Você está na página 1de 15

67

Fundamental

Principles of Ultrafiltration

ANN-SOFI

J6NSSON*

Department

of Chemical Engineering I, Lund University,

P.O. Box 124, S-221 00 Lund (Sweden)

GUNTRAGARDH
Department
(Received

of Food Engineering, Lund University,

P.O. Box 124, S-221 00 Lund (Sweden)

April 24, 1989; in final form October 5, 1989)

Abstract
Different theoretical models describing the influence of the operating parameters are treated in this paper. The
osmotic pressure, gel layer and resistance in series models are presented. The influence of different operating
parameters, such as the operating pressure, temperature, cross-flow velocity and concentration is demonstrated.
The complex fouling phenomenon is reviewed. Finally, various pretreatment and cleaning operations are
presented.
Introduction
Ultrafiltration
(UF) has become an important
industrial operation in many areas of application. A
highly successful application of ultrafiltration is the
recovery of electrodeposition
paints [ 1, 21. This
application is so established that ultrafiltration
equipment is considered a standard part of all electrodeposition systems nowadays.
A large number of commercial ultrafiltration
plants are also in operation in the food industry
[3-61. The separation of oil-water emulsions [7] and
the treatment of industrial effluents from the pulp
and paper industry [8] are other important applications.
Although commercially successful in many areas,
the complex, fundamental mechanisms of the ultrafiltration process are still poorly understood.
Ultrafiltration of macrosolutes causes an instantaneous and inevitable reduction in flux relative to the
pure water flux of the membrane. The polarization
phenomenon to which this loss of flux is attributed
has been explained by classical fluid mechanical and
mass transfer theory. The three most widespread
theories are
- the osmotic pressure model,
_ the gel layer model, and
- the resistance in series model.
As a result of fouling there is also a flux decline
which is not reversible by simply altering the operating conditions. Thus, the problem of fouling is often
superimposed upon the concentration polarization.
Its severity depends on the membrane material, the
*To whom correspondence should be addressed.

02552701/90/%3.50

Chem. Eng. Process.,

nature of the solutes, and other variables such as pH,


ionic strength, solution temperature and operating
pressure. So far, the prediction of fouling processes
has not been successful.
General tremfs
There are some general trends in ultrafiltration
that a successful theoretical model must be able to
predict.
(1) When the operating pressure is increased the
flux first increases almost linearly. This flux increase
levels off as the pressure is raised further, and finally
may even decrease at elevated pressures.
(2) Membranes with an initially high flux exhibit
greater flux declines than low flux membranes.
(3) Flux increases with temperature.
(4) Flux decreases as the solute concentration is
increased.
(5) An increase in the cross-flow velocity causes
an increase in the flux. The effect is reduced as the
velocity is increased further.
(6) Flux decreases with time. The decrease can be
more or less pronounced. The initial flux can usually
be restored by cleaning.
(7) Hydrophobic membranes have a greater fouling tendency than hydrophilic membranes.
(8) Hydrophobic solutes are known to be more
readily adsorbed onto membrane surfaces than hydrophilic solutes.
As ultrafiltration is such a complex process there
are, of course, exceptions to the above rules.
The performance of a membrane is very sensitive
to the actual operating conditions such as pressure,
temperature and pH, but also to the prehistory of

27 (1990) 67-81

Elsevier Sequoia/Printed in The Netherlands

68
the membrane.
For example, a membrane
that is
cleaned before use has quite a different performance
than that of one that has not been cleaned.
Real-life

performance

It may be argued that the real-life performance


of a membrane can only be obtained by industrial,
long-term, evaluations of the membrane. Theoretical
models would thus be merely of scientific interest.
We agree that experimental investigations are important, but we are also convinced
that theoretical
modelling of the ultrafiltration
process is necessary if
we are to understand,
and predict, the performance
of UF membranes.
The goal is, of course, to be able to design and
optimize systems where the ultrafiltration
equipment
is an essential, but unnoticed, part of the system, as
for example in electrodeposition
systems. In order to
reach this goal we need theoretical models to explain
the (too often unpredictable)
behaviour of ultrafiltration membranes.

