Journal of Membrane Science 165 (2000) 8388

Fouling of inorganic membranes by adsorption of whey proteins

Marijana D
- . Caric, Spasenija D. Milanovic, Darko M. Krstic, Miodrag N. Tekic
Faculty of Technology, University of Novi Sad, Bul. Cara Lazara 1, 21000 Novi Sad, Yugoslavia
Received 2 December 1998; received in revised form 5 July 1999; accepted 6 July 1999

Abstract
The adsorption of proteins to membrane surfaces can lead to the reduction of a permeate flux and represents a serious
impediment to efficient membrane filtration operations. The factors influencing protein adsorption, permeate flux and overall
membrane fouling during cross-flow filtration of whey protein solutions using 50 nm pore size ultrafiltration zirconia membrane
and 200 nm pore size microfiltration alumina membrane were examined in this study. The permeate flux was observed to be
a function of protein concentration and transmembrane pressure and followed classic membrane filtration behavior for the
membranes studied. Studies of the fouling resistances, coupled with static adsorption studies, indicated that adsorption-related
pore plugging plays a significant role in the larger pore alumina microfiltration membranes. 2000 Elsevier Science B.V. All
rights reserved.
Keywords: Inorganic membranes; Whey proteins; Ultrafiltration; Microfiltration; Protein adsorption; Membrane fouling

1. Introduction
For about 20 years, the dairy industry has been
preparing a wide range of whey protein concentrates
with a relative purity of 3585% protein in total solids
by cross-flow ultrafiltration (UF) accompanied with
diafiltration [1]. During recent years cross-flow microfiltration (MF) has became increasingly important
in the dairy industry, both for the removal of bacteria and for fat, caseins and whey proteins separation
[24]. The use of inorganic membranes have enabled
the development of a novel approach to the configuration of microfiltration hydraulic circuits by regulating
the pressure differential across the membrane (Alfa
Laval BactocatchTM process) [5].

Corresponding author. Tel.: +381-2154988;

fax: +381-21450413.

The acceptance of the cross-flow ultrafiltration and

microfiltration for whey processing has been relatively slow mainly because of decrease in permeation
flux through the membrane during operation. The
permeate flux declines from the very beginning of
filtration, falling rapidly at first and then eventually
leveling off to a rate which is dependent on the degree of concentration and the flow conditions close
to membrane surface [3,6,7]. This flux decline during
ultrafiltration and microfiltration of whey has been
attributed to concentration polarization and membrane fouling (including deposition, pore plugging
and protein adsorption in the pores of the secondary
cake and the membrane). Some studies on fouling
by whey proteins of polymeric [810] and inorganic
membranes [1114] have been reported in the literature.
The objective of this study was to examine membrane fouling of the chosen inorganic membranes by

0376-7388/00/$ see front matter 2000 Elsevier Science B.V. All rights reserved.
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whey proteins during cross-flow ultrafiltration and microfiltration. The influence of protein concentration
and transmembrane pressure on protein adsorption and
deposit formation by convection were examined.

2. Experimental
2.1. Membranes
The membranes studied were Membralox membranes (SCT, Bazet, France), configured as single
cylindrical tubes, 250 mm long, 7 mm ID and 10 mm
OD with a internal membrane surface area of 55 cm2 .
The ultrafiltration membrane with mean pore diameter of 50 nm, made of ZrO2 layer on an -alumina
support, was compared with microfiltration membrane with mean pore diameter of 200 nm, made of a
thin -alumina layer on an -alumina support.

2.4. Filtration tests

The experiments were carried out in a MF/UF
cross-flow filtration unit. The feed was circulated by
M pump with plunger head (HM/92/SS2C, Metering
Pumps, London). The flow velocity through the tubular membrane element was adjusted at 0.7 m s1 . The
permeate was returned to the feed reservoir in order
to prevent concentration of feed solution (volumetric
concentration factor, VCF = 1). The transmembrane
pressure difference (TMP) was adjusted by the regulation valve, and varied from 40 to 200 kPa. All
experiments were carried out at 25 C.
The membrane was cleaned according to the recommendation of the manufacturer prior to each experiment and the water flux of the cleaned membrane
was measured. The cleaning procedure was repeated
until the original water flux was restored.

