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Abstract
This work presents a numerical simulation of an ultraltration process of bovine serum albumin in solution, using hollow-
ber membranes. Such membranes are constituted of tiny polymer cylinders disposed in a tube-and-shell arrangement. The
concentrate ows through the interior of the bers and the pure solvent is recovered in the shell, assuming perfect solute
rejection. In modeling the process, the ow of concentrate inside the bers was considered to be laminar, with constant
density, viscosity and solute diffusivity. Axial diffusion and angular effects were ignored. The model combines the effect of
concentration polarization and adsorption, which are the two main limiting phenomena in ultraltration processes. The
pressure on the shell side was considered constant and inside the bers a linear pressure prole, dependent on the axial
position, was adopted. The solution of the problem was achieved with the method of orthogonal collocation, with adequate
choice of the weight function in the radial direction. In the axial direction, a nite-difference method was used. The numerical
results were compared with experimental data available in the literature. # 1999 Elsevier Science B.V. All rights reserved.
Keywords: Hollow-ber membranes; Ultraltration; Membrane process simulation; Concentration polarization; Adsorption
0376-7388/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 6 - 7 3 8 8 ( 9 9 ) 0 0 0 9 1 - 5
256 A.R. Secchi et al. / Journal of Membrane Science 160 (1999) 255265
2. Mathematical model
ad cm (11)
1 k2 cm direction, a variable change was proceeded in the
radial coordinate, in the way that xR2. This was
where the constants k1 and k2 are estimated with done before the application of the method of ortho-
experimental data available. gonal collocation. In this new system of coordinates,
The osmotic pressurecomposition relationship for Eq. (1) assumes the form
the bovine albumin solution, was determined from the
work of Scatchard et al. [3]. In the operating condi- @C 4 @ @C @C @C
x W U (15)
tions of the experimental data (of Ma et al. [2]), @ Pe @x @x @x @y
temperature and pH values were, respectively, 378C
Eqs. (7) and (8) become, respectively,
(310.15 K) and 6.7. The empirical relationship for the
osmotic pressure, in kPa, has the following polyno- Ux; y 21 2Vm y1 x (16)
mial form Wx; y 2Vm 2x x2 (17)
2 3
m ! 37:20! 243:98! 487:96! (12) and the boundary conditions given by Eqs. (3) and (4)
258 A.R. Secchi et al. / Journal of Membrane Science 160 (1999) 255265
become
@C
finite (18)
@x x0
@C Pe
Vm yC; 1; y (19)
@x x1 2
The nite value in Eq. (18) results
pfrom the chain
rule applied to Eq. (3): @C=@R 2 x@C=@x, and
at x0 (or R0) it is sufcient that (@C/@x) be nite.
Table 1
Experimental data from literature [2] and predicted by the model
The form of the pressure drop equation was deter- obtained by a linear tting with the experimental data,
mined considering a HagenPoiseuille ow, which with a correlation coefcient of 0.996.
predicts the proportionality between the pressure drop Fig. 8 shows the variation of the solute concentra-
and the mean ow velocity. The equation for pressure tion at the membrane surface along the ber length.
drop as a function of the entrance velocity was The abrupt increase of concentration for small values
Fig. 4. Dimensionless evolution of the solute concentration profile inside of the fiber.
A.R. Secchi et al. / Journal of Membrane Science 160 (1999) 255265 261
Fig. 5. Velocity field for transmembrane pressure Pre20.66 kPa Fig. 7. Permeate rate and recovery as a function of the feed flow
with dimensionless coordinates. rate for two models of the pressure drop in the axial direction, Pax
(
uo is the bulk axial velocity at z0).
Fig. 6. Velocity field for transmembrane pressure Pre0 with Fig. 8. Dimensionless concentration versus dimensionless axial
dimensionless coordinates. coordinate for different values of transmembrane pressure.
262 A.R. Secchi et al. / Journal of Membrane Science 160 (1999) 255265
Fig. 12. Dimensionless concentration at the membrane surface as a Fig. 14. Osmotic pressure as a function of the dimensionless axial
function of the dimensionless axial coordinate for different feed coordinate for different feed flow rates.
flow rates.
effect can be explained by the increase of the polar- The reduction of concentration after the maximum
ization in the entrance of the ber due to a larger point is due to the fast reduction of the effective
pressure difference through the membrane in this transmembrane pressure difference. For high feed
region. Ma et al. [2] also predicted this phenomenon ow rates, the increase of concentration in the con-
but at lower feed ow rates. centrate stream, when passing through the ber, is not
very signicant. Thus, the concentration gradient in
the radial direction is larger for higher ow rates,
favoring the diffusion of the solute at the membrane
surface to the bulk stream. This effect contributes
essentially to the reduction of the solute concentration
at the membrane surface as shown by the curve
q8.0 cm3/s.
In Fig. 13, the area under the curve vm versus Z is
proportional to the permeation rate. It can be observed
that as the ow increases the permeation rate
increases.
5. Conclusions
This indicates the need to consider the polarization U dimensionless axial velocity, u=uo
effect together with the effect of adsorption for the u axial velocity (cm/s) R
r
problem in study. Although the model need two more u bulk axial velocity, r22 0m rudr (cm/s)
m
adjustable parameters, the inclusion of the resistance V dimensionless radial velocity (v/vmi)
due to solute adsorption in the membrane permeability v radial velocity (cm/s)
is of fundamental importance to better elucidate this W 2RV
phenomenon. New experiments are being planned in w weight function
order to verify the actual contribution of the surface x R2
effects over the membrane permeability. y dimensionless axial coordinate, zvmi =uo rm
The results can be considered very close to the y axial discretization interval
experimental data available in the literature. However, Z dimensionless axial coordinate (z/L)
it is been planned to build a pilot equipment for tests, z axial coordinate (cm)
from where more experimental data will be obtained
for comparison effects.
The use of orthogonal collocation in the radial Greek letters
direction reduced the two-dimensional mesh of
2160 points, used by Ma et al. [2] with nite differ- weight function parameter
ences, to a two-dimensional mesh of 360 points. The weight function parameter
methodology used to select the weight function shows dimensionless number (rmvor/m)
to be very useful to determine an adequate polynomial viscosity (g/cm s)
approximation with reduced order for non-linear osmotic pressure (kPa)
PDEs. This methodology has been successfully density (g/cm3)
applied to other systems by the authors. dimensionless time (tvmi/rm)
specific volume (cm3/g)
resistance to permeation (kPa s/cm)
6. Nomenclature ! mass ratio, g protein/g solvent
[2] R.P. Ma, C.H. Gooding, W.K. Alexander, A dynamic model [4] A.R. Secchi, F.A. Pereira, DASSLC: User's Manual - Version
for low-pressure, hollow-fiber ultrafiltration, AIChE J. 31 2.2. ENQLIB, http://www.enq.ufrgs.br/enqlib/numeric/,
(1985) 1728. 1997.
[3] G. Scatchard et al., Preparation and properties of serum and [5] S.W. Yuan, A.B. Finkelstein, Laminar pipe flow with
shapes proteins. VII: osmotic equilibrium in concentrated injection and suction through porous wall, Trans. ASME 78
solutions of serum albumin, J. Am. Chem. Soc. 68 (1946) (1956) 719.
610.