Desalination 224 (2008) 28–33

A new energy-integrated pervaporation distillation approach

M.T. Del Pozo Gomez*, Andreas Klein, Jens-Uwe Repke, Günter Wozny
Institut für Dynamik und Betrieb technischer Anlage, TU–Berlin,
Straße des 17 Juni. 135, Sekr. KWT-9, 10623 Berlin, Germany
Tel. +49 (30) 3147 9818; Fax: +49 (30) 3142 6915; email: delpozo@dynamik.fb10.TU-Berlin.de

Received 15 January 2007; Accepted 11 April 2007

Abstract
Hybrid-pervaporation-distillation processes have been intensely studied in the last years and considered as a good
alternative in the separation of homogeneous azeotropic mixtures. Compared with the techniques in use in the
chemical industry, they can reduce the energy consumption and avoid the use of entrainers. However, due to the
evaporation enthalpy, a temperature drop is presented along the membrane and external heat exchangers are required
between two consecutive pervaporation steps. In the present paper, a process approach has been developed in order
to avoid the external energy support and the temperature drop along the module. The novel energy integration
concept utilizes the distillate vapor stream of a distillation column as heating medium in the membrane. The vapor
condenses partially and energy is released directly into the module. For the study of the new energy integrated
process, a novel membrane configuration is developed and a mathematical model is built. Simulation results show
that the new process can yield to higher permeation fluxes and smaller temperature drop in the membrane, what also
means a reduction in the required membrane area, if a constant purity in the product is considered. Due to the energy
integration concept, there is no need of external heat supply in the pervaporation and the permeate flux rises, which
can reduce the operation and investment costs.

Keywords: Energy integration; Hybrid process; Pervaporation and distillation; Azeotropic mixture

1. Introduction
Hybrid pervaporation distillation processes
represent a potential alternative in the separation
of homogeneous azeotropic mixtures. It has been
*Corresponding author.
seen in the literature [1–3] that compared with the
techniques in use, they can reduce the energy
consumption, avoid the use of entrainers and
present a simple process structure. However, tem-
perature and concentration polarisation become
the performance bottleneck in the pervaporation

Presented at the 11th Aachen Membrane Colloquium, 28–29 March, 2007, Aachen, Germany.

0011-9164/08/$– See front matter © 2008 Published by Elsevier B.V.

doi:10.1016/j.desal.2007.04.075
 M.T. Del Pozo Gomez et al. / Desalination 224 (2008) 28–33 29

techniques [4]. In the last years large efforts have

been done in order to reduce these effects [5,6].
In the present work, a process approach has been
developed in order to decrease external energy
support and temperature and concentration polari-
sation effects. The separation of an acetonitrile
(ACN)–water mixture has been taken as an
example. For all process calculations the com-
mercial software gPROMS is used. Simulation
results show that the new process can present
higher permeation fluxes and smaller temperature
drop in the module, which means a reduction in
the required membrane area, if a constant purity
in the product is desired. Due to the energy Fig. 1. Hybrid process flow sheet principle (new heat
integration concept, there is no need of external integrated approach).
heat supply in the pervaporation. As a result, the
new process flow sheet can yield to a reduction in
the operation and investment costs.

2. Energy integration concept

2.1. Process flow sheet
In Fig. 1 the principle flow sheet of the energy
integrated process is presented for a feed lower
than the azeotropic point. The process is com-
posed of a high-pressure distillation unit and a
pervaporation unit for the separation of the homo-
geneous azeotropic binary mixture acetonitrile–
water. The feed is led into the distillation column.
At the bottom of the column an almost pure
component is obtained and at the top the azeo-
tropic concentration 58 mol% (ACN) at 3.5 bar is
achieved. This stream is fed into a heat exchange
located in the pervaporation unit. It condenses
partially and the condensation energy is released
into the pervaporation process. After that, the
heating stream will be totally condensed and split
in two flows: the reflux flow of the column and
the feed of the pervaporation module. Here, the
retentate is composed of pure acetonitrile and the
aqueous permeate is composed of almost pure
water.
Fig. 2. Heat integration inside the membrane module.
2.2. Pervaporation module design
The proposed novel structure of a heat inte-
grated pervaporation unit is shown in detail in
Fig. 2. A heat exchange pipe is located in the
membrane feed side. The steam going out of the
distillation process is fed in this pipe. A heat
exchange process takes place between the heating
steam (vapour azeotropic mixture) and the fluid
(liquid azeotropic mixture) in the retentate side. It
causes a partial condensation of the vapour
stream in the heating pipe, a reduction of the tem-
perature drop along the membrane, and a rise in
the permeate flux. On the other hand, with the
introduction of a heat exchange pipe, the space in
the retentate side decreases and the velocity of the
fluid increases. The effect is an increase in the
turbulent character of the flux and a decrease in
the concentration polarisation, which supports the
mass transport.
30 M.T. Del Pozo Gomez et al. / Desalination 224 (2008) 28–33
Fig. 3. Improved designs of the heat integrated module.
In the present paper, two improved designs are
proposed. In Fig. 3 (left), a ripped internal heat-
ing pipe increases the turbulent flow over the
membrane and the heat transfer. Another possi-
bility is a corrugated active membrane surface,
(see Fig. 3, right). It increases the pervaporation
surface and also the turbulent flow. Compared
with the hybrid process (Fig. 2), these two new
designs should offer a major permeation flux and
minor concentration polarisation effect, saving
energy in the process and increasing the permeate
flux through the membrane.
3. Mathematical model
To describe the hybrid process, a dynamic
model was developed in gPROMS®. For the
column, a previously described model validated
at the pilot plant at the TU-Berlin was used [7].
The tray hydraulics were calculated with the
Francis Weir formula, the phase equilibrium with
the Wilson equation, and the tray efficiency by
Murphree. The pressure drop was calculated on
each tray and within the heat exchangers. For the
pervaporation system, the thermodynamical prin-
ciples previously developed [8] were used. The
permeability coefficients were calculated using an
Arrhenius temperature function. The necessary
coefficients were obtained from the literature [2].
Activity coefficients were calculated with the
Wilson equation and partial pressure values with
the Antoine equation. In the computation the
pervaporation membrane was discretised in 50
intervals using the differential equation tool in
gPROMS®, and a partial differential equation
system was defined along the axial direction.
4. Simulation results of a case study
With the model defined above a case study
was simulated. The feed stream was set at 10 l/h
(saturated liquid) with a concentration of
30 mol% ACN. The desired product purity in the
column was 99 mol% water at the bottom and
58 mol% ACN at the top. The column (pilot plant
at TU–Berlin) had 28 trays and a 114 mm dia-
meter, and the working pressure was 3.5 bar. It
was supposed a silica active surface in the mem-
brane. After reaching the stationary point, 7.7 l/h
distillate stream at 390.98 K was obtained. It was
assumed an external constant heat support in the
system in order to quantify the influence of the
energy supply in the pervaporation. This value
was taken smaller than the total energy released
by the condensation of the steam leaving the
column. The corresponding percent values are
shown in Table 1.
 M.T. Del Pozo Gomez et al. / Desalination 224 (2008) 28–33 31

