methane can be
used alternatively in the set up. In addition, nitrogen is used for
purging the separation system. In the current study, pure
methane and CO2 are used to evaluate the performance of
separation system. Thermocouples and pressure gauges are
installed before and after the permeation test cell to monitor
the temperature and pressure drop across the membrane module.
Furthermore, a back pressure regulator is xed after the membrane module in order to generate trans-membrane pressure
required for the separation of gases. The whole system except
feed cylinders and compressor is placed in an oven to maintain
the temperature of system and isolate from external effects.
Coriolis ow meters are used to measure the mass ow rates of
streams. Similarly, Infrared analyzer is used to measure the
composition of feed, permeate and retentate streams. They are
connected to data acquisition system in order to record the gas
concentrations of streams at different times.

required ber numbers and ber length are calculated based on

the diameter of hollow bers and the length of module with an
assumption of 4050% packing density. Fifty bers having length
of 28 cm have been cut for the purpose of bench-scale testing in
the current study.
Using the same procedure for bundle preparation as explained in
the published literature [27,48], the bers are cut to a desired length
and visibly defective bers are removed. Finally, the remaining
bers are placed in parallel order while putting them together as a
ber bundle. A piece of barrier lm (Paralm Ms) has been taken,
stretched and wrapped it on one end of the ber bundle. The end of
the ber bundle will become denser because of the shrinkage of the
lm. The wrapped side is cut with a sharp razor blade to yield a
smooth end. The end has to be encircled with string in order to be
sure that its diameter is less than the shell diameter.
The shells made of stainless steel (SS 316) having outer diameter
of 1/2 in (1.27 cm) and 1 in (2.54 cm) are used in this study. In order
to assemble the module, the shell is placed vertically on a holder
with enough space under it to accommodate the ber bundle. With
the help of string, ber bundle is housed in the shell.
The void space between the bers and the internal wall of the
shell was potted i.e., lled with epoxy glue (Loctites E-30CL
Hysols adhesive). The purpose is to isolate the permeate stream
from the retentate stream. Unlike the open side, the other side of
bers are completely sealed by the epoxy glue to form a dead end.
The glue hardens in several minutes but reaches the maximum
strength in 24 h. The openings of the bers have to be inspected
carefully to make sure that all of them are properly embedded in
glue and not closed or deformed by cutting.

4. Results and discussions

4.1. Model validation
To demonstrate the applicability of the model, the simulated
model with non ideal effects is validated with experiments
performed in laboratory. Feed gas containing 50% CO2 is maintained at 10 l per minute ow rate while at temperature of 50 1C.
On the other hand, feed pressure is maintained at 10 bar. The
number of bers is xed to 50 and CO2 concentration in the feed
gas is varied from 10% to 70% in order to nd the temperature
drop across the membrane measured by thermocouple installed
in the equipment. The experimental results are compared with
simulated results for the simplest design conguration with no

3.2. Gas separation testing unit

Hollow ber membrane module is installed in the experimental set up as shown in Fig. 3. The testing unit mainly consists of

Pressure guage Thermocouple

P

T
F

Pressure guage

Flow meter

Flow meter
F

Pressure guage Thermocouple

Backpressure
Regulator

Thermocouple

Hollow Fiber
Membrane Module

Flow meter

Static mixer

Flow
controller

Feed Vessel

Natural gas

CH4

CO2

Infrared Analyzer

N2

Fig. 3. Flow sheet of gas separation testing unit for experimental validation.

Data Acquisition
System (Computer)