Influence

of pressure

Fluid flow through porous media is usually


scribed by the well-known Darcy equation
91
J=-

de-

KAP
p AL

(1)

where J is the water flux, K is the specific permeability of the medium, AP is the pressure difference
across the medium, p is the fluid viscosity and AL is
the thickness of the medium.
It is, however, difficult to measure the effective
thickness of an asymmetric membrane. The thickness
and the specific permeability
of the membrane are
therefore usually combined to form a medium-specific parameter, the hydraulic resistance of the membrane, R, = AL/K.
In ultrafiltration,
solutes and/or particles are retained by the porous medium, the membrane.
This
makes the introduction
of more involved relations
than eqn. (1) necessary.
Solute is transmitted
by convection
towards the
membrane
as soon as the transport
of solvent
through the membrane commences, and the concentration is increased on the feed side of the membrane
as solute is retained. The osmotic pressure difference
Ail across the membrane can then become substantial. The driving force of the fluid is in this case given
by AP - c AD, according
to the three-parameter
model of Kedem and Katchalsky
[ 10, 111. The reflection coefficient 0 indicates the degree of permselectivity of the membrane. When CJ = 1 the solute is totally
retained and when 0 = 0 it is totally permeable.
The resistance of the accumulated
solute at the
membrane
surface is sometimes
represented
as a
hydraulic resistance R,. If we introduce hydraulic
resistances instead of permeability in Darcys equation and take the osmotic pressure of the solute into

Fig. 1. Alternative models of concentration polarization: (a) the


osmotic pressure model, (b) the gel layer model and (c) the
resistance in series model. The concentrations c,, cb, cP, and ca
denote the concentrations at the membrane wall, in the bulk
solution, the permeate, and the gel, respectively. The hydraulic
resistances are: the membrane resistance R,,,, the resistance of the
gel layer R,, and the resistance of the solute R,.

consideration,
the ultrafiltration
flux
scribed by the generalized equation

may

be de-

AP--AII
J=

/4%+%)

The theoretical models that will be treated in this


review can all be related to eqn. (2). These models
are the osmotic pressure model, the gel layer model
and the resistance in series model. Figure 1 shows
concentration
polarization
as represented
by the
different models.
Theoretical

models

In the osmotic pressure model the solute hydraulic


resistance R, is substituted by a continuous,
steep,
concentration
gradient at the membrane, resulting in
a substantial osmotic pressure.
In the gel layer model it is assumed that the solute
concentration
at the membrane
surface reaches a
limiting value, the gel concentration
cg.
In the resistance in series model the resistance to
flow is represented by a hydraulic resistance of the
solute, R,. The osmotic pressure AII is neglected.
The osmotic

pressure

model

At typical UF feed concentrations


the osmotic
pressure
of macrosolutes
is negligible.
Osmotic
effects are therefore frequently ignored. Very high
concentrations
at the membrane
wall and subsequently substantial osmotic pressures have, however,
been demonstrated
for dextran and whey protein
solutions, for example [ 121.
The concentration
at the membrane
surface depends on the ratio between the convective transport
of material to the membrane
and the diffusion of
material back to the bulk stream. During normal
ultrafiltration
conditions the solute concentration
at
the membrane wall, c,, may rise rapidly from the
bulk value, cb (see Fig. l(a)). The fluid flow through
the boundary
layer adjacent
to the membrane
is
frequently described by the film model as

69
where c,, is the concentration in the permeate and k
is the mass transfer coefficient.
Taking the osmotic pressure at the membrane
wall into account, Wijmans et al. [ 131 have derived a
relation between pressure and flux. Their calculated
results have been found to be in good accordance
with experimental results [ 141.
Wijmans et al. [ 131 used the following relationship
between the osmotic pressure and the concentration
at the membrane wall:
I
(4)

lT, = ac,

where a and II are solution-dependent constants.


When the solute is totally retained (d = 1 and
cp = 0), and the hydraulic resistance of the solute, R,,
is neglected, combination of eqns. (2)-(4)
gives the
following expression relating flux and applied pressure [13]:
J = AP - ac,, exp(nJ/k)

(5)

11&

A limitation of eqn. (5) is the availability of osmotic


pressure data for solutions containing high concentrations of macromolecules.
The pure water permeability (PWP) of ultrafiltration membranes is given as the pure water flux
(PWF) per unit pressure difference:
PWP = (PWFIAP),,

= = l/(pR,)

(6)

The flux as a function of operating pressure has been


calculated for three membranes with varying pure
water fluxes. The results are given in Fig. 2.
Initially, the flux increases linearly with pressure,
as can be seen in Fig. 2. As the flux increases further,
more and more material is transported to the membrane wall and concentration polarization increases.
The flux levels off as a consequence of the increasing
concentration polarization (see point ( 1) under General trends).

