ELSEVIER Journal of Membrane Science 89 ( 1994) 153- 169

A generalized solution-diffusion model of the pervaporation

process through composite membranes
Part II. Concentration polarization, coupled diffusion and the
influence of the porous support layer
A. Heintz*, W. Stephan
UniversitSit Heidelberg, Physikalisch-Chemisches Institut. Im Neuenheimer Feld 253, D-69120 Heidelberg, Germany
(Received May 20, 1993; accepted in revised form December 8, 1993)

Abstract

The central part of the model is based on the solution-diffusion process which describes fluxes of low molecular
weight components in the dense active layer. Using the Maxwell-Stefan theory, coupled equations for the diffusive
fluxes through the dense layer are derived. The concentrations on the phase boundaries inside the membrane are
determined by solubility equilibria with the adjacent phases of the feed and permeate phase, respectively. They are
calculated using the UNIQUAC model as described in Part I of this series. Fluxes through the porous sublayer are
calculated by a general kinetic gas flow model which includes Knudsen flow and laminar flow as special cases. The
solution-diffusion model and the pore flow model are combined resulting in a resistance-in-series model for fluxes
through the dense layer and the support layer.
The generalized model is applied to the pervaporation of six aqueous/organic mixtures through the standard
poly (vinyl alcohol) /poly (acrylonitrile ) (PVA/PAN) composite membrane. It turns out that the strong non-ideal
solubility behavior of the liquid mixture components in PVA and diffusive coupling effects play the dominant
roles in the pervaporation process. More simplified models which do not account for these physico-chemical ef-
fects fail to describe fluxes and separation diagrams in PVAIPAN membranes. Introducing the influence of the
porous support layer leads to almost complete agreement with experimental data even at elevated permeate
pressures.
The influence of concentration polarization has also been studied in some detail and is found to be of minor
importance compared to the other contributions.

Key words: Transport theory; pervaporation; Maxwell-Stefan theory; Pore flow model; Poly(viny1 alcohol) membrane

1. Introduction through dense membranes [ l-5 1. In the case of

It has been known for many years that the so-
called solution-diffusion model is suitable for
describing transport processes in pervaporation
*Corresponding author.
composite membranes the porous sublayer sup-
porting the dense active layer on the down-
stream side may exert an additional effect on the
fluxes and separation potential. This has been
pointed out by several authors [ 3,6,7 1. Further-
more, concentration polarization in front of the

0376-7388/94/$07.00 0 1994 Elsevier Science B.V. All rights reserved

SSDIO376-7388(93) E0223-7
154 A. Heintz, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169
feed side of the active layer can influence the
fluxes and separation characteristics under spe-
cial conditions [ 1,6,8-lo].
In this paper we develop a generalized model
which accounts for these contributions simulta-
neously. The importance of each contribution is
discussed quantitatively. Whenever it is possible
and justified by the results, simplifications and/
or assumptions have been made in order to re-
duce the complexity of the calculation procedure.
The composite membrane model is illustrated
in Fig. 1. Generally, a system consisting of three
layers is considered. On the left side in the liquid
feed mixture the composition is given by the
weight fractions wjF (or mole fraction xii?) where
i indicates that component i permeating the
composite membrane. For each component it
holds that the molar flux Ji is constant and has
the same value at any location in the composite
membrane under steady state conditions. The
layer in front of the active layer is the diffusive
laminar layer of the feed mixture which might
give rise to concentration polarization resulting
in weight fractions “t, of the liquid mixture at
the boundary to the membrane which differ from
the bulk weight fractions wLF.
In the framework of the solution-diffusion
model it is assumed that thermodynamic solu-
bility equilibrium exists between the liquid phase
outside the membrane and the swollen mem-
brane phase adjacent to the phase boundary. As
a consequence there exists equality of the ther-
modynamic activity Ui at the phase boundaries
of the liquid/membrane (CZiF=a iF) .
ei)iF (or wjF if no concentration polarization oc-
curs) and w:F, the weight fraction inside the ac-
tive membrane layer at the feed side boundary,
are connected by the phase equilibrium condi-
tion. Inside the active layer the components move
by diffusion according to the gradients of their
weight fractions w:.
At the boundary to the pore space of the po-
rous support layer, again the existence of solubil-
ity equilibrium is assumed between w& (inside
the active layer) and w$ (outside the active
layer). x7 is the mole fraction corresponding to
the weight fraction wTP.The flux through the po-
res of the support layer is considered to be a gas-
eous flow caused by the driving force of a pres-
sure gradient P - Pp. Pp is the permeate pressure.
There is no phase change when the components
leave the support layer entering the permeate
space with the weight fraction wip (mole fraction
xiP)-
In the following sections the model is devel-
oped stepwise and tested for increasing levels of
complexity by comparison with experimental
data.
2. Solution-diffusion model and the influence of
concentration polarization
We consider the flux Ji through the active layer
of the composite membrane. If diffusive cou-
pling is neglected, the fluxes J, are independent
from each other and it holds for J, according to
the solution-diffusion model:
J.=~.di”(,. .$, _S .w? )
(1)
’ J,f* 6” lF IF lP IP
where p is the membrane density, Mi and DiM are
the molar mass of component i and its averaged
diffusion coefficient in the active layer,
respectively.
DijiMis defined by
%F. SF
DiM( w:)dw:
F
*J
DiM= ;;;f:sjF
- wTp .SiP) (2)
SiF=w&/$;F and Sjp are the solubility coeffl-
cients at the feed side and the permeate side of
the active layer, respectively. SiF and Sip are
quantitative measures for the solubility equilib-
rium of component i between the mixture phase
and the membrane phase of the active layer ma-
terial. At a given Weight fraction tt;F (or w:p ) in
the liquid feed (or permeate) mixture, w:F (or
wip ) can be calculated if SiF (or Sip) is known
from experimental solubility data or from theo-
retical model calculations. In this paper S, and
Sip are calculated using the UNIQUAC model for
all mixtures studied. Details of calculating S, and
S,, at given $iF and wTp are described in part I
[Ill.
 A. Heintz, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169 155