50

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455

recycle stream as shown in Fig. 4. It can be seen that suggested

model is in agreement with experimental results with maximum
percentage error less than 8%. The small difference in values
might be due to the experimental errors and precision limitations
of instruments (thermocouples).
The non ideal model is further compared to experimental data
published by Pan [6] as shown in Fig. 5. The data is based on the
experiments performed on sour natural gas. Feed conditions used
are 48.5% CO2, 27.9% CH4, 16.26% C2H6 and 7.34% C3H8. The
membrane material is cellulose acetate with permeance values of
40.05 for CO2, 1.11 for CH4, 0.31 for C2H6 and 0.06 for C3H8 [6].
Thus, it can be assumed that most of heavy hydrocarbons (such as
C2H6 and C3H8) pass to the retentate/product without permeating
though the membrane. The simulations are performed in Aspen
HYSYS on the basis of 48.5% CO2 and 27.9% of CH4 in the feed with
membrane permeance values of 40.05 and 1.11, respectively
while allowing other components to pass across the module
without permeation.
The temperature and pressure values of the gas are 10 1C and
35.28 bars, respectively, while the permeate pressure is 9.28 bar.
The selectivity is assumed to be 25. The same process conditions
are maintained for the simulated model and compared with the
experimental data. Fig. 5 shows that the suggested model gives
good approximation to the experimental data with maximum
percentage error less than 3%.

4.2. Temperature and pressure effects

50

45
40

45

Temperature Drop (C)

40
35

Experimental
30

Simulated (Non ideal)

model

25

20

40

60

40 % CO2

30

70 % CO2

25
20
15
10
5

20
0

10 % CO2

35

80

10

20

Fig. 4. Model validation with experimental results at feed temperature 50 1C,

feed pressure 10 bar, feed ow rate 10 l/min and number of bers 50.

40

50

60

Fig. 6. Effect of stage cut on temperature drop (Feed temperature 323 K).

45

25

40
0.95

Temperature drop (C)

Permeate CO2 mole fraction

30

Stage Cut

CO2 contents in feed (%)

0.9
0.85
0.8
0.75
0.7
0.4

Experimental data by
Pan [10]
Simulation results by
suggested model

20

35
30

15

25
20

10

15

Temperature drop

10

Permeance of CO2

0
0.45

0.5

5
0.55

0.6

Stage Cut
Fig. 5. Model Validation with published literature by Pan [10].

0.65

10

20

30

40

50

0
60

Stage Cut
Fig. 7. Effect of stage Cut on CO2 permeance of for 70% CO2 feed.

Permeance of CO2 (GPU)

Temperature of permeate stream (C)

Stage cut has a large impact on the gas thermodynamics

properties and contributes to temperature drop. As an initial step,
the membrane permeation properties are taken to be constant at
the values characteristic of the feed temperature (50 1C) in order

to isolate the effect of temperature changes entirely due to

expansion-driven cooling. The feed pressure is maintained at
59.6 bar while permeate pressure at 1.8 bar. Fig. 6 reports the
effect of stage cut on temperature change across the module for
different feed concentrations of CO2. It can be observed that
temperature change across the module can be as large as 40 C and
is strongly dependent upon the stage cut as well as CO2 concentration in the feed. At the same stage cut, gas mixtures with more
CO2 in the feed experience larger temperature decreases from the
feed to residue ends of the module. It is due to the reason that
feed composition changes not only the amount of permeating gas
across the ber wall but also the thermodynamic properties (such
as heat capacity and PVT properties) of the gas mixtures in the
residue and permeate streams [22].
In general, gas permeance values are taken to be independent
of temperature in order to isolate the inuence of gas-phase
composition and stage cut on expansion-driven temperature
changes. However, signicant temperature changes across the
module are observed. Thus, simulations are performed in order to
study the effect of stage cut and temperature drop on membrane
permeance of CO2 and CH4. As an example, the effect of stage cut
and temperature drop on CO2 permeance for higher concentration
feed (70% CO2) is shown in Fig. 7. Similarly, the effect of stage cut
and temperature drop on CH4 permeance for higher concentration
feed (70% CO2) is shown in Fig. 8. It can be seen that permeance of
both CO2 and CH4 decreases with the increase in stage cut. It is
due to the reason that the increase in stage cut increases the
temperature drop which results in change of CO2 and CH4
permeance being dependent on temperature.
Feed pressure due to partial pressure of gases in the feed also
affects the membrane permeance. It is due to the reason that the
mass transport of membranes for the separation of CO2/CH4
mixtures is determined by competitive sorption and plasticization

0.9

40

0.8

35

0.7

30

0.6

25

0.5

20

0.4
0.3

15
10
5
0

Temperature drop

0.2

Permeance of CH4

0.1

20

30

40

50

Ideal model (constant

permeance)