250
f

200

150

100
50
0

0.2

0.4

0.6

PRESSURE

0.8

1.0

1.2

(MPa)

Fig. 2. The effect of operating pressure on flux for three ultrafiltration membranes with varying permeabilities, calculated using
eqn. (5). The PWPs of the three membranes were 1000, 250 and
1C01m-2h-
MPa-
at
T=2OC
(this
corresponds
to
& = 3.6 X 102, 14.4 x 10 and 36.0 x 10tZm~, respectively).
Lines without symbols represent the pure water fluxes of the three
membranes and lines with symbols represent the flux of a
1.0 wt.% solution (c, = O.Ol), which has an osmotic pressure of
0.1 MPa at a concentration of 10 wt.% (a = 10 MPa and n = 2).
This applies fairly well to solutions of dextran [ 141. The value of
the mass transfer coefficient was 2 x 10m5 m SK.

The influence of the pure water j?ux


Compare, for example, the two membranes with
PWP = 1000 and 100 1 m- h- MPa- in Fig. 2. As
can be seen, the increase of the flux declines faster
for the high permeability membrane than for the low
permeability membrane. This explains why membranes with an initially high flux exhibit greater flux
declines than low permeability membranes (see point
(2) under General trends).
The influence of concentration polarization is
small for membranes with low pure water fluxes.
They are, consequently, almost linearly dependent
on pressure, as stated in Darcys equation.
Membranes with high pure water fluxes (those
that look so promising in membrane tables!) suffer
from high osmotic pressures which are caused by
high concentrations at the membrane wall. Owing to
this high osmotic pressure, the flux of these membranes is much lower than the pure water flux.
A reasonable question is, of course, if we can ever
reach the level of the pure water flux of the high
permeability membranes. One way of accomplishing
this is by increasing the mass transfer coefficient k.
The influence of other parameters may be obtained
from the derivative of eqn. (5). The derivative of this
equation is [ 131

dJ=L(l
d AP

pR,

+A!%)-

The order of magnitude of the deviation from the


pure water flux is given by the second term in eqn.
(7), AfI n/pR,k.
The product flux is affected by, for
example, the permeability of the membrane (the
effect of R, is demonstrated in Fig. 2), the temperature of the solution (which affects p), the osmotic
pressure (AD and n) and the cross-flow velocity
(affects k). These parameters are discussed further
later in this paper.
The gel layer model
The pressure independence of flux when the operating pressure is increased was originally explained
by Blatt et al. [ 151 as being due to the formation of
a gel layer at the membrane surface. They stated that
a limiting flux value is reached when the concentration of solute in the boundary layer reaches the gel
concentration cg. The flux-limiting value for a totally
retained solute (cr = 0) at gel layer conditions is
given by eqn. (3) as
J=kln

2
(8)
0
In the gel layer model the osmotic pressure is
assumed to be zero. The fluid flow is then described
by
AP
J=
(9)
14Rm + Rs)
When the concentration
at the wall has not
yet reached the gel concentration,
the polarized

70
boundary layer offers a resistance to the flux,H&,
and R, = R,, . Under gel layer conditions
the resistance of the gel layer represents the resistance of the
solute, R, = R,. When both concentration
and gel
polarization
occur the resistance
of the solute is
R,= R,+Rb,
[15].
The gel layer model predicts the flux to be independent of operating pressure. An increased pressure
merely results in a thicker gel layer (larger &),
which retards the flux to its original value.
The gel layer model has been frequently used to
correlate experimental
limiting fluxes [ 16- 181. The
gel concentration
may be obtained by extrapolation
of a plot of J versus In cb. It has, however, been
shown that the information
obtained on gel concentrations is not reliable. For identical solutions different authors have found widely varying values at cg

[191.

