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Abstract
Membrane technology is used for a wide range of separations from particle-liquid separations to gaseous and liquidliquid
separations. In this paper, we introduce a detailed model that describes a general membrane separation. The model disregards
many common assumptions such as plug flow; constant temperature; constant pressure; binary mixture; steady-state conditions;
and constant physical properties. Our approach is applicable to any membrane separation and in this paper we demonstrate its
application to both liquid mixture separation (pervaporation) and gas separation in hollow-fibre modules. Both cases are seen to
exemplify the need for a detailed model. 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Liquid liquid separation; Reynolds number; Hollow fibre
1. Nomenclature
A
D
E
F
fv
H
J
K
k
L
P
Q
R
r
T
t
U
V
6
Membrane area
Dispersion coefficient
Energy flux
Viscous and diffusive flux
Friction factor
Molar enthalpy
Molar mass flux through membrane
Molar kinetic energy
Thermal conductivity
Fibre length
Pressure
Energy flux through membrane
Fibre radius
Radial dimension
Temperature
Time
Molar internal energy
Volume
Velocity
z
z
zm
Subscripts
i
r
z
Axial direction
Molar density
Mass density
Component i
r-direction
z-direction
2. Introduction
During the last 30 years, the search for alternatives to
traditional energy intensive separation methods such as
distillation has led to the introduction of processes
based on membranes. Membrane processes often offer
cheaper capital and utility costs and can be used for a
wide range of separations: from particle-liquid separation, such as reverse osmosis, to gaseous and liquid
liquid separation. To achieve a desired separation, a
large membrane area is often required. In an industrial
plant, this area is supplied in a modular configuration
for which there are a number of variations. Historically,
plate-and-frame modules have been used, but more
recently, spiral-wound and hollow-fibre modules have
attracted a lot of interest as these offer much higher
packing densities (Krovvidi, Krovvali, Vemury, &
Khan, 1992).
0098-1354/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 9 8 - 1 3 5 4 ( 0 1 ) 0 0 6 7 0 - 6
694
In many areas of chemical process design and operation the use of mathematical models for process synthesis, optimisation and for control studies has shown
significant benefit. The application of these methods to
the design of membrane processes is now beginning to
be considered (El-Halwagi, 1992; Qi & Henson, 1998;
Marriott, Srensen, & Bogle, 1999). However, to minimise the technical risk that is inherent in the design of
any new process, it is essential that detailed unit models are used. Unfortunately, to the best of our knowledge, a detailed model of a general membrane
separation process is not currently available from published literature. Although a number of models do exist
(Krovvidi et al., 1992; Qi & Henson, 1997; Coker,
Freemann, & Fleming, 1998), due to the complex nature of flow through membrane modules, these usually
rely on a number of fixed assumptions. These include:
plug flow; constant temperature; constant pressure; bi-
Sub-model
1-D
2-D
Yes
Yes
Yes
Yes
Yes
Yes
Yes
Yes
No
Yes
No
Yes
Yes
Yes
Yes
Yes
3. Mathematical model
We have developed a consistent modelling approach
that can consider spiral-wound, plate-and-frame, tubular, and hollow-fibre membrane modules. However, in
this paper, we will demonstrate the approach on the
latter. Hollow-fibre modules contain a large number of
membrane fibres housed in a module shell. Feed can be
introduced on either the fibre or the shell side and
permeate is withdrawn in a co-current, counter-current,
or cross-current manner. The flow pattern in a hollowfibre module with fibre side feed and a counter-current
permeate stream is illustrated in Fig. 1.
To simulate a membrane module three sub-models
are required; two to describe the flow on either side of
the membrane and a third model which characterises
the separative properties of the membrane and any
porous support material. Two alternate flow sub-models have been developed: a one dimensional (1-D) flow
model and a two dimensional (2-D) flow model. Both
models are developed from rigorous dynamic mass,
momentum and energy balances, and thus are applicable to any membrane separation. The model characteristics are summarised in Table 1 and the main model
equations are given in the Appendix.
The 2-D sub-model formally describes axial variations in concentration, velocity, temperature and pressure and radial variations in velocity and concentration (concentration polarisation). However, whilst it
provides the most rigorous approach, the 2-D
sub-model is limited to flow inside the fibres. In
contrast, the 1-D (plug flow) sub-model is more versatile but an additional empirical parameter is required
to describe concentration polarisation (this is discussed
in more detail in Section 4.1). Both models disregard
common assumptions such as isothermal flow, binary
mixture, negligible axial diffusion, steady-state conditions, and constant physical properties (Table 1).
Therefore, it is apparent that model accuracy is
now mainly constrained by uncertainty in parameter
values, such as molecular diffusivity, and uncertainty in
3.2. Summary
A detailed model of a hollow fibre membrane module has been described in this section. The model is
applicable to any membrane separation and can be
used for a wide range of applications, from steadystate simulation and process synthesis, to investigating
control issues and dynamic optimisation. In future
work, we will address many of these issues using the
detailed model. However, in this work we have restricted our studies to the steady-state simulation1 of
two different membrane systems: a pervaporation separation and a gas separation.
4. Model application
We now investigate some of the features of the
detailed model described in the previous section. To
demonstrate the generality of the model, both liquid
mixture (pervaporation) and gas mixture separation are
considered.
