Journal of Membrane Science 163 (1999) 63–74

Analysis of CaSO
4
scale formation mechanism in various
nanofiltration modules
Sangho Lee, Jaehong Kim, Chung-Hak Lee

School of Chemical Engineering, College of Engineering, Seoul National University, Seoul 151-742, South Korea
Received 15 July 1998; accepted 12 April 1999
Abstract
Scale formation of sparingly soluble salts has a significant effect on flux decline in nanofiltration (NF) system. This study
focuses on the elucidation of the different mechanisms of scale formation according to membrane modules in NF system.
In unstirred batch NF, flux decline was mainly due to surface (heterogeneous) crystallization, while in crossflow NF,
fouling was attributed to both surface and bulk crystallization. However, the extent of contribution of each crystallization
to the fouling depended on the NF modules. The bulk (homogeneous) crystallization followed by crystal deposition on the
surface of the nanofilter played a major role in flux decline in the spiral wound module whereas surface blockage due to the
surface crystallization does in the tubular module. When an on-line microfiler was introduced to prevent crystal deposition
during the concentration run, flux improvement was pronounced only in case of the spiral wound module, whereas it was
negligible in case of the tubular module. This was because the microfilter could only remove crystals formed in the retentate
through the bulk crystallization which is the dominant fouling mechanism in the spiral wound module.
A modified resistance-in-series model was applied to assess the fouling characteristics of each NF module based on the
bulk and the surface crystallization. The greatest extent of the fouling due to surface crystallization in tubular module was
attributed to its highest concentration polarization modulus compared with the other two modules at the same crossflow rate.
©1999 Elsevier Science B.V. All rights reserved.
Keywords: Nanofiltration; Calcium sulfate; Crystallization; Membrane fouling; Membrane module
1. Introduction
In recent years, nanofiltration (NF) technology has
been widely applied to water purification, municipal
and industrial wastewater treatment and reuse, etc.
One of the most promising applications of NF may be
water softening. Selective retention characteristics in
NF make it possible to economically remove multiva-

Corresponding author. Tel.: +82-2-880-7075; fax:
+82-2-888-1604
E-mail address: leech@snu.ac.kr (C.-H. Lee)
lent ions from water. However, in water softening, a
serious problem to overcome is the membrane fouling
due to scale formation. Controlling of the membrane
fouling due to the scale formation is a major expense
in designing and operation of practical NF membrane
plant. Sparingly soluble salts such as CaCO
3
, CaSO
4
and SiO
2
could precipitate on the membrane surface
when their concentration exceeds the solubility lim-
its and subsequently decrease the product flow rate
through the membrane. Various means have been pro-
posed to address the scale formation control, but none
have solved this problem with satisfactory results.
0376-7388/99/$ – see front matter ©1999 Elsevier Science B.V. All rights reserved.
PII: S0376- 7388( 99) 00156- 8
64 S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74
Several recent publications have dealt with the
mechanisms of calcium sulfate scale formation on
membranes: Okazaki and Kimura [1] used basic con-
cepts from nucleation and crystallization kinetics in
conjunction with a cake filtration model to interpret
flux decline curves and assumed that crystal nucle-
ation occurred on the membrane surface and nuclei
formation rate is dependent on the degree of the su-
persaturation. Gilron and Hasson [2] considered that
the flux decline was due to the blockage of the mem-
brane surface by lateral growth of the deposit (surface
or heterogeneous crystallization). On the other hand,
Pervov [3] suggested that crystal formation took place
in the bulk solution due to strong oversaturation in the
deadlocks (bulk or homogeneous crystallization) and
then the crystals came out of the sites sediment on the
membrane surface, which led to the flux decline. Sev-
eral other researchers attempted to model the fouling
process [4–6]. However, few studies have been done
on the crystal formation mechanisms according to the
types of the membrane modules.
The purpose of this study was to elucidate the dif-
ferent pathways toward the membrane fouling dur-
ing the NF of calcium sulfate solution. Special efforts
were made to examine the effect of the types of the
NF modules on membrane fouling. A new approach
for flux enhancement was also attempted based on the
different scale formation mechanisms.
2. Theory
2.1. Concentration polarization
In pressure-driven membrane process concentration
polarization arises when solute is largely rejected by
the membrane. Due to this phenomenon, the concen-
tration of soluble salts easily become supersaturated at
the NF membrane surface even though the bulk con-
centration is still undersaturated. In the NF of the feed
solution containing mainly divalent ions, the concen-
tration of salt in the permeate is negligible with re-
spect to concentration (C
m
) at membrane surface and
bulk concentration (C
b
). Therefore, the concentration
polarization modulus, which is defined by the ratio
C
m
and C
b
(C
m
/C
b
), is given as the Eq. (1) [7]:
C
m
C
b
= exp


