Desalination 144 (2002) 319–324

Mechanisms of flux decline during ultrafiltration of dairy

products and influence of pH on flux rates of whey
and buttermilk
H.G. Ramachandra Rao
Department of Food Science & Technology, University of Reading, Whiteknights, RG6 2AP, UK
Present address: Department of Dairy Technology, University of Agricultural Sciences, Bangalore-560024, India
Tel. 080-6675249, Fax: 080-3414848; email: hgrrao@indiatimes.com

Received 1 February 2002; accepted 1 April 2002

Abstract
The flux pattern during the ultrafiltration (UF) of milk systems (whole milk, skim milk and butter milk) was quite
different to sweet or acid whey. With whey, the initial flux was higher, but it fell with time as a result of membrane
fouling. Milk systems gave a lower initial flux, but flux remained unaltered during processing despite an increase in
the fouling coefficient. The higher concentration of protein in the milk systems seems to promote concentration
polarization which controls permeate flux. The flux pattern for sweet whey and buttermilk was strongly influenced by
pH. Increasing the pH of buttermilk from 6.6 up to 8.0 tended to reduce initial flux values and reduced deposit
formation. Buttermilk flux at high pH range (6.6 and above) was mostly controlled by concentration polarization.
Reducing the pH below 6.0 increased the initial flux, but caused more deposit on the membrane. Almost the opposite
was noticed in sweet whey. The initial flux increased as pH increased, followed by considerable flux decline during
1-h period of operation, which is linked to greater fouling of the membrane. Reducing the pH significantly reduced
initial flux, but deposit formation was at lower levels. These changes are brought about by the effect of pH change on
proteins and minerals of milk and whey.

Keywords: Membrane; Flux pattern; Fouling coefficient; Concentration polarization; Buttermilk; Whey; pH;
Ultrafiltration

1. Introduction
due to fouling and concentration polarisation
The major limiting factor in ultrafiltration (CP). To gain a better understanding of CP and
(UF) of dairy products is the fall in flux with time fouling, and the roles of the major components of
milk in these phenomena, would be desirable. In
Presented at the International Congress on Membranes and Membrane Processes (ICOM), Toulouse, France,
July 7–12, 2002.
0011-9164/02/$– See front matter © 2002 Elsevier Science B.V. All rights reserved
320 H.G. Ramachandra Rao / Desalination 144 (2002) 319–324
this study, we have attempted to observe the two
parameters independently using a fouling coeffi-
cient (FC) and by considering the initial reduction
in flux during UF of a range of dairy products.
Most previous studies have investigated flux
reduction during batch concentration. However,
in these cases changes in the viscosity and other
physical properties further complicate the
analysis. These experiments have attempted to
eliminate the effects of concentrating com-
ponents by carrying out UF in the total recycle
mode in which retentate and permeate were
continuously returned to the feed tank. In
particular, the behaviors of whey systems and
milk systems have been compared.
There is some evidence to show that calcium
phosphate precipitation plays a role in fouling
during UF of whey. Two studies on fouling in the
absence of proteins have been revealing. Hayes et
al. [1] found that when acid casein whey per-
meates was ultrafiltered, increasing the pH to 5.4
by addition of sodium hydroxide decreased the
flux, but upon readjustment of pH the flux
returned to near its original value. They noticed
that addition of NaOH resulted in the formation
of a white suspended solid, presumably calcium
phosphate, which was thought to be responsible
for the loss of flux rates when the permeate was
ultrafiltered. The process appeared reversible,
which is not usually the case in fouling. Kessler
et al. [2] studied the effect of low-molecular-
weight milk components such as salts and lactose
on the flux during UF. They concluded that in the
absence of protein, all dissolved low-molecular-
weight components normally present in milk
passed through the membrane without causing
fouling. However, when a deposit of protein was
present on the membrane, calcium had a con-
siderable effect on the resistance of the deposit,
and hence the flux. Calcium was observed to
produce considerable hardening of the deposited
layer, which was further enhanced by an increase
in UF pressure.
2. Materials and methods
Pasteurized milk and skimmed milk were
obtained from Grange Farm, Beaconsfield,
Bucks., UK. Fresh buttermilk was obtained from
Severnside Dairy, Stone house, Gloucestershire.
Cheese whey (sweet) was obtained from Village
Maid, Riseley, Berkshire, UK. Acid casein whey
was produced in the Department of Food Science
and Technology, Reading University. The pH of
permeates varied from 6.95 to 7.10.
2.1. Methods of ultrafiltration
A PCI minor UF module (Paterson Candy
International, Hants, UK) was fitted with ES 625
membranes (tubular polyethersulphone) with a
membrane area of 0.8 m2, molecular weight cut-
off value 25,000 and 99% retention of whey
proteins (manufacturer’s specifications). The unit
was operated with an inlet pressure (pressure at
the retentate side) of 0.6 MPa and outlet pressure
(pressure at the permeate side) of 0.2 MPa at
50°±1°C. Retentate flow rate was maintained at
1360 kg h!1 unless otherwise stated. The unit was
fitted with a mono pump. In all experiments feed
composition was kept constant by continuous
recycling of both feed and retentate back to the
feed tank (total recycle or constant composition
run).
The temperature, flow velocity and inlet and
outlet pressures were continuously monitored
throughout the experiments. Samples of feed and
permeate were taken for analysis at intervals. All
UF experiments were repeated in triplicate and
the flux values given are averages of three runs.
The reproducibility was good, statistical analysis
(F test) showed no significant differences
between replicate trials at the 1% level. Unless
otherwise stated, flux was measured over a period
of 60 min.
2.2. Fouling coefficient (FC)
FC is a measure of extent of deposit on the
membrane after each UF run. Values range from
0 (no fouling) to 1.0 (completely fouled). FC was
 H.G. Ramachandra Rao / Desalination 144 (2002) 319–324 321