Experimental
evidence [ 151 indicates that the viscous solution in the boundary layer approaches
a
close-packed
configuration
of low hydraulic permeability. It has been argued, however, that it is only
materials
such as agar, pectin, gelatin and some
proteins that might denaturate
at the membrane
surface to give true gels [ 141. It has also been shown
that feed solutions
of various macrosolutes
with
concentration
cb = cg did not give zero flux [20].
Based on their analysis, Wijmans et al. [ 131 concluded that osmotic pressure limitations would be
expected in the ultrafiltration
of macrosolutes
with
molecular weights of 10 000- 100 000, and gel layer
limitations would be expected for larger molecules.
The resistance in series model
The concentrated
solution of macromolecules
at
the membrane
wall provides a physical barrier to
solvent and solute transport. The resistance of this
boundary
layer may be treated as one or several
resistances in series with the membrane,
as already
discussed in the gel layer model.
The resistance in series model has been shown to
apply for dextran solutions [21]. The resistance of
the solute in this investigation
was estimated from
independently
measured sedimentation
coefficients.
The results were also in reasonable agreement with
results obtained from the osmotic pressure model.
The resistance in series model predicts a pressureindependent flux, as does the gel layer model. That is
to say, an increase in the pressure results in a thicker
gel layer and an increased hydraulic resistance.
An advantage with the resistance in series model
is that it makes it possible to distinguish between th0
influence of different flux decline phenomena.
The resistance to flow may be accounted for by a
number of resistances: the resistance R, of the membrane, the boundary
layer resistance
R,,, the gel
layer resistance R,, and the adsorbed layer resistance
R,. Equation (2) may then be written as
AP
J=p(R,+R,+R,+Rh,)

(10)

01

1000

2000

ROTATION

3000

SPEED

b
4000

(rpm)

Fig. 3. Determination
of the influence of the membrane
resistance, boundary layer resistance, gel layer resistance and adsorbed
layer resistance
for 1.0 wt.% BSA at 0.5 MPa. The numbers
denote the order in which the measurements
were performed. The
rotary module is described in detail in ref. 22.

The influence of different resistances on flux has


been investigated for bovine serum albumin (BSA) in
a rotary module [22]. Different flow resistance regions were distinguished
by varying the rotation
speed. Figure 3 shows the experimental results.
First, the membrane
resistance
&
was determined by ultrafiltration
of pure water at high rotation
velocity.
From
the pure water
flux the
membrane resistance could be calculated as, in this
case, R, = R, = Rb, = 0.
The pure water was then replaced by a 1.0% BSA
solution.
The flux was measured
at decreasing
rotation velocities. Concentration
polarization
and
gel layer formation
were assumed
to be zero
(R, = R,, = 0) as long as the flux remained constant.
The flux began to decrease when the velocity was
decreased to about 2400 rev min- as can be seen in
Fig. 3. As long as it was possible to restore the initial
flux value by increasing the rotation velocity to the
original value, the influence of the gel layer was
assumed to be zero, i.e. R, = 0.
Down
to about
1000 rev min-
the original permeate flux was almost completely restored when the
velocity was increased. When it was no longer possible to attain the original flux values when the velocity was increased, it was deduced that an irreversible
phenomenon
had taken place, namely gel layer formation.
Compaction of membrane and gel layer
The theoretical models described above all predict
a limiting flux value at increasing pressure. They do
not, however, explain why the flux may decrease
when pressure is increased. This phenomenon
may,
however, be explained as being the result of compaction of the membrane and/or the gel layer.
The membrane
pure water permeability
K has
been related to pressure for reverse osmosis cellulose
acetate membranes by [23]
K=&exp(-uP)

(11)

where K,, is the specific membrane permeability


at
zero pressure and LXis a measure of the susceptibility
of the membrane to compaction.
It has been questioned whether the porosity of
ultrafiltration
membranes is influenced to any appre-

71
ciable extent by the low applied pressures that are
encountered during ultrafiltration. It is, however, a
reasonable assumption that as the porosity of the
membranes increases, the susceptibility to deformation also increases.
For a membrane with surface porosity S,, and
cylindrical membrane pores with radius rp, the
Hagen-Poiseuille
equation [ 241 applies:
S, rp2 AP
8pAL

J=

(12)

Combination of eqns. (1) and (12) reveals that the


specific membrane permeability is proportional to
the inverse of the square of the pore radius and
A, AL

(13)
rZ12
where A, is a proportionality constant and AL is the
membrane thickness. Equation ( 13) shows that even
a modest decrease in the pore radius may lead to a
significant increase in the resistance of the membrane.
The hydraulic permeability of a gel, Kg, may be
approximated by the Kozeny -Carman relation [ 151,
R,=-