feed laminar active support permeate

layer layer layer

PP
aiF

aiP

WiF
wiP
(XiF)
@iPI

i I
=Q I I
Y
pressure

K
Pp 1
pore length

Fig. 1. Concentrations and pressures in the pervaporation process through composite membranes. w,&xiF): weight fractions
(mole fractions) in the feed mixture; titiF:weight fraction in the feed mixture adjacent to the active membrane layer; w&: weight
fraction inside the active membrane layer facing the feed mixture; w&: weight fraction inside the active membrane layer facing
the support layer; xt, P*: mole fraction and total pressure at the upstream side of the porous layer; ( w~~(x,~): weight fraction
(mole fraction) in the gaseous permeate identical to the values at the downstream side of the porous layer; Pp: total permeate
pressure.

For the following discussion of concentration The theory of concentration polarization pro-
polarization we neglect the second term in Eq. vides a functional connection between iCZFand
( 1 ), i.e., S’ip*w$ =O. This simplification makes WiFin the feed mixture. For binary mixtures the
the discussion easier and it is also justified by the basic equation for concentration polarization in
fact that w& is usually close to zero in pervapor- non-electrolyte fluids (liquids or gases) is given
ation since the permeate pressure Pp (and as a by [ 1,10,12]:
consequence also P*) is kept as low as possible I’, -J1 + V, . J2 @,F(z=#)--7,
in real situations. Because the effect of concen- ew (3)
( k > @IF(Z=O) -.&
=
tration polarization decreases at higher per-
meate pressures, the discussion at Sip* w*, =O is with k=D12/d’, the feed side mass transfer coef-
sufficient in order to estimate the maximal effect. ficient, and
156 A. Heintz, W. Stephan /JournalofMembrane
XlF * K
@IF= l-&= (4)
X1F’ VI +kF’ v,
the volume fraction of 1 at z=8’ and z=O, re-
spectively (see Fig. 1) . D1 2 is the binary diffu-
sion coefficient in the feed mixture and V, and
V, are the molar volumes of component 1 and 2
in the feed mixture. VIJ1+ V2J2 is the total vol-
ume flow which has the meaning of an averaged
velocity. J1 is defined as
~~=v,.J,/(v,.J,+v*.J,)=l-~~ (5)
With ,!&* w*, = 0, Eq. ( 1) can be rewritten as
(6)
By substituting Eq. ( 5 ) into (6 ) and Eq. (6 ) into
(3 ) we obtain an equation which allows to deter-
mine @rF(z=#) at agiven @~F(z=O) provided
the DiM, SiF and p Values, as Well as 6” and k are
known.
Furthermore, we have made the assumptions
that @IF(z=S~)~CTJ~F and @~F(z=O)~W~F
which means that the volume fractions have been
replaced by the corresponding weight fractions.
Eq. (3) makes clear that $I,?% wlF is only ob-
tained if the exponent on the left side of Eq. ( 3 )
is close to zero which is the case when DiM.SiF/
da-pi is small compared to k.
S,= at a given & can be predicted by the UNI-
QUAC model. The calculation procedure is de-
scribed in detail in Part I [ 111. DiM are averaged
diffusion coefficients according to Eq. (2 ) . They
have been calculated using the concentration-de-
pendent coefftcients Di ( w: ) of the pure compo-
nents in the membrane material of the active
layer. Data of water at 333 K are available from
time-dependent vapor sorption experiments with
flat polymer sheets by measuring the mass up-
take of pure solvent vapor as function of time and
analyzing the data on the basis of Fick’s second
law of diffusion [ 13 1. The diffusion coefficient
of water used in the integral of Eq. (2) for cal-
culating &o depends strongly on the concen-
tration passing a maximum. The experimental
data of the diffusion coefficients of the organic
components are not very accurate and therefore
Science89 (1994) 153-169
constant values for DiM adjusted to the fluxes of
the pure organic components through the PVA/
PAN membrane were used in the model calcula-
tions rather than the experimental data taken
from the kinetic vapor sorption isotherms. 6”, p
and DiM are taken from the data listed in Tables
1 (left column ) and 2.
For the example ethanol/water and the PVA/
PAN composite membrane we calculated the
fluxes Ji using Eq. (6) with GiF obtained from
Eq. (3) at a given feed composition w,F. The S,,
values were calculated according to the proce-
dure described in Part I [ 111 and the Di, values
for water in PVA were obtained from Eq. (2 ) us-
ing experimental data [ 13 1.
The results for the partial mass fluxes jHzO =
J Hz0 %H20 and JEtOH-MElOHare shown in Fig. 2
for the cases k=m (no concentration polariza-
tion, $LF= WiF) and k= lop3 (cm/s). This latter
value for k was chosen because it corresponds to
the hydrodynamic situation in a plate and frame
module [ lo] used in the equipment for measur-
ingjHzO and&OH [ 1 4 1.
From Fig. 2 two conclusions can be drawn.
First, the solution-diffusion model in the sim-
plified form of Eq. ( 1) with uncoupled diffusion
is not able to describe the experimental data of
the fluxes adequately. Secondly, the effect of
concentration polarization is small. This is dem-
onstrated in more detail in Fig. 3. The flux ratio
ji( k) /ji( k= m) is larger than 90% for water and
95% for ethanol in the k region of plate and frame
modules for concentrations which are of practi-
cal interest for dewatering organic solvents.
Fig. 3 reveals that the flux of ethanol, the com-
ponent with the smaller permeability, is de-
creased by concentration polarization as well as
the water flux. Usually a higher flux of ethanol
would be expected since &on,,> WE~OH,Fbut this
is overcompensated by the fact that the concen-
tration-dependent solubility coefficient S,,,,,,
leads to lower solubilities of ethanol in the PVA
membrane when the weight fraction of ethanol
in the liquid mixture increases in this range of
liquid mixture concentration. This is due to the
strong synergistic solubility effect of ethanol in
PVA described in detail in Part I of this series
ill].
 A. He&z. W. Stephan /Journal ofMembrane Science 89 (1994) 153-169 157