2.5. Fouling under static conditions

2.2. Whey protein solutions
Whey protein concentrate of following characteristics: protein 72%, lactose 11.5%, fat 7%, ash 3%, water 4.5%, pH = 6.5, obtained from Denmark protein
A/S, Denmark, was dissolved in distilled water at various protein concentrations (10, 20, 40 and 60 g l1 ).
The pH value was adjusted by using 0.1 M NaOH to
pH = 6.6. The protein concentration was measured according to Lowry [15].
2.3. Equilibrium adsorption
Equilibrium adsorption of whey proteins to membranes was measured by following the change in protein concentration of 0.5 l; of protein solution in test
tanks made of glass in which the membranes were
soaked. The amount of protein adsorbed was calculated from the difference between the initial and final
solution concentrations once changes in the solution
concentration were no longer observed. Since several
days were required to reach equilibrium, adsorption
experiments were performed at 4 C to avoid bacterial
contamination. Studies were made for various protein
concentrations in the range 1060 g l1 , at pH value
of 6.6.

After the equilibrium adsorption of proteins was

reached, the membranes were rinsed with distilled water and tested for the pure water flux. The obtained
hydraulic resistance (termed Rw in this work) should
be attributed to membrane itself (Rm ) and that due to
protein adsorption (Rads ).
2.6. Fouling under dynamic conditions
After a cleaning procedure, membranes were used
for cross-flow filtration of whey protein solutions. The
permeate flux was calculated from the time needed
to collect 5 ml of permeate. The protein concentration
varied from 10 to 60 g l1 . The pH value of solutions
was 6.6 for all experiments.
The total hydraulic resistance (Rt ) was calculated
as [11]: Rt = TMP/(Jp ) where TMP is the transmembrane pressure difference, p the permeate dynamic
viscosity and J the permeate flux. This total resistance
can be represented as the summation of the two components: resistance of clean membrane (Rm ) and overall fouling resistance (Rf ) which is considered as an
additional resistance resulting from adsorption, concentration polarization and solute and particles deposition by convection.

M. .T.M..x Caric et al. / Journal of Membrane Science 165 (2000) 8388

85

The sieving characteristics of the membranes were

expressed in terms of the protein transmission ratio
(PTR)
PTR =

protein transmission for alumina membrane

protein transmission for zirconia membrane
(1)

Protein transmissions were calculated as

Protein transmission (%) =

Cperm
100
Cfeed

(2)

where Cperm and Cfeed are the protein concentrations

in the permeate and feed, respectively.

3. Results and discussion

3.1. Protein adsorption
The time profiles for the adsorption of whey proteins
from 40 g l1 protein solution on membrane surfaces
are shown in Fig. 1. There is an initial period of rapid
adsorption followed by a slower approach to a limiting value. It should be noted that the adsorbed quantities reported (in grams of proteins per m2 of external
membrane surface) include the adsorption of proteins
on the active layers and alumina membrane supports.
The protein adsorption on the glass of the test vessel
was negligible. The obtained time profiles were similar at all protein concentrations studied. The existence
of a limiting amount of adsorption which depends on

Fig. 2. Adsorption isotherms at 4 C for whey proteins on (N)

ZrO2 (50 nm) and () Al2 O3 (200 nm) membranes.

the whey protein concentration in solution indicates

that it should be possible to analyze the data in terms
of an equilibrium between the proteins in solution and
adsorbed proteins. Fig. 2 shows the measured adsorption isotherms for examined membranes submerged
in protein solutions. The adsorption increases and approaches a limiting value with increasing solution concentration, for both membranes. The protein adsorption on alumina membrane was higher than that in the
case of zirconia membrane. The changes in amounts
of adsorbed proteins can be explained by differences
in pore sizes and membrane materials. The obtained
results suggest that internal adsorption has significant
contribution to overall adsorption, especially in the
case of alumina microfiltration membrane which has
the pore sizes four times greater than that of zirconia
membrane pores.
3.2. Cross-flow filtration results

Fig. 1. Adsorption of whey proteins from a 40 g l1 protein solution

on membrane surfaces as a function of time. Membrane type: (N)
ZrO2 (50 nm); () Al2 O3 (200 nm).