D

(1)
where, J is the permeation flux, δ the characteristic
boundary layer thickness and D the diffusivity of
solute.
Since the hydrodynamic conditions of membrane
modules are different, the extent of concentration
polarization may be different from one another even
at the same crossflow velocity. For instance, the con-
centration polarization is less severe in spiral wound
module than in plate-and-frame module since the feed
spacer in spiral wound module promotes turbulent
flow. Table 1 summarizes the concentration polariza-
tion modulus in spiral wound, plate-and-frame, and
tubular modules.
2.2. Mechanisms for the scale formation
There are two ways for explaining flux decline
mechanisms due to scale formation in RO/NF mem-
branes; cake formation and surface blockage mecha-
nism [2,3].
In cake formation mechanism, crystal particles
which are formed in bulk phase through bulk (homo-
geneous) or secondary crystallization deposit on the
membrane to form a layer. Therefore, the flux de-
cline comes up with the accumulation of the porous
layer of precipitate and could be described by a
resistance-in-series model:
J =
P −π
η (R
m
+R
c
)
(2)
where P is the transmembrane pressure, π the os-
motic pressure, η the permeate viscosity, R
m
the mem-
brane resistance and R
c
the resistance due to cake for-
mation.
On the other hand, in surface blockage mechanism
scale formation may occur due to surface (heteroge-
neous) crystallization on membrane surface and the
membrane surface becomes blocked by the lateral
growth of crystals. Assuming the areas occupied by
crystals are completely impermeable, the flux in the
absence of the cake formation could be expressed as
follows:
J =
P −π
ηR
m
A
free
A
t
(3)
where A
t
is the total membrane area and A
free
the
membrane area unoccupied by surface (heteroge-
neous) crystallization
S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74 65
Table 1
Equations for concentration polarization modulus
a
[8–11]
Type Concentration polarization modulus Flow condition
Spiral wound exp