Table 1
Diffusion coefftcients and Maxwell-Stefan interaction parameters

6,x-10”” &r(~‘H20)-10”b L& (HZO/organic)-10”

(cm’/s) (cm’/s) (cm*/s)

Methanol 223 100+exp(-~I~25)~125 20

Ethanol 30 lO+ (W’,/0.36)‘-50 25
nPropano1 20 lO+ (m’, /0.36)‘-30 25
i-Propanol 20 lO+ (~;/0.36)‘-30 40
Dioxane 30 10+(~;/0.36)2~15 0.1
THF 25 lO+ (W’,/0.36)2*20 0.1

‘Constant values adjusted to the fluxes of the pure organic compounds (used in the calculations shown in Fig. 4).
bAdjusted to the experimental partial fluxes of the mixtures depending on the mean weight fraction of water in PVA:
*; = (whzo.P+ WL2O.P) /2 (used in the calculations shown in Fig. 5 and Figs. 7- 12 ) .

Table 2
1 .O
Membrane specific parameters for the PVA/PAN composite
membrane

(a) Active PVA layer: (b ) Porous PAN support 0.8

layer
F
p= 1.2 g/cm3 d,,,,=1.6-lo-sm II 0.6
6”=1.3*10-‘m 6P=1*10-4m 5
N=7 P
Y 0.4

k (cm/s)
Fig. 3. Ratio J(k) / J( k= co) calculated for the pervapora-
tion of a mixture water/ethanol at 333 K and different weight
fractions of water in the feed. w,,,,,,= 0.05: ( n ) water, ( A )
ethanol; w,,,.~_~= 0.01: (0 ) water, (A ) ethanol.

Since the effect of concentration polarization

is small we neglect this effect in the following
sections where increasingly more complicated
models are developed and tested which account
for diffusive coupling in the active layer and the
effect of the porous support layer.

3. Solution-diffusion model and the influence of

0.0 0.2 0.4 0.6 0.8 1.0 coupled diffusion according to the Maxwell-
wzFof ethanol in feed Stefan theory