(4 &I2
180(1 -E)~

(14)

where d, is the diameter of the solute molecules and


E the porosity of the gel. The hydraulic resistance of
the gel,

(1%
is thus obviously very sensitive to the molecule size
and porosity. AL, in eqn. (15) is the thickness of the
gel layer.
The porosity of the gel, E, and the pore size of the
membrane, rp, are affected by the operating pressure.
The porosity of the gel, as well as the membrane
pore radius, decreases (at least to some extent) when
the pressure increases. This results in increasing hydraulic resistances, according to eqns. ( 13) and ( 15).
The increasing hydraulic resistances would then explain why flux may decrease when the operating
pressure is increased.
Furthermore, for many porous materials compression is an irreversible process. When the pressure
is decreased the material does not expand to its
original size. This means that if a high pressure has
been applied to the gel layer, the flux may not be
restored by decreasing the pressure again.

Influence

of temperature

The viscosity of the solution decreases when the


temperature is increased. This results in an increase
in the fluid flow through the membrane. According
to Darcys equation, (I), the fluid flow is proportional to the inverse of the viscosity. Equation (5),
which takes the concentration polarization into con-

Fia. 4. The influence of temoerature on flux. calculated usine ean.


(ST. The solid line represents the pure wate; flux for a memiraie
with PWP=2501m-2h-MPa-
at T=20C
(R,=1.4x
IOl3 m-l). Lines with symbols represent the ultrafiltration flux at
three bulk concentrations, 0.5, 1.0 and 2.0 wt.%. The values of the
other parameters in eqn. (5) were: AP = 0.5 MPa, k = 2 x
10-5ms-,a=10MPaandn=2.

250,

0.2

0.4

0.6

PRESSURE

0.8

1.0

1.2

(MPa)

Fig. 5. The influence of pressure on pure water Aux and ultrafiltration flux at 20 and 60 C. The values of the parameters in eqn.
(5)were:PWP=2501m-Zh-MPa-at
T=20C(R,=1.4x
IO m-l),
AP = 0.5 MPa, cb = 1.0 wt.%, k = 2 x 10e5 m SK,
n=lOMPaandn=2.

sideration, predicts, however, a less pronounced dependence. The deviation from the ideal behaviour
(the pure water flux) increases when the conccntration increases, as can be seen in Fig. 4.
The difference between the idea1 behaviour and
the real flux becomes larger as the temperature is
increased. This is quite natural as the concentration
polarization, and thus the osmotic pressure at the
membrane, increases when flux increases as a consequence of the elevated temperature. This phenomenon is also illustrated in Fig. 5.
The membrane resistance R, is not influenced by
variations in the temperature, whereas the pure water flux is. This means that when studying the influence of pressure at different temperatures a new
PWP line is obtained at each temperature. As can be
seen in Fig. 5 the difference between the pure water
and ultrafiltration flux becomes larger as the temperature and pure water flux increase. This is in analogy
with the behaviour shown in Fig. 2, where we
demonstrated that the difference between the pure
water and ultrafiltration flux was largest for the
membrane with the highest PWP.
Influence of feed concentration
A general trend is that flux decreases as the bulk
concentration increases (see point (4) under General

72
250

200

200

150

150

100

100
50
50
0
0

10

CONCENTRATION
Fig.
ing
eon.
(R,
n =

15

20

IN BULK (w-%)

6. The influence of bulk concentration


on flux at two operatpressures, 0.5 and 1.0 MPa. The values of the parameters
in
(5) were:
PWP-2501m-2h-MPa-1
at
T=2OC
= 1.4 x lOI rn-),
k = 2 x 10e5 m s-,
(I = 10 MPa
and
2.

trends). The film model (eqn. (3)) predicts, for example, that the flux J varies proportionally with the
logarithm of the bulk concentration ct,, and the gel
layer model predicts that the intercept of a plot of J
versus In ct, corresponds to the gel concentration cg.
The variation of flux with concentration, as predicted by the osmotic pressure model (eqn. (S)), is
shown in Fig. 6.
The flux is, as expected, higher at the high operating pressure. But, although the pure water flux (at
c,, = 0 in Fig. 6) is doubled when the pressure is
doubled, this considerable difference between the two
flux curves vanishes as the concentration increases.
The two flux curves in Fig. 6 approach zero at the
bulk concentration at which the osmotic pressure
equals the operating pressure. It is thus possible to
increase the final concentration of the solution by
increasing the operating pressure.
The osmotic-pressure-concentration
relationship
of the solution not only determines the final retentate