17Jν
0.625
h
0.875
u
0.875
D
0.75

Turbulent
Plate-and-frame exp

Jd
0.33
h
L
0.33
1.86u
0.33
D
0.67

Laminar
Tubular exp

Jd
0.11
t
ν
0.56
0.023u
0.89
D
0.67

Turbulent
a
J: flux, ν: kinematic viscosity, h: channel height, u: crossflow velocity, D: diffusion coefficient, d
t
: tube diameter, d
h
: hydraulic diameter.
Fig. 1. Scale formation mechanisms in NF membrane.
The two different schemes are depicted in Fig. 1.
When the bulk phase becomes supersaturated due
to increasing concentration, it is possible that both
mechanisms of crystallization simultaneously occur in
NF system. In this case the flux may be represented
by combining Eqs. (2) and (3);
J =
P −π
η (R
m
+R
c
)
A
free
A
t
(4)
Assuming that the thickness of crystal layer formed
on the membrane surface is constant [6], A
free
could
be defined as follows:
A
free
= A
t
−βm
s
(5)
where β is the area occupied per unit mass and m
s
the weight of scale which is crystallized on membrane
surface
If the crystal slurry is incompressible, cake resis-
tance R
c
can be calculated based on a conventional
cake filtration theory:
R
c
=
αm
c
A
t
(6)
where α is the specific cake resistance factor per unit
weight of cake, m
c
the accumulated weight of precip-
itated scale
Based on these equations, the most predominant
mechanism may be determined if the relationship be-
tween flux and precipitated mass is identified. A lin-
ear relationship between J and surface crystal mass m
s
should be obtained when the surface blockage mech-
anism is predominant whereas J
−1
should be pro-
portional to cake mass m
c
when the cake formation
mechanism is predominant. The total mass of crystals
formed both on membrane surface and in bulk phase
can be calculated through the following mass balance.
m
t
= m
s
+m
c
= c
f
V
f
−c
r
V
r
−c
p
V
p
(7)
where m
t
is the total mass of crystals; c
f
, c
r
, c
p
the
solute concentrations of feed, retentate and permeate,
respectively and V
f
, V
r
, V
p
the volumes of feed, re-
tentate and permeate, respectively.
2.3. Analysis of each resistance term
In the NF of CaSO
4
solution with three kinds of NF
modules (tubular, plate-and-frame, spiral wound, re-
spectively), the boundary layer thicknesses were cal-
culated using the equations shown in Table 1. As their
values were only around 10 ␮m for all the tested mod-
ules, we assumed that the bulk crystallization within
the boundry layer is negligible [2]. Since the cake re-
sistance, R
c
is directly related to the amount of the
crystals formed in bulk phase, R
c
could be eliminated
from Eq. (4) if the retentate is continuously prefiltered
on-line by 0.45 ␮m microfilter in order to remove the
suspended crystals.
66 S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74
In this context, the following procedure was adopted
to evaluate each resistance term and fraction of free
area, A
free
/A
t
for each NF module:
1. Membrane resistance (R
m
) is obtained from
pure water flux. In our cases the osmotic pres-
sure was calculated from Gibbs equation. It
was small enough (about 0.7 kgf/cm
2
) to be ne-
glected compared with the operation pressure for
NF(10 kgf/cm
2
).
2. According to Eq. (3), A
free
/A
t
is estimated from
the steady-state flux of NF with a microfilter since
the cake resistance (R
c
) is removed in this case.
3. The cake resistance (R
c
) is the difference in resis-
tance between the case with and without microfil-
ter and thus, R
c
is calculated based on the Eq. (4).
3. Experimental
3.1. Batch nanofiltration cell experiments
The dead end filtration cell(volume capacity;
100 ml) was pressurized at 10 bar by N
2
gas. The
membrane used was NF-45(Filmtech) and the effec-
tive membrane area was 22.1 cm
2
. The feed solution
was 2000 ppm of CaSO
4
. In all the experiments, the
feed solution temperature was kept between 20 and
25