estimated for all products after 1 h operation, and

at 5, 10, 20, 40 and 60 min during UF of
buttermilk and sweet whey.

2.3. Analytical
Milk and whey samples: Fat was measured by
the Gerber method; protein was measured by the
macro-Kjeldahl method [5]. Lactose contents of
milk and whey samples were measured using a
spectrophotometer, as described previously by
Lawrence [3].
Total calcium was determined in a Pye Uni-
cam Atomic Absorption Spectroscope, model
SP9, Pye Unicam Limited, Cambridge, UK.
Ionic calcium was determined using an ion
selective electrode ISE Ca++/pH Analyzer (Ciba
Corning Diagnostics Limited, Essex, UK).
The kinematic viscosity of products was
determined by using Ostwald U-tube capillary
flow viscometer using the British standard
method for determination of the viscosity of
liquids [4].
The pH of buttermilk and sweet whey was
adjusted at 25°C by using NaOH (500 g l!1) or
5 M HCl.
Fig. 1. Time course of flux of buttermilk during
ultrafiltration in total recycle mode at pH: ", 4-0; !, 4-6;
), 5-0; •, 6-0; Q, 6-6 (natural pH); O, 7-0; X, 8-0. For
experimental details, see text.
3. Results and discussion
The flux patterns of whole milk, skimmed
milk, buttermilk, sweet whey and acid casein
whey are shown in Fig 1. The initial flux rates for
both sweet and acid whey were higher than for
the milk products. The higher initial flux in whey
products could be due to a number of factors
including their lower total solids, casein, mine-
rals and fat contents (Table 1). The viscosities of
whey products were also slightly lower (Table 1).
However, the subsequent reductions in flux in
acid and sweet wheys over the 1-h period were
much greater than for the other products

Table 1
Composition of dairy products (all values are means of three replicates)