CONCENTRATION

two
and
and
eqn.
and

concentration. It also determines the magnitude of


the ultrafiltration flux. In Fig. 7 the flux of two
solutions with different osmotic-pressure-concentration relationships is shown. The high osmotic-pressure-concentration
relationship applies fairly well to
a solution of polyethylene glycol (PEG) and the low
osmotic-pressure-concentration
relationship applies
to a solution of dextran [14]. As shown in the
Figure, the flux of the solute with the higher osmotic
pressure (PEG) was not only lower, but also decreased faster.
When the concentration in the feed increases, the
flux becomes less and less affected by the PWP of the
membrane, as can be seen in Fig. 8. Thus, the flux at
the end of the concentration operation cannot be
increased by the introduction of a membrane with a
higher pure water flux.
Wijmans et al. [ 131 have rearranged the osmotic
pressure model relationship, eqn. (5), to give
-= dJ

d In ct,

150

IN BULK (W-/o)

Fig. 8. The influence of bulk concentration


on flux for
membranes
with different pure water permeabihties,
1000
250 1 rnpz hh MPa-
at
T=20C
(&=3.6x
IO*
1.4 x IOr m-, respectively). The values of the parameters
in
(5) were: AP = 0.5 MPa, k = 2 x IO-srn s-r, a = 10 MPa
n = 2.

1 + &, k/AII n

(16)

Equation ( 16) predicts a slope approaching -k for


the J versus In c,, plot at high bulk concentrations
(high AII values). This is also predicted by the gel
layer model.

125

100

E2
=

s
k

The mass

75

trader

coefficient

The flux is thus very sensitive to operational


parameters that may affect the mass transfer coefficient k. The mass transfer coefficient may be
obtained from correlations of the form

50

25

CONCENTRATION

IN BULK

(W-%)

Fig. 7. The influence of bulk concentration


on flux for two solutes
with different osmotic pressure-concentration
relationships.
The
high osmotic pressure solute (a = 23 and n = 2) corresponds
to a
solution
of PEG. The low osmotic
pressure
solute (a = 10
and n = 2) corresponds
to a solution of dextran. The values of
other parameters
in eon. (5) were: PWP = 250 1 m mz h MPa
T = 20 C
(R, = 1.4 x 10s mm),
AP = 0.5 MPa
and
at
k = 2 x 10VSm s-r.

where d,, is the hydraulic diameter of the flow channel, D the diffusivity, and Sh, Re and Sc are the
Sherwood, Reynolds and Schmidt numbers. The
constants A, a, b and c vary with flow conditions.
The mass transfer coefficient has been shown to
have a slight tendency to decrease with increasing
pressure and bulk concentration [ 121. The decrease
in flux with increasing pressure at elevated pressures

73
was suggested earlier in this paper to be the result of
the compaction of the membrane and gel layer at
high pressures. The decrease in the mass transfer
coefficient with increasing pressure has been put
forward as another explanation of this phenomenon
[141.
The diffusivity of macrosolutes is usually dependent on concentration. Owing to the concentration
polarization, the concentration at the membrane surface may differ significantly from the concentration
in the bulk, This may, of course, modify the effective
mass transfer coefficient. The diffusivity is also increased by an increase in the temperature. However,
the operational parameter that has the largest impact
on the mass transfer coefficient is the cross-flow
velocity.
Influence

of the cross$ow

velocity

In both the osmotic pressure and the gel layer


models it is presumed that the mass transfer coefficient is proportional to un, where u is the crossflow velocity and a is the Reynolds number exponent
in eqn. ( 17). The value of the exponent has been
much debated. A thorough review of different mass
transfer coefficients, together with their adaption to
ultrafiltration, is given in ref. 25.
In Figs. 9 and 10 a value of II = 0.75 according to
the Chilton-Colburn
model has been used. The influence of the cross-flow velocity on the flux for two
membranes of differing pure water flux (Fig. 9) and
at varying bulk concentrations (Fig. 10) has been
calculated from eqn. (5).
The influence of the cross-flow velocity increases
as the permeability of the membrane increases, as
can be seen in Fig. 9. This is easily understood as we
know that the concentration polarization is more
pronounced for membranes with higher pure water
fluxes.
It is, perhaps, not that easy to anticipate how the
cross-flow velocity influences the flux at various concentrations. As a rule, we can say that flux becomes
independent of cross-flow velocity at a much lower
velocity for low concentration solutions. In Fig. 10
it can be seen, for example, that the solution with
250 ,