In the cross-flow filtration studies, the decline in

permeate flux typical for membrane fouling was observed. Initially the flux was high, but the resistance
due to concentration polarization, gelling and/or
pore blockage rapidly increased and the flux declined to pseudo-steady state values. Fig. 3 shows the
pseudo-steady state permeate fluxes as the functions
of TMP and protein concentrations for the zirconia
and alumina membranes studied. The flux first increased with increasing pressure and finally reached
a limiting value leading to a pressure-independent
filtration. As the protein concentration increased,

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M. .T.M..x Caric et al. / Journal of Membrane Science 165 (2000) 8388

Fig. 3. Permeate flux for cross-flow UF/MF of whey protein solutions vs. transmembrane pressure using (A) zirconia and (B) alumina
membrane. Protein concentration: () 10 g l1 ; () 20 g l1 ; () 40 g l1 ; (N) 60 g l1 .

the flux achieved a limiting value at lower TMPs. It

can be seen that up to TMP of 200 kPa, the limiting
value of flux was not achieved during experiments at
protein concentration of 10 g l1 for both examined
membranes. The fluxes obtained with the alumina
membrane were higher then those obtained with the
zirconia membrane. From Fig. 3, it can be seen that
the differences in permeate fluxes of both membranes
at the same TMPs were lower as the protein concentration increased. Furthermore, limiting flux values
were achieved at lower TMPs in the case of the alumina membrane than those in the case of zirconia
membrane.
Table 1 shows the PTR as a function of filtration
time. The transmission of proteins was higher for the
alumina membrane than this obtained with the zirconia membrane, as expected. Nevertheless, the PTR
continually decreased during filtration. These results,
together with the flux variations with TMP and protein
concentration (Fig. 3) indicate that the pore plugging
Table 1
Changes in protein transmission ratio (PTR) with cross-flow filtration of 60 g l1 whey protein solution. TMP = 200 kPa
Filtration time (min)

Protein transmission ratio (PTR)

30
90
150

1.48
1.23
1.19

has greater contribution to overall fouling in the case

of larger pore alumina membrane.

3.3. Fouling analysis

In order to investigate the membrane fouling, the
different fouling resistances were calculated. The water flux of clean membranes were determined at a
feed flow velocity of 0.7 m s1 and at various TMPs.
The clean membrane resistances (Rm ) were found
to be 1.20 1012 and 0.68 1012 m1 for ziconia
and alumina membrane, respectively. The calculated hydraulic resistances (Rt and Rw ) at a TMP of
200 kPa for various protein concentrations are listed in
Table 2.
Fouling resistance during filtration (Rf ) and resistance due to protein adsorption (Rads ) increased
as protein concentration increased. Although, the
calculated resistances were greater for the zirconia
membrane than those in the case of the alumina
membrane, the normalized resistances (Rf /Rm and
Rads /Rm ) were greater for the alumina membrane.
This increased fouling of the alumina membrane is
probably due to larger pore sizes of this membrane
then the ones of the zirconia membrane. From the
ratios of Rads and Rf , it can be seen that the adsorption had greater contribution to overall fouling as the
protein concentration increased.

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87

Table 2
Calculations of different membrane resistances for experiments at the TMP of 200 kPa
Protein concentration (g l1 )
Resistance

(1012

Rt = R m + R f
Rw = Rm + Rads
Rf /Rm
Rads /Rm
Rads /Rf

m1 )

10

20

60

10

Zirconia (50 nm)

9.39
2.12
6.83
0.77
0.11

12.52
3.24
9.43
1.70
0.18

The variations of Rf /Rm and Rads /Rm versus TMP

for two protein concentrations are shown in Fig. 4.
As the TMP increased, Rf /Rm continuously increased
for the larger pore alumina membrane. In the case of
the zirconia membrane, the Rf /Rm was not influenced
to any significant extent by TMP at protein concentration of 10 g l1 (Fig. 4(A)). At higher protein concentrations, as the TMP was increased, the increase of
Rf /Rm was observed for the zirconia membrane, but
was not so pronounced as in the case of the alumina
membrane. From Fig. 4 it can be noticed that the protein adsorption on the alumina membrane had greater
influence on the overall fouling then the adsorption
on the zirconia membrane (also Rads /Rf in Table 2).
This phenomenon was more pronounced at higher protein concentrations and lower values of TMP (Fig.
4(B)). The results of fouling analysis indicate a different fouling mechanism for the zirconia membrane
than for the larger pore size alumina membrane, and
are in agreement with the observed flux behavior and
protein transmission for both membranes.