3.5
3

Non-ideal model
(variable permeance)

2.5
2
1.5
1
0.5

0
10

51

4.5

Retentate CO2
Composition (%)

45

Permeance of CH4 (GPU)

Temerature drop (C)

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455

60

100

Stage Cut

200

300

400

Fiber length (cm)

Fig. 8. Effect of stage cut on CH4 permeance of for 70% CO2 feed.
25

20

0.5
15
0.45
10
0.4

CO2
5

0.35

CH4

Methane loss (%)

Permeance of CO2 (GPU)

0.55

Permeance of CH4 (GPU)

0.6

25

20
15
10

Ideal model (constant

permeance)

Non-ideal model
(variable permeance)

0
0

100

200

300

400

Fiber length (cm)

0.3

0
0

10

20

30

40

50

60

Pressure Ratio

0.35
0.3

Fig. 9. Effect of pressure ratio on membrane permeance of CO2 and CH4 for 70%
CO2 feed.

Stage Cut

[49,50]. Fig. 9 shows the effect of pressure ratio on the CO2 and
CH4 permeance of the membrane material for the higher CO2
concentration feed. It can be seen that permeance value increases
with the increase in pressure ratio and vice versa. Thus, pressure
ratio is an important factor to determine the non ideal permeance
of the separation system.

0.25
0.2
0.15

Ideal model (constant

permeance)

0.1

Non-ideal model
(variable permeance)

0.05
0
0

4.3. Membrane performance study

A case study of CO2 separation from methane was performed in
order to evaluate the performance of non-ideal model (with temperature and pressure effects on membrane permeance) in terms of
product/retentate composition, methane loss and stage cut. Moreover, it is compared with ideal model having constant permeance.
Fig. 10(a) reports the mole fraction of CO2 on the retentate/
product side of the system as a function of ber length for feed
CO2 composition of 10%. It can be seen that mole fraction of CO2
decreases with the increase in ber length of module. The reason
is that the increase in ber length (or membrane separation area)
improves the amount of CO2 permeating through the membrane
leading to lower retentate/product CO2 composition. It can also be
observed that non ideal model (variable permeance) shows higher
CO2 composition in the retentate/product for the same ber
length in comparison with the ideal model (constant permeance).
The maximum difference between ideal and non ideal models at
the same ber length is almost 18%. It is due to the fact that
membrane permeance of CO2 decreases as a result of pressure
drop and resultant temperature drop due to JT effect as explained
in the previous section. As a result of membrane permeance
change in non ideal model, the composition of CO2 increases in
retentate/product.
Methane (CH4) loss can be described as the percentage of methane
lost in the permeate stream to the methane present in the feed
stream. It increases with the increase in ber length due to increase of

100

200

300

400

Fiber length (cm)

Fig. 10. Comparison of (a) retentate CO2 composition (b) Methane loss (c) stage
cut by ideal model (constant permeance) with non ideal model (temperature and
pressure dependent permeance) for 10% CO2 feed.

membrane separation- area and vice versa [7]. Fig. 10(b) presents the
methane loss as a function of ber length for both ideal and real
scenario. Methane loss increases with the increase in ber length as
expected but it is less pronounced in non ideal case (with maximum
difference of 6%) where permeance of both CO2 and CH4 decreases
with the temperature and pressure drop.
Fig. 10(c) shows the effect of ber length on stage cut. Stage
cut increases with the increase in ber length. For the same ber
length, non ideal case shows lower stage cut in comparison with
ideal case with maximum difference of 4%. It is due to the reason
that ow rate of permeate stream decreases due to decrease in
permeance of CO2 and CH4. As a result, stage cut being ratio of
permeate ow rate to feed ow rate, gets reduced for the non
ideal case. The results are consistent with those obtained by Safari
et al. [39] and Schloz et al. [25].
All these results are repeated for medium CO2 feed concentration
of 40% as shown in Fig. 11 and higher concentration of 70% as shown
in Fig. 12. It can be seen that the performances at the higher feed
concentration is an amplication of the results obtained at the lower
feed concentration. For example, the maximum difference between
ideal and non ideal cases for retentate/product CO2 composition is