1
Steady-state simulation is easily achieved using a dynamic model
by setting all the time derivatives to zero.
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4.1. Per6aporation
Many of the liquid mixtures which need to be separated in the fine and speciality chemical industries
are either close-boiling or azeotropic in nature. Extractive distillation is a common technique for separating
such mixtures, however, it is energy intensive and requires the addition of a solvent to change the relative
volatilities of the various components. The solvent is
often toxic (e.g. benzene) and later must itself be separated from the mixture. These drawbacks fuel continuous research looking for new and better separation
techniques. The use of pervaporation as an alternative
to distillation for difficult separations has been suggested for a number of cases. In particular, the use of
pervaporation to separate organics from water is becoming increasingly important (Fleming and Slater,
1992).
In this process, the membrane forms a semi-permeable barrier between a liquid feed and a low pressure
gaseous product. Consequently, heat must be supplied
to evaporate the permeating material-typically resulting
in a feed stream temperature drop. However, in contrast to distillation, only the heat of evaporation for a
small fraction of the mixture, the permeating material,
must be provided. Thus, the energy requirements of a
pervaporation plant are much lower. Furthermore,
when compared to distillation, pervaporation offers a
number of additional advantages (Fleming and Slater,
1992), such as: lower capital costs, modular design
(easier retrofitting and de-bottlenecking), and often superior separations as it is not constrained by thermodynamic azeotropes.
In this section, we consider two important pervaporation systems: the removal of organics from wastewater and the dehydration of azeotropic ethanol/water
mixtures.
696
Fig. 2. Radial concentration profile (2-D model). Radial concentration profile assuming a stagnant boundary layer (1-D model).
Single module
Plant
(nine modules)
248.5
96.8
100
94
60
400
60
13.3400
44.8
94
60
400
97.3
97.2
97.4
97.4
99.7
99.8
Table 3
Multicomponent gas separation system (Pan, 1986)a
Feed temperature (K)
Feed pressure (bar)
Permeate pressure (bar)
H2 permeability (1010 mol/m2 s
N2 permeability (1010 mol/m2 s
Ar permeability (1010 mol/m2 s
CH4 permeability (1010 mol/m2
a
Pa)
Pa)
Pa)
s Pa)
298
69.64
11.23
284
2.95
2.84
7.70
697
698
Table 4
Binary gas separation system (Smith et al., 1996)a
Case
Flow pattern
Feed composition (H2 fraction)
Feed temperature (K)
Feed pressure (bar)
Permeate pressure (bar)
H2 permeability (1010 mol/m2 s
Pa)
N2 permeability (1010 mol/m2 s
Pa)
Co-current
20%
308
137.9
1.379
109.3
Counter-current
85%
308
137.9
27.58
109.3
10.93
0.607
5. Conclusions
In this paper, a detailed model that describes a
general membrane separation has been introduced. The
699
Appendix A. Appendix
Equations
Boundary
condition
Mass
balance
Momentum
balance
#(z mwz )
#(z mw 2z ) #P 2fw
=
#t
#z
#z R
z (0, L]
Energy
balance
#(z(U+K))
#(Ez ) AQ
=
+
#t
#z
V
z (0, L)
z (0, L)
Ez = zwz (H+K)k
#(F zi )
=0
#z z = L
#T
=0
#z z = L
#T
#z
The main equations in the 1-D and 2-D flow submodels are presented in Table 5 and Table 6. For a full
derivation of the model equations please refer to Marriott (2001).The 2-D sub-model is derived assuming
radially symmetric laminar flow through a circular conduit. In addition, radial variations in temperature and
pressure are neglected. The 1-D sub-model assumes
plug flow through a conduit, for which pressure losses
are characterised using the frictional parameter f6.
For both flow sub-models the membrane flux variables, J and Q, are calculated by a coupled membrane
sub-model. This model characterises the separative
properties of the membrane. However, the model used
depends on the type of separation (several were used in
this work) and hence is not given here.
References
model is developed from rigorous mass, momentum
and energy balances and disregards many common
assumptions. The use of the model to investigate complex modelling issues in a liquid separation system has
been demonstrated. The model has also been used to
assess the performance of approximate models in a gas
separation system. In both these cases it is seen that a
detailed model is essential. In future work, we will
investigate the use of the model for the optimal design
of different membrane systems.
Table 6
2-D flow sub-model
Mass
balance
Momentum
balance
Equations
Boundary
condition
#t
#z
r #r
#z
z
F i = zi wzDi i
#z
#zi
r
F i = zi wrDi
#r
Z (0, L)
r (0, R)
#(z mwz )
#(z mw 2z ) #P
=
#t
#z
#z
z (0, L]
r (0, R)
Energy
balance
F ri r = R = JI
1 #(rz mwrwz )
#2w
1 # #wz
r
+ 2z
+v
r
#z
#r
r #r #r
#(z(U+K))
#(Ez ) AQ
=
+
#t
#z
V
Ez = zwz (H+K)k
#T
#z
#(F zi )
=0
#z z = L
z (0, L)
#wr
=0
#r r = R
wz r = R = 0
#T
=0
#z z = L
700