Fig. 2. Partial fluxes for the system water/ethanol/PVA at In this section the solution-diffusion model in
333 K. Experiments [ 141: (0) water, (A ) ethanol, Pp=20 the active layer is extended by introducing dif-
mbar; calculation: (---) k=cq (-) k= lo-’ (cm/s). fusion coupling of the permeating components
158 A. Heintz, W. Stephan /Journal ofMembrane
using a modified Maxwell-Stefan approach. This
approach is described in the Appendix.
The equations of coupled diffusion [Eqs.
(A 15 ) and (A 16 ) ] can be rearranged by divid-
ing Eq. (A16) by (A15):
tw;.&M +42) -D,,-h
(7)
This differential equation can be solved for given
permeate pressure, values of w:, and ratios of J2/
J, providing values of wiP and finally Wipe The
integration has been performed numerically by
the following procedure. At a given composition
W$, W:F= &!?;r* WiFcan be calculated according to
the UNIQUAC model. At a given permeate pres-
sure Pp the unknown weight fractions in the per-
meate wip have to be estimated in a first attempt.
Using the UNIQUAC model for gaseous mixture
solubilities, the corresponding equilibrium
weight fractions in the membrane w’,~ and wip
are obtained. The partial fluxes are connected
with the permeate weight fraction wip by
J, -MI 1
(8)
W1P=J1441 +J2.M2=l+J2M2/J,M,
wip defines the ratio J,M,/J,M, to be substi-
tuted into Eq. (7 ). Numerical integration of Eq.
( 7 ) provides values of w’,~ and wip which will
differ from the first estimate and, consequently,
from these values new values for wlp and J2M2/
J&f, are obtained. Solving Eq. ( 7 ) again gives a
third set of solution for wip. The iterative proce-
dure is repeated until two following sets of solu-
tion for wIp differ by less than 0.0 1%.
Eq. (7 ) has to be solved in each iteration step.
This calculation method is tedious and time con-
suming. Eqs. (A15) and (A16) can also be
solved by an approximation which deals with
difference equations rather than differential
equations. Therefore, Eqs. (Al 5) and (Al 6) can
be rewritten as:
Science 89 (1994) 153-169
D,,\?I;
Aw; +1>,M
D12 +w’, D,, +\?I;&., >-
~/(PM,)-Aw; (9)
D,,\?I;
Aw; +&,
D,2 +jcl;D,, +‘%‘;D,, >’
p/(S”.M2)-Aw; (10)
DiM in Eqs. (9) and ( 10) are averaged diffu-
sion coefficients for the pure components as de-
fined by Eq. (2 ) with W:r = WjF’sir. The concen-
tration polarization is neglected ( WiF= Gir) and
D12 has to be adjusted to the experimental par-
tial fluxes. Eqs. (9 ) and ( 10) represent non-lin-
ear equations for w’,~ and wip at given values of
W;F and wiF. Solving Eqs. (9) and (10) is much
more convenient than Eq. ( 7 ). Approximate so-
lutions for w ‘,p and w ip deviate less than 5% from
the values obtained by the exact solution of Eq.
(7) in all cases. In order to obtain consistent re-
sults for the permeate composition ( wlp, wzp) at
a given permeate pressure, the iteration process
has to be repeated until the Wipvalues fulfill Eq.
( 8 ) and are simultaneously in equilibrium with
the wip values according to the UNIQUAC cal-
culations. The effect of diffusion coupling is
demonstrated in Fig. 4.
The solid lines represent the model predic-
tions with coupled diffusion and the broken lines
without coupling. Obviously the introduction of
diffusion coupling according to the modified
Maxwell-Stefan theory leads to a decrease of the
water flux. The ‘fast moving’ component water
is slowed down by frictional interaction with the
‘slow moving’ organic compound. The flux of the
organic compound is slightly increased because
the slow moving organic compound is speed up
by the fast moving water. Both fluxes are shifted
into the direction required for an improved pre-
 A. Heintz, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169
0.0 0.2 , 0.4 0.6
w of ethanol in feed
0.8
I
1.0
iP
Fig. 4. Partial fluxes for the system water/ethanol/PVA at
333 K. Experiments [ 141: (0 ) water, (A ) ethanol,
Pr= mbar; calculation: (---) uncoupled diffusion, (-) cou-
pled diffusion.
diction. This was achieved by introducing the
additional adjustable parameter D12 which is a
measure for the mutual friction effect of water
and the organic compound. Parameters used for
all systems studied are listed in Tables 1 and
2(a).
In order to obtain better agreement with the
experimental data, it is necessary to make the av-
eraged diffusion coefficients of the organic com-
pounds 6,M dependent on the average water con-
centration in the PVA layer. In Table 1 6, is
given as function of WHzo, the average weight
fraction of water in the membrane. The numeri-
cal parameters of these functions have been ad-
justed to partial flux data. As an example for the
obtained improvement Fig. 5 shows the calcu-
lated partial fluxes for the system water-ethanol
at three different permeate pressures with diffu-
sion coupling and the diffusion coefficient of
ethanol adjusted to the experimental partial flux
over the whole range of composition. The same
D,z value has been used as in Fig. 4.
These results show that diffusion in multi
component mixtures depends not only on the
coupling parameter Q2 but also influences to
some extent the diffusion coefficients of the in-
dividual components.
159
0.0 0.2 0.4 0.6 0.8 1.0
WF of ethonol in feed
Fig. 5. Partial fluxes for the system water/ethanol/PVA at
333 K. Experiments [ 141: (0) water, (A ) ethanol, P,=20
mbar; ( n ) water, ( A ) ethanol, Pp= 100 mbar; (0 ) water,
(0 ) ethanol, Pp= 200 mbar. Calculation: coupled diffusion,
diffusion coefficient of ethanol adjusted to experimental par-
tial flux data (see text); (-) P,=20, (----) Pp= 100, (--
- -) Pp= 200 mbar.
At low permeate pressures (20-30 mbar) the
model predictions using coupled diffusion and
adjusted diffusion coefficients of the organic
components in the dense layer are satisfactory.
However, at higher permeate pressures ( 100-200
mbar) significant deviations of the calculated
fluxes from the experimental data are observed
(Fig. 5 ). In all cases the predicted water flux was
to high at higher permeate pressures. It turned
out that a further improvement could only be
achieved by taking into account the influence of
the membrane porous support layer which acts
essentially as a flow resistance.
4. The influence of the porous support layer on
the fluxes and separation diagrams
The porous support layer of a composite mem-
brane is usually 50-1000 times thicker than the
dense, active layer. The porous.support acts es-
sentially as a mechanical stabilization, but it can
160 A. Heintz, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169

also have an effect on the separation character- starting with the Maxwell-Stefan equations as
istics of the membrane. After leaving the thin discussed in the Appendix. The following equa-
dense active membrane layer, the components tions are derived for the molar fluxes J, and J2:
enter the porous support layer as a gaseous mix-
ture with a certain mole fraction xl at pressure 4x1 ‘P)
dz
P* as illustrated in Fig. 1. The driving force for

1 (12)
the flux through the pores is the pressure differ-
+L-B ‘XI .P dP
----+x, -A-P%
ence between P and the permeate pressure Pp.
l+B.P dz
The gaseous composition Xip inside the porous
layer may also differ from XT. d((l-x,)-P)
The support layer is assumed to consist of a dz
bundle of pores with different diameters d. The

1
pore distribution can be described by the follow- +s,-B. (1 -xl).P dP
sz+ ( 1 -x, )-A-P$
ing function according to Rosin, Rammler and 1 +B*P
Sperling [ 15 ] : (13)
Eqs. ( 12 ) and ( 13 ) were first derived by Present
and de Bethune [ 17 ] on the basis of the kinetic
theory of gases. The parameters A, B, b, a, and
where Y(d) is the probability of finding a pore f, are defined in the Appendix. They include the
of diameter d statistically weighted by the area molecular parameters which are listed in Table
rr- (d/2)2. The parameters N and d,,, were ad- 3. The general condition of the steady state re-
justed to the experimental pore size distribution quires that
data [ 16 1. They are listed in Table 2b. The pore
size distribution function used in the model cal- -- Jl J1
-- XIP
(14)
culations is shown in Fig. 6. x’p-J, +J2 Or JZ-l-x,p
The flow of a gaseous mixture through a single
A solution of Eqs. ( 12) and ( 13) is obtained
pore of a given pore diameter d can be treated
when Eq. ( 12) is divided by Eq. ( 13 ). This leads
to the following differential equation:

4’oE+081 h(x,,).P.$+ [h(X,p) +c, .p+c, .P2] ‘2,

+(cuO--l)~x~p~(l-x,p)=O (15)
with
h(XIp)=l+(Q)o-l)*(l -x1p) (16)
X1 =x1 +x1p (17)
c1 =f;B+A (18)
c2 =A.B (19)
A solution of Eq. ( 15 ) gives x, as a function
,i - _,_
of P inside the pore at given values P=P, and
O.OE+OO -
0 10 20 30 40 x1 =xIp at the right-hand side of the pore (z= 6’,
pore diameter (nm) seeFig. 1) [16]:
~%-wx,P~w-X1P)_
Fig. 6. Pore size distribution function V(d) of the PAN sup- x, =x*p -
h(XlP).P
port layer.
 A. Heintz, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169 161

P Eq. (20) represents an approximate solution

accurate to within l-2% of the exact numerical
exp( -c”). exp(c’)dP (20)
I result. For x1 =xr and P=P, Eq. (20) is the so-
Pp lution of pressure and gaseous composition at the
with left-hand side of the pore (see Fig. 1).
The following steps have to be performed in
c, ~F+o.5~c*~F2 order to obtain a complete solution for a com-
c’ = (21)
h(xw) posite membrane consisting of an active layer and
C, ~P+o.5~C2~P2
a porous layer represented by a single pore hav-
C” = (22) ing a diameter d and length Sp.
h&P) (a) Since J, and J2 are functions of P only at
Table 3
a given feed composition according to the pro-
Parameters used for calculating gas mixture viscosities at 333 cedure described in the previous section, xIp is a
K 1151 function of P* at a given feed composition due
to Eq. (14).
elk P’ 0
(b) Ifthis functionx,p(P) is now substituted
(K) (nm) ~m’/mol)
into Eq. (20) with x1 =x; and P=P, x: is ob-
Water 775 1.0 0.252 18.4 tained as function of P* at a given permeate
Methanol 417 0.5 0.369 42.5 pressure Pp. xlp has been eliminated.
Ethanol 431 0.3 0.431 61 (c) A definite solution for x7 and P is ob-
n-Propanol 495 0.2 0.47 1 77.9 tained from calculating the total flux Jt,,t= J1 + J2.
i-Propanol 518 0.2 0.464 79.9
THF 362 0.08
Addition of Eqs. ( 12) and ( 13) and combina-
0.549 85.04
Dioxane 450 0.1 0.5 87.1 tion with Eq. ( 15 ) gives:

+f~.A(x’).P].g
I

(23)
Since x1 is a function of P at given values of xlp
and Pp [ Eq. (20) 1, Eq. (23) can be integrated:

*A(x,(P))-P
1
-dP (24)

Since Jtoton the left-hand side of Eq. (24) is a

definite function of P at a given feed composi-
tion as described in the previous section, Eq.
(24) provides a definite solution for P. As a
0.0 0.2 0.4 0.6 0.8 1 .o
W~F of methanol in feed consequence x7 has also been fixed now in a def-
inite way.
Fig. 7. Partial fluxes for the system water/methanol/PVA at
Eventually values of x:, PC and xlp are ob-
333 K. Experiments [ 141: (0 ) water, (A ) methanol, Pr= 30
mbar; ( n ) water, ( A ) methanol, Pp = 120 mbar. Calcula- tained at a given feed composition and permeate
tion: coupled diffusion including effect of support layer, (-) pressure Pp providing the complete mathemati-
P,=30, (-- ) Pp= 120 mbar. cal solution of the transport problem of binary
162 A. Heintz, W. Stephan /Journal of Membrane Science 89 (1994) 153-169

0.0 0.2 0.4 0.6 0.6

&
1.0
0.0 0.2
WIFof
0.4
i-propanol
0.6 0.6
in feed
4
1 .o
wiF of ethanol in feed
Fig. 9. Partial fluxes for the system water/i-propanol/PVA at
Fig. 8. Partial fluxes for the system water/ethanol/PVA at 333 K. Experiments [ 141: (0) water, (A) i-propanol,
333 K. Experiments [ 141: (0) water, (A ) ethanol, &.=20 Pr=30 mbar; (m) water, (A ) i-propanol, Pr= 130 mbar.
mbar; ( n ) water, (A ) ethanol, &.= 100 mbar; (0 ) water, Calculation: coupled diffusion including effect of support
(0 ) ethanol, Pr = 200 mbar. Calculation: coupled diffusion, layer; (-) P,=30, (-----) Pp= 130 mbar.
including effect of support layer, experimental partial flux data
(seetext); (-) P,=20, (--) P,=lOO, (----) P,=200
mbar.