Table 1 5. Conclusions
Influence of the energy support in the process parameters
In the present paper, a novel heat integration
Q (MJ/h) 0 0.9 1.5 2.4 concept for a hybrid distillation pervaporation
% QCond 0 10.6 17.7 28.3 process has been developed and two membrane
XACN-exit 0.74 0.82 0.88 0.98 module designs have been presented. Simulation
JPermeate (kg/m2 h) 1.62 2.4 2.78 3.26 results show that using heat integration obtains
increase of product purity (up to 30% in the
present case study) and significant membrane
surface reduction if desired product purity is
fixed. With the new process design an increase in
the turbulence and a decrease in the temperature
and concentration polarization phenomena (prob-
lems of the pervaporation performance) are
solved. It has to be pointed out that no additional
external energy supply is needed in the pervapo-
ration process because the condensation energy of
the distillate stream is sufficient for heating the
membrane module.

Fig. 4. Permeate flux and acetonitrile molar fraction of

the product vs. Q. 6. Symbols
JPermeate — Permeation flux, kg/m2 h
In Fig. 4 and Table 1 the influence of the heat Q — Energy supply, MJ/h
integration in the pervaporation process is %QCond — Condensation energy, %
analysed for a fixed membrane area of 0.44 m2 X — Molar fraction
and with a permeate pressure of 3 mbar. It can be
seen that a small energy support compared to the
distillation energy input benefits the perva- Acknowledgments
poration by increasing the permeate flux and the The authors would like to thank EFRE
molar fraction of acetonitrile at the exit of the (request number 10134788) for sponsoring this
module. That reduces the required membrane area project.
(for a constant purity in the product) and the
supplied energy can be totally obtained from the
condensation of the distillate product (8.43 MJ/h
in this case study). References
For the experimental analysis of the developed
[1] F. Lipnizki, R.W. Field and P.-K. Ten, Pervapo-
membrane model, a new laboratory plant was ration-based hybrid process: a review of process
developed at the TU–Berlin and prepared for the design, applications and economics, J. Membr. Sci.,
connection with the distillation column (see 153 (1999) 183–210.
Fig. 5). With this plant different module analyses [2] S. Sommer, Pervaporation und vapour permeation
with or without a coupling to a high-pressure with microporous inorganic membranes, PhD Thesis,
distillation plant [9] are in progress. RWTH Aachen, Germany, 2003.
32 M.T. Del Pozo Gomez et al. / Desalination 224 (2008) 28–33
Fig. 5. Newly developed laboratory plant.
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[3] J. Fontalvo, P. Cuellar, J.M.K. Timmer, M.A.G.
Vorstman, J.G. Wijers and J.T.F. Keurentjes, Com-
paring pervaporation and vapour permeation hybrid
distillation processes, Amer. Chem. Soc., 0.1021/
ie049225z, 2004.
[4] S. Sommer, B. Klinkhammer, M. Schleger and T.
Melin, Performance efficiency of tubular inorganic
membrane modules for pervaporation, AIChE J., 51
(2005) 162–177.
[5] J. Fontalvo, M.A.G. Vorstman, J.G. Wijers and
J.T.F. Keurentjes, Heat supply and reduction of
polarization effects in pervaporation by two-phase
feed, J. Membr. Sci., 279 (2006) 156–164.
33
[6] M.V. Leland and R.A. Franklin, Vibrating per-
vaporation modules: Effect of module design on
performance, J. Membr. Sci., 255 (2005) 213–224.
[7] J.-U. Repke, F. Forner and A. Klein, Separation of
homogeneous azeotropic mixtures by pressure swing
distillation — Analysis of the operation performance,
Chem. Eng. Techn., 28 (2006) 1551–1557.
[8] J.G. Wijmans and R.W. Baker, A simple predictive
treatment of the permeation process in pervaporation,
J. Membr. Sci., 79 (1993) 101–113.
[9] A. Klein, J.-U. Repke, M.T. Del Pozo Gómez and G.
Wozny, Annual Meeting, AJChE, San Francisco,
409 Separation Design, 2006.