C, and all the flux data were corrected at 25

C by
the following equation:
Flux at 25

C
= Flux at T

C ×
Viscocity at T

C
Viscocity at 25

C
(8)
3.2. Crossflow filtration
Fig. 2 shows a schematic diagram of the crossflow
NF system combined with on-line microfiltration. The
system with a total working volume of 4–8 l consisted
of a feed vessel, temperature controller, high pressure
pump, MF and NF module. Three kinds of mem-
brane modules were tested to investigate the effect of
module type on fouling phenomena: plate-and-frame,
spiral wound and tubular modules. The membranes
having similar ion rejection characteristics were used
in each module. Table 2 summarizes the modules
and membranes tested in the experiments. The cross-
flow velocity was fixed at 0.6 m/sec and the feed
Fig. 2. Schematic diagram of crossflow NF equipment.
solution was 2000 ppm of CaSO
4
for all the three
modules.
The crossflow experiments were carried out in both
continuous concentration(Fig. 3(a)) and total recycle
modes(Fig. 3(b)). At the start of each run, the water
flux was measured with ultra pure water (a resistiv-
ity ; ca. 18 MOhmcm). In the concentration runs, the
equipment was operated with and without a micro-
filter by recirculating only the retentate and continu-
ously collecting the permeate. In total recycle runs,
both the retentate at the supersaturation degree (SD)
of 2.5 and the permeate were recycled with and with-
out a microfilter in order to study the fouling mecha-
nisms in depth. The microfilter was a polypropylene
cartridge filter (Osmonics, Hydrex II) with a pore size
of 0.45 ␮m.
3.3. Analytical methods
The analytical methods from Standard Methods
[12] were adopted for measurement of feed, retentate
and permeate ion concentration: an ion chromatog-
raphy (DIONEX 4000I) and an atomic absorption
spectroscopy(NIPPON jarrell Ash, AA-880 mark II).
A conductivity cell (ATI Orion, Model 170) was
S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74 67
Table 2
Specifications of NF membranes
Membrane Surface area (m
2
) Hydraulic radius (mm) Channel length (mm) Rejection of inorganic salts
Plate-and-frame NF-45 0.018 0.5 50 MgSO
4
2000 ppm: 99%
Spiral wound NF-40 0.3 0.25 350 NaCl 2000 ppm: 45%
Tubular MPT-34A 0.024 6.35 600 NaCl 50,000 ppm: 35%
Fig. 3. Schematics of NF operation mode; (a) concentration runs
(b) total recycle runs.
installed on-line for the continuous monitoring of
total soluble ion concentrations. The supersaturation
degree (SD) of CaSO
4
in retentate was evaluated by
the ratio of the retentate concentration to the saturated
one (C
b
/C
s
) which is proportional to the solution
conductivity. The turbidity was measured by a neph-
elometer (HF DRT-100B turbidimeter). The mean
size and size distribution of crystal particles in the
retentate were evaluated using a laser light scattering
instrument(Malvern Mastersizer/E).
4. Results and discussion
4.1. Crystal formation and flux decline in unstirred
batch nanofiltration
The variation of flux during the NF of CaSO
4
so-
lution was illustrated as a function of CF in Fig. 4.
Rapid and continuous flux decline was observed from
the first stage, even though the SD of less than 1.1
was maintained and the turbidity of bulk phase was
quite low(less than 1 NTU) throughout the NF. It sug-
gested that no significant bulk crystallization occurred
in the bulk phase, but fast crystallization occurred at
the membrane surface. The concentration polarization
is not increasing with time due to the continuous crys-
tal formation near membrane surface [5], so the effect
of osmotic pressure on flux decline with time could
be neglected.
Fig. 4. Flux decline in dead-end NF.
68 S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74
Fig. 5. Estimation of mass of crystal grown on the membrane
surface in case of dead-end NF.
The amount of the CaSO
4
crystals which formed on
the membrane surface was estimated to be 11.3 g/m
2
of
membrane from the mass balance Eq. (8) for CaSO
4
.
A linear relationship was observed between the mass
of CaSO
4
crystals and flux as depicted in Fig. 5, which
indicates that flux decline was mainly due to the sur-
face crystallization on the membrane surface, as de-
scribed in Section 2. This is what one would expect
since, in unstirred batch filtration, surface crystalliza-
tion could be dominant due to the severe concentra-
tion polarization at the membrane surface. This result
coincides with some previous studies [2].
4.2. Comparison of flux and supersaturation
degree between nanofiltration modules in crossflow
nanofiltration
Fig. 6 illustrates the results of crossflow NF of satu-