20

40

60

11.31
4.99
15.63
6.26
0.39

13.30
5.30
18.56
6.71
0.37

Alumina (200 nm)

15.19
4.91
11.66
3.09
0.27

7.02
2.19
9.32
2.18
0.24

10.53

14.49

4. Conclusions
Adsorption under static conditions and dynamic
fouling of 50 nm zirconia ultrafiltration membrane
and 200 nm alumina microfiltration membrane with
whey proteins were investigated. Static adsorption
studies indicated that membrane material and sizes
of the membrane pores have a considerable influence on the amount of protein adsorbed, and on the
effect this adsorption shows on permeate flux and
protein transmission. During cross-flow filtration,
flux followed classic membrane filtration behavior for the membranes studied, with flux increasing with increasing TMP up to a limiting value.
The limiting flux increased with increases in membrane pore size, but decreased with increasing protein concentration, as expected. The transmission of
proteins was higher in the case of alumina membrane, but decreasing of the protein transmission
ratio was observed during filtration. The protein
adsorption resistance controls the flux to a greater

Fig. 4. Rf /Rm and Rads /Rm as the functions of TMP for protein concentrations of (A) 10 g l1 and (B) 60 g l1 . Rf /Rm : () zirconia; ()
alumina. Rads /Rm : () zirconia; () alumina.

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M. .T.M..x Caric et al. / Journal of Membrane Science 165 (2000) 8388

extent for 200 nm pore size alumina membrane, than

for that with 50 nm pore sizes, where a resistance
due to fouling tends to dominate. The increasing
of fouling resistance with increasing TMP and protein concentration was especially pronounced in
the case of alumina membrane, which indicate a
different fouling mechanism for this type of membrane; it seems than adsorption-related pore plugging is more important in the larger pore alumina
membrane.

References
[1] J.H. Hanemaaijer, J. Hiddink, The expansion of membrane
filtration in the dairy industry, North. Eur. Dairy J. 51(2)
(1985) 33.
[2] R.J. Pearce, S.C. Marshall, J.A. Dunkerley, Reduction of
lipids in whey protein concentrates by microfiltration Effect
of functional properties, Int. Dairy Fed. 9201 (1991) 118.
[3] G. Gesan, U. Merin, G. Daufin, J.J. Maugas, Performance
of an industrial cross-flow microfiltration plant for clarifying
rennet whey, Neth. Milk Dairy J. 47 (1993) 121.
[4] M. Rosenberg, Current and future applications for membrane
processes in the dairy industry, Trends Food Sci. Technol. 6
(1995) 12.
[5] P.M. Kelly, Bacterial removal from milk by microfiltration
Application of new technology, farm and food, Summer
(1997) 26.

[6] R.S. Patel, H. Reuter, Deposit formation on hollow-fiber

ultrafiltration membrane during concentration of skimmilk,
Milchwiss. 40(10) (1985) 592.
[7] P. Aimar, C. Taddei, J.-P. Lafaille, V. Sanchez, Mass transfer
limitations during ultrafiltration of cheese whey with inorganic
membranes, J. Membr. Sci. 38 (1988) 203.
[8] D.N. Lee, R.L. Merson, Examination of cottage whey proteins
by scanning electron microscopy: relationship to membrane
fouling during ultrafiltration, J. Dairy Sci. 58(10) (1975) 1423.
[9] D.N. Lee, M.G. Miranda, R.L. Merson, Scanning electron
microscope studies of membrane deposits from whey
ultrafiltration, J. Food Technol. 10 (1975) 139.
[10] J.H. Hanemaaijer, T. Robbertsen, Th. van den Boomgaard,
J.W. Gunnink, Fouling of ultrafiltration membranes The role
of protein adsorption and salt precipitation, J. Membr. Sci.
40 (1989) 199.
[11] C. Taddei, G. Daufin, P. Aimar, V. Sanchez, Role of some
whey components on the mass transfer in ultrafiltration,
Biotechnol. Bioeng. 34 (1989) 171.
[12] J.-P. Labbe, A. Quemerais, F. Michel, G. Daufin, Fouling of
inorganic membranes during whey ultrafiltration: analytical
methodology, J. Membr. Sci. 51 (1990) 293.
[13] P. Savello, M. Caric, R. Mahmoud, Fouling of ceramic
membrane by milk proteins during microfiltration, Aust. J.
Dairy Technol. 52 (1997) 60.
[14] M. Caric, M. Tekic, S. Milanovic, D. Gavaric, D
- . Vatai,
H. Lipovcan, Adsorption of whey preteins on inorganic
ultrafiltration membranes (in Serbian), X Meeting, Modern
Trends in Dairy Technology, Novi Sad, 1994.
[15] O.H. Lowry, N.J. Rosebrough, A.L. Farr, R.J. Randall, Protein
measurement with the folin phenol reagent, J. Biol. Chem.
193 (1951) 265.