52

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455

Retentate CO2
Composition (%)

Ideal model (contstant

Permeance)
Non ideal model (variable
permeance)

15

10

100

200

300

400

Retentate CO2 Composition

(%)

35
20

25

Non-ideal model
(variable permeance)

20
15
10
5
0

Fiber length (cm)

Ideal model (constant

permeance)

30

100

200

300

400

Fiber length (cm)

40
60

30

50

25
20
15

Ideal model (constant

permeance)

10

Non ideal model (variable

permeance)

Methane loss (%)

Methane loss (%)

35

100

200

300

30

Ideal model (constant

permeance)

20

Non-ideal model
(variable permeance)

10

0
0

40

400
0

Fiber length (cm)

100

200

300

400

Fiber length (cm)

0.4
0.5
0.35

0.25

Ideal model (constant

permability

0.2

Non ideal model (variable

permeance)

0.15
0.1

100

200

300

400

Fiber length (cm)

Stage Cut (%)

Stage Cut

0.45
0.3
0.4
0.35

Ideal model (constant

permeance)

0.3

Non-ideal model
(variable permeance)

0.25
0.2

100

200

300

400

Fiber length (cm)

Fig. 11. Comparison of (a) retentate CO2 composition (b) Methane loss (c) stage
cut by ideal model (constant permeance) with non ideal model (temperature and
pressure dependent permeance) for 40% CO2 feed.

increased to 10% (for 40% CO2 concentration feed) and 15% (for 70%
CO2 concentration feed). More concentration of CO2 in feed causes
more temperature drop due to JT effect that leads to decrease in
membrane permeance. As a result, retentate CO2 composition tends
to increase while stage cut and methane loss tend to decrease
further for non ideal model.
4.4. Process economics study
In order to evaluate the process economics of the system, feed
gas composition of CO2 is xed at 40% while methane purity at
96% (4% CO2 in retentate stream) and the effect of ber length on
the compressor power requirement and gas processing cost has
been investigated both for the ideal and non ideal case of
membrane permeance. The simulations conditions are same as
mentioned in the Section 2.4 (Feed pressure59.6 bar, permeate
pressure1.8 bar, feed temperature323 K and feed ow
rate1.3 MMSCF). The compressor efciency of 80% is used as
shown in Table 1.
The effect of membrane module characteristics on the compressor power requirement has been investigated for the proposed design conguration (double stage with permeate recycle)

Fig. 12. Comparison of (a) retentate CO2 composition (b) Methane loss (c) stage
cut by ideal model (constant permeance) with non ideal model (temperature and
pressure dependent permeance) for 70% CO2 feed.

The compressor power is given by the expression [51].

W cp hp Rg T

 
ph
Q p, n ln
n1:341
pl,n
n1
2
X

33

where Qp is the permeate ow rate, n is the index of membrane

stage, T is the temperature and Rg is ideal gas constant.
Fig. 13 shows the comparison of ideal and non ideal model for
compressor power as a function of ber length. It can be seen that
compressor power requirement increases with the increase in
ber length. In fact, these ber length change the membrane
separation area which causes the change of stage cut as explained
in the previous section. Keeping the feed ow rate constant, the
change in stage cut would mean the change in permeate ow
rate. It can be seen from Eq. (33) that compressor power depends
on the permeate ow rate along with feed and permeate pressures. Thus, the change in permeate ow rate change results in
change of compressor power requirement accordingly. It can also
be observed that compressor power requirement change is less
pronounced in non-ideal case for the same ber length. The
maximum difference between compressor power for ideal and

300

350

250

300

200
150

Ideal model (constant

permeance)

100
50

Non ideal model (variable

permeance)

Compressor Power (hp)

Compressor power (hp)

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455

250
200

100

200

300

400

Ideal model (constant

permeance)

150
100

Non ideal model

(variable permeance)

50
0

0
500

100

200

300

400

500

Fiber length (cm)

Fiber length(cm)
Fig. 13. Comparison of compressor power by ideal model (constant permeance)
with non ideal model (temperature and pressure dependent permeance) at feed
CO2 composition 40% and methane purity 96%.