rated calcium sulfate solution of 2000 ppm with three
kinds of NF modules. The permeate flux and super-
saturation degree (SD) of CaSO
4
in the retentate are
shown as a function of CF. In contrast to the dead-end
filtration, the permeate flux was maintained at rela-
tively high initial value below the CF of 2 regardless
of the membrane modules. The SD continuously in-
creased with the CF before reaching a certain point
(SD=2.7), but after that it abruptly decreased.
From this result, three distinct periods of behav-
ior could be identified as shown in Fig. 6. During the
early phase of the run (Period 1), no significant flux
decline is observed for all the three modules (Fig.
6(a–c)). Even though the bulk and membrane wall
concentration exceed the CaSO
4
saturation concentra-
tion, neither bulk nor surface crystallization occurs in
this period since the concentration is less than a crit-
ical supersaturation level that needs to initiate crystal
nucleation. In contrast to the dead-end mode(Fig. 4),
even the surface crystallization did not occur on the
membrane surface in the crossflow mode. It could be
attributed to the fact that the concentration polariza-
tion modulus in crossflow mode should be less than
that in a dead-end mode.
During Period 2, the ionic concentrations within
the boundary layer exceeds the critical value so that
the surface crystallization begins. The crystal layer
on the membrane surface blocks the membrane and
subsequently decreases the permeate flux. Since the
membrane wall concentration is always higher than
the bulk concentration, the bulk crystallization in the
bulk retentate does not occur yet. No crystal forma-
tion was observed in the retentate and the turbidity of
the retentate solution was as low as the initial feed
solution.
As the fluid is removed through the membrane in
concentration run, the ionic concentrations in the bulk
solution increase and approach the critical value at
which bulk crystallization starts (Period 3). During
Period 3, the SD is abruptly decreased and the bulk
turbidity is increased due to the formation of crystal
particles in the retentate. From this point the retentate
became very turbid, and simultaneously the average
particle size of crystal formed in retentate increased
up to about 100 ␮m. As shown in Fig. 6(a–c), the in-
tensive bulk crystallization started mostly at SD=2.7
and progressed thereafter regardless of the membrane
modules. During this period, flux decline is attributed
to both surface and bulk crystallization.
However, it is worth noting that the length of Period
2 is quite different from module to module. The length
of Period 2 is shortest in spiral wound module (Fig.
6(a)) whereas it is longest in tubular module (Fig.
6(b)). The plate-and-frame module takes intermediate
length (Fig. 6(c)). As the intensive bulk crystallization
starts at Period 3, the shortest length of Period 2 means
that the bulk crystallization contributes little to flux
S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74 69
Fig. 6. Flux SD and retentate turbidity vs. concentration factor according to membrane module type; Crossflow velocity for all the three
modules =0.6 m/s; (a) spiral wound (b) tubular (c) plate-and-frame.
decline. On the other hand, the longest length of Period
2 means that the flux decline results mostly from the
surface crystallization. It is very important factor to
design a hybrid NF system to enhance the permeate
flux. This will be discussed in more detail in Section
4.3.
Since the surface crystallization on the membrane
was in close relationship with concentration polariza-
70 S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74
Fig. 7. Effects of flow rate on flux decline in plate-and-frame
module.
tion, the rate of flux decline was expected to be af-
fected by the crossflow recirculation rate. Fig. 7 shows
that in plate-and-frame module the higher the cross-
flow rate, the longer the non-fouling region (Period 1).
As the wall shear rate would increase with the cross-
flow rate, it would be reasonable to assume that the
increase in the crossflow rate would lower the solute
wall concentration and thus make the condition un-
favorable for the surface crystallization on the mem-
brane surface by increasing the wall shear rate. But
the flux improvement by increasing flow rate was not
so effective beyond the CF of 3.0 even at the high-
est crossflow rate (0.76 m/sec) since the bulk crystal-
lization in the retentate became important beyond this
point due to the great extent of SD.
4.3. Flux enhancement by introducing microfiltration
on-line to the nanofiltration
In order to verify the dominant crystal formation