mixtures permeating the active layer combined

with a pore flow in series at a given pore diame-
ter d. At this point it is necessary to account for
the fact that the real porous layer consists of a
bundle of pores rather than of a single pore. Us-
ing the pore distribution function of Eq. ( 11) for
calculating the molar fluxes Jr and .& averaged
over the whole surface of the composite mem-
brane one obtains
co
Ji(d)*Y(d).dd
I
.ig o3 (25)
P(d)-dd
s 0.0 y c
0
0.0 0.2 0.4 0.6 0.8 1.0
WIF of methanol in feed
JI and & can be calculated at a given feed com-
Fig. 10. Separation diagram for the system water/methanol/
position and a given total permeate pressure.
PVAat333K.Experiments[14]:(0)P,=3O,(~)P,=120
Figs. 7 to 9 show the results of the combined mbar. Calculations: coupled diffusion including effect of the
model for three selected examples of the six sys- support layer; (-) Pp= 30, (-----) Pr= 120 mbar. Upper
tems studied including coupled diffusion and the curve: (----) VLE, thermodynamic vapor liquid equilibrium.
 A. He&z, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169
0.8
0.0
0.0 0.2 0.4 0.6 0.8 1.0
WIF of ethanol in feed
Fig. 11. Separation diagram for the system water/ethanol/
VAat333K.Experiments[14]:(Cl)Pr=20,(~)Pr=100,
( 0 ) I+ 200 mbar. Calculations: coupled diffusion includ-
ingeffect of the support layer; (-) Pr=20, (---) Pp= 100,
(- - -) &.=200 mbar. Upper curve: (---) VLE, thermo-
dynamic vapor liquid equilibrium.
influence of the porous support layer as de-
scribed above. The diffusion coeffkients of the
organic components and coupling parameters
have been used as presented in Table 1 (middle
and left column). The flow resistance of the po-
rous support layer causes a decrease in the pre-
dicted water flux especially at higher permeate
pressures ( 100-200 mbar). It has to be pointed
out that no capillary condensation effects are ac-
counted for in the theoretical treatment of the
flow through the porous layer. Separation dia-
grams of the three system examples are shown in
Figs. 10 to 12 demonstrating the almost quanti-
tative agreement of the theoretical with the ex-
perimental results. Similar quality of the results
is obtained for all other systems studied.
5. Conclusions
Pervaporation of mixtures through PVA/PAN
composite membranes is a complex process
which is influenced by several factors. Our model
163
0.8
0
s
i
a 0.6
.c
7
x
g 0.4
.-I
%
B
3 0.2
0.0 0.2 0.4 0.6 0.8 1.0
WF of i-proponol in feed
Fig. 12. Separation diagram for the system waterli-pro-
panol/PVA at 333 K. Experiments [ 141: (Cl) Pr=30, (m)
Pr= 130 mbar. Calculations: coupled diffusion including ef-
fect of the support layer; (-) Pp = 30, (---) Pr.= 130 mbar.
Upper curve: (----) VLE, thermodynamic vapor liquid
equilibrium.
takes into account non-ideal multicomponent
solubility effects, non-ideal diffusivity behav-
iour, diffusion coupling and the influence of the
porous support layer in order to describe semi-
quantitatively the performance of a pervapora-
tion membrane for a given separation problem.
The effect of concentration polarization has also
be studied and found to be of minor importance.
Therefore it has been neglected. A few experi-
mental data such as pure component vapour
sorption isotherms, pure component diffusion
coefficients (both available from vapor sorption
experiments with the PVA membrane material)
and vapor/liquid equilibrium data of the binary
mixture components are required for applying
the model. The most simple calculation proce-
dure is based on the neglection of diffusion cou-
pling in the active layer and neglection of of the
porous support layer. In this case the results are
unsatisfactory. Essential improvement of the
model description can be achieved by introduc-
tion of diffusion coupling using the Maxwell-
Stefan model with one additional adjustable pa-
164 A. Heintz, W. Stephan /Journal OfMembraneScience
rameter. Introducing a flow resistance of the po-
rous support layer leads to further improvement
particularly at higher permeate pressures. This
pore flow model requires experimental data
about the structure of the porous support layer.
This extended model leads to a satisfying de-
scription of all systems investigated over wide
ranges of feed concentrations and permeate
pressures.
With respect to practical applications it might
be sufficient to use a simple empirical expression
for the flow resistance of the support layer rather
than the quite complicated pore flow model in
order to reduce the amount of computational
work. However, UNIQUAC model calculations
and accounting for diffusion coupling based on
the Maxwell-Stefan theory is recommended
whenever the solution-diffusion model is ap-
plied to diffusive resistance in pervaporation
membranes.
6. Appendix
A generalized Maxwell-Stefan model for
transport processes of mixtures through dense
and porous membranes
Starting from the concept of irreversible ther-
modynamics, the following expression is ob-
tained for the relation between driving forces and
frictional resistances in a multicomponent
mixture:
(Al 1
Eq. (Al ) is known as the Maxwell-Stefan
equation [ 18 1, where ,uiis the chemical potential
of component i and dpJdz is its local gradient.
Xi are the mole fractions of the components j= 1,
2 .. . n and Vjare their local velocities. The recip-
rocal of 0; has the meaning of a friction coeffi-
cient accounting for the frictional effect exerted
by component j on component i.
The general expression for the chemical poten-
tial pi is given by
89 (1994) 153-169
P
+RTlnaj(T,Po)+JVidp (AZ)
PO
where py( T,P”) is the standard chemical po-
tential of pure component i in the ideal gas state,
A,,( T,P”) is the fugacity of the real pure fluid at
a standard pressure P” and temperature T. V, is
the partial molar volume of component i and P
the considered value of pressure. ai is the ther-
modynamic activity defined by
(A3)
whereJ( T,P”) is the fugacity of component i in
the mixture and yi is the corresponding activity
coefficient.
For the special case of ideal gas mixtures, Eq.
(A2 ) can be written
~i=~~(T,P”)+RTltio+RTl~~+RTlnP
P0
=pp(T,P“)+RTln(p.xi) (A4)
and for the case of condensed liquid mixtures one
obtains if liquid compressibility is neglected:
~i=~~“(Typ”)+RTln(xi*yi)+~(p-po)
(A5)
with
T,P”) +RTln&( T,P”)
~2” =pp( (Ah)
Usually the last term in Eq. (A5 ) can be ne-
glected at ambient pressure (pmp’). pgq is the
chemical potential of the pure liquid at p” and T.
In the cases where polymer substances are in-
volved, Eq. (A 1) is modified using the following
expression:
(A7)
where @j is the volume fraction of component j,
(A81
V, and b are the partial molar volumes of the
corresponding components. Replacing Xj by @j
 A. Heintz, W. Stephan /Journal of Membrane Science 89 (1994) 153-169 165