Fig. 15. Comparison of compressor power by ideal model (constant permeance)

with non ideal model (temperature and pressure dependent permeance) at feed
CO2 composition 70% and methane purity 96%.

0.07

0.08

0.06

GPC (MSCF of product)

GPC (USD/MSCF of product)

53

0.05
0.04
0.03

Ideal model (constant

permeance)

0.02

Non ideal model (variable

permeance)

0.01
0
0

100

200

300

400

500

0.07
0.06
0.05
0.04

Ideal model (constant

permeance)

0.03
0.02

Non ideal model

(variable permeance)

0.01
0
0

Fig. 14. Comparison of gas processing cost by ideal model (constant permeance)
with non ideal model (temperature and pressure dependent permeance) at feed
CO2 composition 40% and methane purity 96%.

non ideal case at the same ber length is 6%. It is explained by the
reason that compressor power mainly depends on the permeate
ow rate and thus stage cut. With the decrease in stage cut due to
decrease of membrane permeance for gases, there will be low
requirement of compressor power in non-ideal case where
membrane permeance is dependent on temperature and pressure.
The effect of ber length on gas processing cost (GPC) for both
ideal and non ideal cases is shown in Fig. 14. It can be noted that
larger ber lengths yield higher GPC. It is due to the reason that GPC
mainly depends on membrane module cost (MC), compressor cost
(CC) and annual cost of CH4 lost in permeate (CH4LS) as shown in
Table 1. With the increase in membrane area (or ber length), the
above mentioned costs increase resulting in the increase of GPC.
It can also be observed that non-ideal case show less GPC in
comparison with ideal case (maximum difference of 8%) for the
same ber length. As stage cut and a compressor power requirement
is decreasing with the decrease in membrane permeance, it leads to
reduce the GPC of the membrane separation system.
In order to see the effect of higher concentration CO2 feed on
process economics, the above procedure is repeated for 70% CO2
in feed gas as shown in Fig. 15 (for compressor power) and Fig. 16
(for gas processing cost). It can be observed that the difference
between performance of ideal and non ideal models are more
pronounced in the case of higher CO2 composition feed. For
example, the maximum difference between ideal and non ideal
cases for gas processing cost is increased from 8% (for 40% CO2
concentration feed) to 15% (for 70% CO2 concentration feed). It is
due to the reason that higher CO2 in feed leads to increase in
temperature drop. As a result, membrane permeance reduces
while contributing to further decrease in compressor power and
gas processing cost.

100

200

300

400

500

Fiber length (cm)

Fiber length (cm)

Fig. 16. Comparison of gas processing cost by ideal model (constant permeance)
with non ideal model (temperature and pressure dependent permeance) at feed
CO2 composition 70% and methane purity 96%.

5. Conclusions
The temperature and pressure dependence of membrane permeance has been investigated for the case involving CO2 separation
from methane. The effect of variable permeance is included in the
cross ow model for hollow ber membrane separation. The model
is then included in the process simulation (Aspen HYSYS) as a user
dened unit operation along with other available unit operations in
order to investigate the membrane performance and process economics. The simulated model is validated with experimental published data where the simulated data exhibit good agreement with
the experimental and published results. The temperature drop due
to Joule Thomson (JT) cooling and its effect on membrane
permeance of both CO2 and CH4 has been studied. Similarly, the
effect of pressure ratio on membrane permeance has been reported.
The inuence of variable permeance (temperature and pressure
dependent) is studied by comparing separation performance (in
terms of retentate/product CO2 composition, methane loss and stage
cut) and process economics (gas processing cost) with the ideal
model where membrane permeance is assumed independent of
temperature and pressure. It has been shown that non ideal model
shows higher CO2 retentate composition, lower stage cut and
methane loss in comparison to ideal model for the same ber
length. It leads to lower compressor power requirements and gas
processing cost for the non ideal hollow ber membrane model. For
highly non ideal conditions (e.g., higher CO2 concentration feed),
non ideal effects related to module operation would be more
signicant in affecting the product quality (CO2 retentate/product
composition), methane loss, stage cut, compressor power and gas
processing cost of hollow ber separation systems. Thus, it is crucial

54

F. Ahmad et al. / Journal of Membrane Science 430 (2013) 4455

to include the effect in the proposed hollow ber membrane model

as an accurate assessment of performance and economics of gas
separation system.