mechanism for each module described in the previous
section, a microfilter (0.45 ␮m) was inserted on-line
to NF as shown in Fig. 4. The role of the microfilter
was to continuously remove crystals formed in the
retentate through the bulk crystallization during the
concentration run.
Fig. 8(a) shows the effect of 0.45 ␮m MF on the flux
in spiral wound module. Below the CF of 2.0 (Period
1, non-fouling region), any significant change was not
observed with the on-line microfiltration. However,
beyond the CF of 2.5 (Period 3), the flux improvement
was much more pronounced compared with the flux
without the microfilter. It is because most of the crys-
tals formed in the retentate through the bulk crystal-
lization were removed by the on-line microfilter and
consequently their deposition on the membrane sur-
face was prevented. It supports the fact that in spiral
wound module, the bulk crystallization in the reten-
tate is more important mechanism of the membrane
fouling and flux decline than surface crystallization.
In contrast, the efficiency of the on-line microfil-
ter in tubular module was negligible during the entire
periods, as shown in Fig. 8(b). This result confirmed
that the flux decline in tubular module has nothing to
do with the crystals formed in the bulk retentate so-
lution but the dominant fouling mechanism is the sur-
face blockage caused by the surface crystallization. In
plate-and-frame module (Fig. 8(c)) the prefilter had a
little effect on flux increment, but it was much less
than that in spiral wound module. It is because both
the bulk and surface crystallization contribute to the
fouling in this module.
In summary, flux enhancement could be achieved
by eliminating crystals suspended in recirculation loop
but the efficiency is greatly different from module to
module. Similar results were observed in some previ-
ous studies [13].
4.4. Analysis of resistances in three modules
To further investigate the fouling mechanism in
depth, the modified resistance-in-series model based
on Eqs. (1)–(8) was applied to quantitatively analyze
the characteristics of membrane fouling for each mod-
ule. Since the osmotic pressure effect on the flux was
negligible in this study, R
c
was experimentally deter-
mined to be the portion of the total resistance which
can be eliminated when the on-line microfilter is used,
while the fraction of free area, A
free
/A
t
is calculated
from the ratio of pure water flux to the steady-state
flux in the presence of the on-line microfilter. When
the steady state flux were obtained after 5 h NF opera-
tion of supersaturated CaSO
4
solution (SD=2.5), the
S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74 71
Fig. 8. Effect of membrane module type on the efficiency of on-line microfilter; (a) spiral wound (b) tubular (c) plate-and-frame.
flux data (J
1
, J
2
) for three modules were measured
under the crossflow velocity of 0.6 m/sec (Table 3).
These equations and the flux data were used to
quantitatively evaluate various resistance terms, and
the fraction of free area for each module under the
same crossflow velocity of 0.6 m/sec (Table 3). These
data could be useful to find out which resistance dom-
inantly affects the permeation flux for each module.
The A
free
/A
t
with spiral wound module was the
highest (0.507) whereas the magnitude of the fraction
of free area is the least in tubular module (0.062). It
clearly illustrates that the fouling due to the surface
72 S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74
Table 3
Composition of resistances, concentration polarization modulus and fraction of free membrane area in various membrane modules
d
Module type J
w
a
(l m
2
/h) J
1
b
(l m
2
/h) J
2
c
(l m
2
/h) R
m
(m
−1
) R
c
(m
−1
) A
free
/A
t
C
m
/C
b
Spiral wound 35.0 4.9 17.7 1.03 ×10
14
2.64 ×10
14
0.507 1.13
Plate-and-frame 40.0 7.5 16.0 0.90 ×10
14
1.02 ×10
14
0.400 1.29
Tubular 40.0 2.0 2.5 0.90 ×10
14
0.23 ×10
14
0.062 1.90
a
J
w
: water flux.
b
J
1
: steady-state flux without microfilter after 5 h operation under the total recycle run.
c
J
2
: steady-state flux with microfilter after 5 h operation under the total recycle run.
d
All values were calculated at the following conditions: the crossflow velocity of 0.6 m/sec, SD 2.5; the steady-state flux was measured
after 5 h.
Fig. 9. Theoretical estimation of concentration modulus with re-
spect to various membrane modules.
crystallization was the most important in tubular mod-
ule. It may be the reason why the removal of suspended
crystals in the retentate was useless in enhancing the
flux in tubular module as shown in Fig. 8(b).