Component Sweet whey Acid casein whey Whole milk Skimmed milk Buttermilk
Fat, % 0.15 0.13 3.7 0.07 0.7
Protein, % 0.9 0.7 3.4 3.4 3.0
Lactose, % 3.5 4.0 4.7 4.7 4.0
Total Ca, mMa 9.8 22.0 27.0 26.0 21.0
Ionic Ca, mM 2.8 17.8 1.8 1.7 1.9
Viscosityb 1.19 1.08 1.46 1.33 1.43
a
Mini-molar solution. b
Kinematic viscosity – (m2s1)×10!6 at 25°C.
Table 2
322 H.G. Ramachandra Rao / Desalination 144 (2002) 319–324

Flux data and fouling coefficient (FC) during UF of milk and whey systems in total recycle mode (all values are ranges
of three replicates)

Sweet whey Acid whey Whole milk Skim milk Buttermilk

pH 6.0–6.3 4.6–4.8 6.6–6.7 6.6–6.7 6.6–6.8

Initial flux, L m!2 h!1 95–100 75–80 42–45 44–46 44–46
Flux 1 h, L m!2 h!1 65–70 42–45 38–40 42–44 42–44
Flux decline, % 25–30 53–55 <5 <5 <5
FC 0.66–0.70 0.82–0.88 0.70–0.71 0.70–0.75 0.65–0.68

(Table 2). This suggests that there is more gradual Table 3

long term fouling in whey products compared to
milk products.
A relatively steady level of flux was attained
more quickly in whole milk, skimmed milk and
buttermilk than in whey systems. This is in
agreement with the findings of Patel and Reuter
[5], who also found a faster attainment of a
steady-state flux in skimmed milk than for whey.
The initial flux with milk systems was consider-
ably lower than whey, but subsequent flux
reduction during 1-h operation was less than 5%
in all cases.
Of the five products studied, FC for acid whey
was the highest, corresponding to a greater fall in
flux (>50%) after 1-h operation (Table 2). Acid
whey had a lower initial flux than sweet whey,
probably due to the higher calcium, most of
which exists in the ionic form (Table 1). Among
the other four products, there was not much
difference in FC even though the flux rates were
much lower in milk products than in sweet whey
(Table 2). A higher FC may indicate the presence
of a hard deposit layer, which could not easily be
removed by rinsing. Nakanishi and Kessler [6]
found that the deposit formed on the membrane
surface consists of at least two parts: a loose
layer, which was easily removed, and a layer
which strongly adhered to the membrane surface.
FC was lower in sweet whey after 5 min
compared to buttermilk, but rose until it had
almost reached the levels of buttermilk after 1 h
Fouling coefficient measured at intervals during UF of
buttermilk and sweet whey
Time, min Buttermilk Sweet whey
5 0.60 0.51
10 0.63 0.57
20 0.64 0.62
40 0.66 0.65
60 0.68 0.67
of operation (Table 3). This rise was probably
related to the flux reduction during this period.
over the 1-h period with buttermilk, but this was
not reflected in reduction in flux in this product,
again showing that there was no direct relation-
ship between FC and flux values in buttermilk.
This suggests that CP is controlling the flux. It
appears that feed with low levels of protein
(sweet/acid whey), flux was controlled by the
fouling resulting from gradual adsorption of whey
proteins to the membrane surface and pore
plugging by precipitated calcium phosphate. With
feeds with higher levels of proteins (whole milk/
buttermilk/skim milk), the formation of a CP
layer within seconds of commencing UF brought
the initial flux to lower levels, but any further
fouling by precipitation of calcium phosphate or
adsorption of whey proteins increased the fouling
coefficient (FC), but had no effect on the flux
rates during 1 h of UF run.
 H.G. Ramachandra Rao / Desalination 144 (2002) 319–324 323