exhibits a generalization of the Maxwell-Stefan -J, =-c,v,

equations. The physical argument is that @j
rather than Xj is a realistic measure of the prob-
ability that the friction influence of component j
on component i contributes to the total friction
force applied to component i. Application of Eq.
(Al ) or (A7) requires the definition of a frame
of reference concerning the velocities Vi and Vj (Al2)
which is given by suitable linear combinations of
-J2=-c2v2
the Ujvalues.
We first consider liquid mixtures by combin-
ing Eq. (A5 ) with Eq. (A7 ). We account for three
components with the condition k= 0 for the
frame of reference (index M denotes the mem-
brane polymer ) :
(A13)
din@, ~ v2-v, ~ v,
7= 277 3_1M Obviously, the fluxes depend on the volume
D
fractions and concentration gradients of both
din@, Q, v, -v2 ~ v2 components. If 6r2+oo, the second term in Eqs.
7= 1x- 37 (A9) (A 12 ) and (A 13 ) disappears and one obtains
D 2M

with (A14)

with DiM =BiM/@M.

(AlO) This is the simple first Fick’s law of diffusion
in the Hittorf frame of reference where DIM is the
diffusion coefficient in the Hittorf system. The
where DUare effective diffusion coefficients gen-
fluxes become independent. If Fick’s frame of
erally dependent on the concentrations of all the reference would be chosen v1@1+v2@2
components present in the mixture. The frame +%&=O, &, instead of DIM appears in Eq.
of reference (v, = 0) chosen in Eq. (A9 ) is called (A14). & is the diffusion coefficient in Fick’s
the Hittorf frame of reference [ 19 1. The low mo- frame of reference. b,, has the meaning of a cou-
lecular weight components 1 and 2, are moving pling parameter with the dimension of a diffu-
against the background of the fixed membrane sion coefficient. 6,, and B2M are the diffusion
polymer component. From this point of view the coefficients of component 1 and 2, respectively,
membrane remains at rest and no swelling of the in the polymer. For practical purposes we use the
membrane would be observed when diffusion Hittorf system. If weight fractions w: instead of
occurs. volume fractions @i are introduced, the follow-
Eq. (A9 ) has now to be rearranged in order to ing equations are obtained from Eqs. (A 12 ) and
obtain the diffisive molar fluxes Ji = c,* Vi with the (A13):
molar concentration ci given by
DZMW; +D,2 dw;
P/Ml x
Dlz+w;D2~+~;4~ >
@i
ci=E (All)
DIM w’, dw;
mfl~
D,,+w;DzM+w;D,M >
Solving Eq. (A9) for J, and J2 is a straightfor-
ward procedure and leads to the result (A151
166 A. Heintz, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169

rangement of Eqs. (Al 7) and (Al 8) gives for

DIM& +Dl2 dw;
-Jz=DZM mf2x the molar fluxes J;’ and Jz :
Dl,+w;D,,+w’,D2~ >

-J: =-X,V,~~

DIM& /i/M2% X1 *d23 +Bl2

+DZM a3 dpl
=-* M
D~,+w;~M+w’,DzM >
RT 012 +X1 -023 +~z.D13 *-iii-
(Ale)
xl dp2
+%._ _‘D23 _
where p is the mean density of the swollen mem- RT 012 +x, -023 +x2.013 YG-
brane. DZM and DIM are the diffusion coeffi- (A21)
cients of 2 and 1 in M if the Hittorf frame of ref-
erence is used and D,2=8,2/@M.
- J2’ = -x~v~;~
The flow of a gaseous mixture through narrow
pores can be considered in a similar way as dif-
o”23 X2.D13 +B,, dp2
fusive fluxes in dense membrane polymers lead- =-* I

ing to solutions which involve laminar flow and RT 012 +~2’D,3 +X1 *D23’dZ
Knudsen flow as limiting situations.
We start with Eq. (Al ) using pi from Eq. (A4). +a._ RT 012 +x2*013
_
x2.0”13

+x,
I

sD23.Z
dpl

We consider a binary gaseous mixture. The ‘third

component’ is the wall of the pore. This auto- (A=)
matically requires that v3= 0. The Maxwell-Ste- J;’ and Jz are molar fluxes in the pore due to
fan equations obtained are diffusive processes only. However, there also ex-
ists a laminar (viscous) flow of the whole mix-
1 dp, v2-Vl Vl
(A17) ture which is superimposed to the individual dif-
p, dz ‘r-d,,
fusive fluxes. A velocity u has to be added to each
1 dP2_x VI -v2 ~2 of the individual velocities Viresulting in the to-
---
p2 dz lb,,-8,,
(Al8) tal velocity Wi = Vi + 24.
According to the theory of viscous flow in cy-
with p1 = Pax, and p2 =x2. d, 3 and o”23 are recip- lindrical pores [ 2 1 ] u is given by
rocal friction coefficients for the interactions of
component 1 and 2 with the wall, respectively. 1 d2 dp
With x2=0 or x1 =O, Eqs. (A17) and (A18) re- (~23)
u= -32’G-z
duce to the Knudsen flow of pure gas 1 and pure
gas 2 through the pore. From the theory of where qmix is the viscosity of the gaseous mix-
Knudsen flow of pure gases it follows that [ 201 ture. Adding u to v, and q in Eq. (A2 1) and
(A22), and substituting Eqs. (A19) and (A20)
ij 13=
J8 RT
_._.
9 nM,
d
(A19)
into Eqs. (A2 1) and (A22 ) one obtains for the
molar fluxes Ji:

J
D23=
8 RT d
-._.
J, =x1 (v, +u)FT
9 RM,
(‘420)
4x1 -f’)
where Ml and M2 are the molar masses of gas 1 (~24)
dz
and 2, respectively, and d is the diameter of the
pore. For x1 > 0 and x2 > 0 the term containing
D12 does not disappear. d,, is the binary diffu-
sion coeffkient in the gaseous mixture. Rear-
 A. Heintz, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169 167

r7,=26.69% [/IPI (A35)

,
= --.
b [ -. 1 d( ( 1 -x1 1 ‘PI where o is the molecular diameter and Qs the so-
NL l+B*P dz called collision integral based on the Stockmeyer

1
potential. The viscosity of a binary mixture gas
fo’B.( l-x,)-P dP
+ mixture according to Chapman and Enskog is

(25)
1 +B.P .dz+(l-x,)./I.Pg [22]:

rtmix = xI tJ1 + x2R WI (A36)

with XI +x2h2 x2 +x,tfJ2,

The parameters 912 for gases are approximated

b=$
Js-4 2
(26) by the method of Brokaw [ 221:

(~27)
@*j=
J $Sjj.A$
J

with the parameters S, and A, containing the di-

(A37)

mensionless Stockmeyer parameter SF and the

(A2g)
reduced temperature TT = kT/Ci as molecular
properties of the pure components. Ei represents
w_ MI ‘M2 the minimum of the intermolecular potential
(~29)
-M, +M2 curve.

(A30) s12 =s21

(A31)

(~32)

A. =m__M70.5.
Y V IJ
(A33)

1
-
JCz=x,*JM,+(l-x,)*,/M, (A34) M.. _&f+“5
1+
Eqs. (A24) and (A25) are identical with cor- 2(l+M~,)~(l+~~45)m,o-’
II
responding equations derived first by Present and l+m,
de Bethune [ 171 using the kinetic gas transport
formalism. The equations are rederived here on (A39)
the basis of the Maxwell-Stefan theory. g,, ap- with
pearing in Eq. (A27 ) can be calculated following

1
0.25
the procedure given by the kinetic theory of gases. 4
The viscosities of the pure substances vi are es- (A40)
(l+M,‘)(l+Mii)
timated according to the method of Chapman
and Enskog [ 22 ] and
 168 A. Heintz, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169

K partial molar volume of component i

(A41) ( cm3/mol)
WiF weight fraction of component i in bulk
If all molecular parameters are known Eqs. feed mixture
(A24) and (A25 ) can be used for calculating $iF weight fraction of component i in feed
fluxes of gaseous mixture components through mixture adjacent to membrane
narrow pores. Table 3 gives parameters taken wiP weight fraction of component i in bulk
from the literature [ 22 1. permeate mixture
ti weight fraction of component i in active
layer at arbitrary location
tiF weight fraction of component i in active
7. List of symbols layer on feed side of membrane
tiP weight fraction of component i in active
ai thermodynamic activity of component i layer on permeate side
ci molar concentration of component i xi mole fraction of component i
(mol/l)
Z axis coordinate perpendicular to mem-
d pore diameter ( m ) brane surface
d max maximum of pore size distribution func-
tion (m) 7.1. Greek letters
Di diffusion coefficient of component i
(cm2/s) volume fraction of component i in
Maxwell-Stefan interaction parameter mixture
(cm2/s) thickness of dense, active layer (m )
effective diffusion coefficient depen- thickness of porous support layer (m)
dent on concentration (cm2/s) Stockmeyer parameter
Dij averaged diffusion coefficient (cm’/s) difference operator
fi‘ fugacity of component i ( mbar ) characteristic energy of component i (J )
Ji molar flux of component i (mol/h m2) activity coefficient of component i
k mass transfer coefficient chemical potential of component i (J/
Mi molar mass of component i (g/m01 ) mol )
number of components viscosity of pure component i (kg/m s)
i parameter for pore size distribution viscosity of gas mixture (kg/m s)
function density of component i ( kg/dm3)
K Avogadro number ( 1/mol) mean density of swollen membrane (g/
P total pressure (mbar) cm3 )
Pi partial pressure of component i in gas- molecular diameter (nm)
eous mixture (mbar ) binary interaction parameter
PP saturation pressure of component i at ( UNIQUAC )
given temperature (mbar ) collision integral based on the Stock-
P” standard pressure (mbar ) meyer potential
R gas constant (J/mol K) pore size distribution function
siF solubility coefficient on feed side of ac-
tive membrane layer
si, solubility coefficient on permeate side of 8. Acknowledgement
active membrane layer
T absolute temperature (K) Financial support of the Bundesministerium
u velocity due to viscous flow (m/s) fur Forschung und Technologie is greatly
vi mean velocity of molecule i (m/s) acknowledged.
 A. Heintz, W. Stephan /Journal ofMembrane Science 89 (1994) 153-169
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