TPI
UC
UCP
VOM

List of symbols

Wcp
x1
x2
y1
y2
Z

Membrane separation area (cm2)

Cross section area of membrane module (cm2)
Cross section area of ber (cm2)
Base plant cost (USD)
Installed compressor cost (USD)
Annual cost of methane loss in permeate (USD/year)
Annual contract and material maintenance cost
(USD/year)
CRC
Annual capital related cost (USD/year)
Cp
Specic Heat capacity (J/g K)
CPI
Ideal heat molar capacity (J/g K)
Cm,p
Heat molar capacity (J/mol K)
DL
Direct labor cost (USD/year)
Dd
Henrys diffusion coefcient (cm2/s)
Dh
Langmuir diffusion coefcient (cm2/s)
di
Inner diameter of bers (cm)
do
Outer diameter of bers(cm)
dm
Diameter of Membrane module (cm)
Ep
Activation energy for permeation (kJ/mol)
FC
Fixed cost (USD)
GPC
Gas processing cost (USD/MSCFD of natural gas product)
J
Gas permeation ux through membrane (MMSCF/
ft2 day)
i
Index of gas component
LOC
Annual labor overhead cost (USD/year)
LTI
Annual local tax and insurance cost (USD/year)
L
Length of bers (cm)
l
Membrane life (years)
M
Molar mass (g/mol)
MC
Total cost of membrane modules (USD)
MMBTU 106 BTU
MMSCFD 106ft3/day
MRC
Annual membrane replacement cost (USD/year)
MSCF
103 standard cubic feet (at standard temperature and
pressure)
NGLS
Annual loss of natural gas (MMSCF/year)
NHV
Heating value of natural gas (1066.8 MMBTU/MMSCF)
NWP
Wellhead price of crude natural gas (USD/MMBTU)
Nf
Number of bers/cross section area of ber (cm  2)
nf
Number of bers
n
index of membrane stage
OSF
On stream factor
P
Project contingency (USD)
Pi
Permeability of component i (mol/MPa-m2-s)
Pj
Permeability of component j (mol/MPa-m2-s)
ph
Pressure on the high pressure side (bar)
pl
Pressure on the low pressure side (bar)
Qf
Feed Flow rate (cm3(STP)/s)
Qp
Permeate ow rate (cm3(STP)/s)
Qr
Product/Retentate ow rate (cm3(STP)/s)
R
Radius of ber bundle (cm)
Rg
Universal gas constant (m3 Pa/kg-mol K)
SC
Start up cost (USD)
SCF
Standard cubic feet (at standard temperature and
pressure)
T
Temperature (K)
Th
Temperature of feed (high temperature) side (K)
Tl
Temperature of permeate (low temperature) side (K)
TFI
Total facilities investment (USD)
A
Am
Af
BPC
CC
CH4LS
CMC

Total plant investment (USD)

Annual utility cost (USD/year)
Utility cost (USD/kw h)
Annual variable operating and maintenance cost
(USD/year)
Power requirement for compressors (hp)
Mole fraction of carbon dioxide on shell side
Mole fraction of methane on shell side
Mole fraction of carbon dioxide on tube (permeate) side
Mole fraction of methane on tube (permeate) side
Compression factor

Greek symbols

aij
b

e
^

DQ
Dr
Dz

rm
rr
Zcp
mJT

Selectivity of the membrane

Pressure ratio
Porosity of the membrane (%)
fugacity coefcient
Packing density (%)
Molar permeation into an element (cm3(STP)/s)
Radial increments
Axial increments
Membrane thickness (cm)
Molar density of gas mixture (mol/cm3)
Reduced density
Compressor efciency (%)
Joule Thomson coefcient (K/bar)

Acknowledgements
This work was done with the nancial and technical support
from CO2 Management (MOR) research group, Universiti Teknologi PETRONAS.
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