It is interesting to note that the cake resistance in
spiral wound module was almost 11 times greater than
that in tubular module and 2.5 times greater than that
in plate-and-frame module. One possible explanation
is that feed spacers in spiral wound module play a sig-
nificant role in cake formation on NF membrane; since
the flow through the spacer under pressure creates
a greater turbulence, secondary nucleation is greatly
promoted by turbulent motion of fluids and thus mem-
brane fouling due to bulk crystallization becomes
important.
Fig. 9 shows the theoretical concentration polariza-
tion modulus versus the crossflow velocity in all the
three modules calculated based on the equations in
Table 1. The flow regimes in all the modules were
turbulent at this interval of the crossflow velocity.
The order of the concentration polarization modulus
was always spiral wound <plate-and-frame <tubular
module and coincides well with the trend of A
free
/A
t
in Table 3. This result indicates that the fouling due to
surface crystallization should depend on the concen-
tration polarization modulus.
A plot of calculated SD at membrane surface versus
steady-state flux with total recycle runs clearly demon-
strates the effect of concentration polarization on sur-
face crystallization (Fig. 10). A linear relationship
Fig. 10. Effect of SD at membrane wall on permeate flux during
total recycle runs.
S. Lee et al. / Journal of Membrane Science 163 (1999) 63–74 73
between SD at membrane surface and flux was ob-
served regardless of module types when an on-line mi-
crofilter was used. This fact also supports that the dif-
ferences in the scale formation mechanisms between
the three modules can be attributed to the wall con-
centration.
5. Conclusions
The scale formation mechanisms in NF of CaSO
4
were examined with different NF modules both exper-
imentally and theoretically. The following conclusions
were withdrawn:
1. Permeation flux in unstirred batch NF was
exponentially decreased even though the reten-
tate concentration was almost unchanged. The
linear relationship between flux and deposited
mass indicates that the NF fouling results from
the surface (heterogeneous) crystallization.
2. In crossflow NF, flux decline was due to not only
surface (heterogeneous) crystallization but also
due to bulk (homogeneous) crystallization. The
surface crystallization played the smaller role in
membrane fouling of spiral wound module in
comparison to the other modules, but it was still
significant.
3. The flux enhancement was attempted through the
hybrid system of the NF with an on-line microfil-
ter by continuously eliminating crystals suspended
in recirculation loop. The greatest flux improve-
ment was more pronounced in spiral wound mod-
ule among the three modules. This is because the
fouling due to surface crystallization, which can-
not be prevented by on-line microfilter, was less
dominant in spiral wound than in plate-and-frame
and tubular module.
4. Analysis of resistances in three types of modules
indicates that the extent of surface fouling in spiral
wound module is smaller than in other modules.
The lowest value of A
free
/A
t
for the tubular module
was attributed to higher concentration polarization
modulus under the same flow condition.
6. List of symbols
A
t
membrane area (m
2
)
A
free
membrane area unoccupied by precipitation
(m
2
)
A
free
/A
t
the fraction of free area
c
f
, c
r
, c
p
solute concentrations of feed, retentate and
permeate, respectively (mg/l)
C
m
solute concentration at membrane surface
C
s
saturation concentration of CaSO
4
(mg/l)
D diffusion coefficient (m
2
/sec)
J flux (l/m
2
/h)
L channel length (m)
R
c
resistance due to cake formation (m
−1
)
R
m
membrane resistance (m
−1
)
V
f
, V
r
, V
p
volumes of feed, retentate and permeate,
respectively (l)
d
h
hydraulic diameter (m)
d
t
tube diameter (m)
h channel height (m)
m
c
accumulated weight of precipitated scale
(kg)
m
s
weight of scale which is crystallized on
membrane surface (kg)
m
t
total mass of crystals (kg)
r
h
hydraulic resistance (m
−1
)
u crossflow velocity (m/sec)
P transmembrane pressure (Pa)
α specific cake resistance factor per unit
weight of cake (kg
−1
m
−1
)
β blocking coefficient (m
2
/kg)
π osmotic pressure (Pa)
ν kinematic viscosity (m
2
/sec)
Acknowledgements
This work was financially supported as a HAN
project by Ministry of Environment in Korea. The
authors are grateful to Mr J.S. Yum and Mrs H.S.
Lee for their assistance during the experiments at the
Institute of Environmental Science & Technology,
Seoul National University.
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