4. Effect of pH on flux patterns of buttermilk polarization. Reducing the pH below 6.6 in-
and sweet whey creased the flux but caused more deposit on the
The flux patterns of sweet whey and butter- membrane as indicated by high fouling coeffi-
milk were strongly influenced by pH. Increasing cient values. Almost the opposite was observed in
the pH of buttermilk from 6.6 to 8.0 tended to sweet whey (Fig. 2, Table 4). The initial flux
reduce initial flux values and reduce deposit increased as pH increased, followed by consider-
formation on the membrane as indicated by lower able flux decline, which was linked to greater
values for fouling coefficient (Fig. 1, Table 4). fouling of the membrane. Reducing the pH
Flux was mostly controlled by concentration reduced the initial flux considerably, but also
reduced further fouling. These changes are
thought to be brought about by the combined
Table 4
effects of pH change on the proteins and mine-
Fouling coefficientsa for sweet whey and buttermilk after rals, and in particular on calcium.
ultrafiltration for 1 h under total recycle mode at a range The proportion of calcium associated with
of pH values micelle was responsible for the strength of the CP
layer during UF of milk [2]. As the pH of
pH Sweet whey Buttermilk buttermilk was reduced, the proportion of soluble
calcium increased, and vice versa. Previous work
8.0 0.75 0.61 [8] has suggested that the initial flux during UF of
7.0 0.73 0.63
buttermilk is controlled by the formation of a CP
6.6 Not determined 0.67
6.0 0.67 0.76
layer. Hence, in the present study, when the pH of
5.0 0.68 0.82 buttermilk was reduced, a lower proportion of
4.6 0.66 0.84 micellar calcium would lead to a weaker CP layer
4.0 0.65 0.81 and a higher initial flux in buttermilk. The reverse
would be true at increased pH. Further FC values
a
For definition see Materials and Methods. (Table 3) of buttermilk indicate that the deposit
formation on the membrane was reduced at a
higher pH even though flux rates were low. In
sweet whey, which has a lower concentration of
protein than buttermilk and no casein micelles,
the effect of CP on initial flux is much lower [8],
and therefore the effect of calcium distribution on
the strength of the CP layer would be less
significant than in buttermilk. The increase in
initial flux at a higher pH in sweet whey could be
due to changes in the status of whey proteins. For
example, "lactoglobulin exists as octomers in the
pH range 3.5–5.2, but disassociates into
monomers under alkaline conditions. The more
rapid flux decline indicated a higher degree of
Fig. 2. Time course of flux of sweet whey during fouling at higher pH levels in sweet whey.
ultrafiltration in total recycle mode at pH: ", 4-0; !, 4-6;
), 5-0; •, 6-0; O, 7-0; X, 8-0. For experimental details,
see text.
324 H.G. Ramachandra Rao / Desalination 144 (2002) 319–324
5. Conclusions
The flux patterns of milk systems (whole/
skim/buttermilk) are quite different from that of
whey systems (acid and sweet whey). In whey
products the initial flux values are higher, but
drops in the flux were also higher with time as a
result of fouling of membranes. Milk products
recorded lower initial flux values, but in this case
the drop in the flux with time was almost
negligible. The high content of protein seems to
be responsible for lower initial flux because of
building up of a strong concentration polarized
layer. Further, pH also had influenced the flux
patterns of milk and whey systems in an opposite
way. In buttermilk at high levels of pH, the initial
flux values were lower, but the drop in flux with
time was also lower, whereas in sweet whey, at
similar levels of pH, the initial flux values were
higher, but the drop in flux with time was also
higher. Almost the opposite was recorded at
lower levels of pH in these two products.
Similarly, studies on fouling coefficient indicated
that in case of buttermilk as the pH increased, the
fouling decreased, whereas with sweet whey,
fouling increased with an increase in pH from 4.0
to 8.0. The effect of pH on flux pattern is attri-
buted to different changes it brought on status of
protein and minerals in whey and buttermilk, and
in particular on calcium.
References
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Griffin, Studies on whey processing by
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132–140.
[2] H.G. Kessler, C. Gernedel and K. Nakanishi, The
effect of low molecular weight milk constituents on
the flux in ultrafiltration, Milchwissenschaft, 37
(1982) 584–587.
[3] A.J. Lawrence, The determination of lactose in milk
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[4] British Standards Institution, Determination of the
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[5] R.S. Kirk and R. Sawyer, Pearson’s Composition and
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