CROSS FLOW VELOCITY

(m/s)

Fig. 9. The influence of the cross-flow velocity on flux for


membranes with different pure water permeabilities,
500
at
T=20C
(R,,,=7.2x
IO*
250 1 m-* h- MPa-
1.4 x IO m-l). The values of the other parameters in eqn.
cb = 1.0 wt.%,
k = 2 x 10-s m s-
were: AP = 0.5 MPa,
cr = 10 MPa and n = 2.
U =4ms-1,

two
and
and
(5)
at

01

CROSS FLOW VELOCITY

10

(m/s)

Fig. 10. The influence of the cross-flow velocity on flux at three


different bulk concentrations,
0.1, 1.0 and 5.0 wt.%. The values
of the parameters
in eqn. (5) were: PWP = 500 1mm*hh
AP = 0.5 MPa,
at T = 20 C (R, = 7.2 x 10 II-),
MPa-
k=2x10-5ms-atu=4ms-.a=10MPaandn=2.

ci, = 0.1 wt.% has reached its maximum flux at a


velocity of approximately 4 m s-l, while the flux of
solution
is still increasing
at
the 5.0 wt.%
u =8ms-.
If a gel layer is formed, the flux may become
independent of cross-flow velocity at low velocities,
even for high concentration solutions, because once
a gel layer has been formed it is not possible to
recover the flux by simply increasing the velocity
(this was illustrated in Fig. 3). Thus, the velocity
ought to be kept, if possible, at such a level that gel
formation is avoided. If the cross-flow velocity is
decreased temporarily during operation, the formation of a gel layer may be avoided if the flux also is
decreased, for example, by temporarily lowering the
operating pressure.
Rotating

modules

The ultrafiltration flux of a membrane is controlled by the rate at which the retained solutes can
be transferred from the membrane wall back into the
bulk fluid. Thus, operational variables that aid backtransport from the membrane will directly increase
the flux.
The shear rate at the membrane wall is, as has
been clear from the above, the major depolarizing
parameter. This fact initiated the development of
rotating modules [26,27]. However, the commercial
success of rotating modules has been limited (due to
high investment costs).
Positive results from tests with a modified plate
and frame rotary module, the ABB CROT filter,
have been reported recently. In pilot-plant equipment, bleaching effluent from a Swedish pulp mill
has been treated successfully over a one-year period.
A larger pilot plant (membrane area 200 m2) has
recently been installed at the same mill.
During ultrafiltration of oil emulsions in a rotary
module it was found that the flux could be increased
further if the roughness of the module wall was
increased [28]. The increase in the wall roughness
was accomplished by the introduction of a net. The
increase in the flux was ascribed to an increase in the
mass transfer coefficient due to the presence of the
net, acting as a static convection promoter.

74
It has also been shown that the mass transfer
coefficient can be increased, not only by increasing
the wall roughness, but also by using corrugated
membranes [29]. It was found that corrugations increased the mass transfer more effectively than an
increase in the cross-flow velocity. These tests were,
however, performed with reverse osmosis membranes, but a similar type of effect of membrane
surface roughness has been demonstrated for ultrafiltration membranes [ 301.
Influence

of suspended

(a)

:,:,:>
D
\\I

\\\
,.;<;.;

(b) ...

Fig. Il. Adsorption of solute molecules: (a) solute molecules


forming a gel layer; (b) solute molecules adsorbed onto pore

solids

Walk.

The presence of suspended solids may enhance the


flux. There are several examples of this phenomenon
[31]. In such cases of flux enhancement it is thought
that the solids intermittently disturb the polarized
layer, sweeping away deposited solutes [32, 331.
Influence

of time

Filtration theory predicts that flux decreases as


t I* under unstirred conditions [34]. This is also
predicted by the gel layer [35] and osmotic pressure
models [ 361.
The influence of time under cross-flow conditions
is more complicated. The film mode1 predicts that a
rapid drop in flux occurs as the boundary layer is
built up. Several workers have studied the initial
polarization period experimentally. Polarization time
varied from about 5 to 50 s [ 181. The flux at the end
of the initial polarization period should be the limiting flux predicted by eqn. (8).
The gel layer model, as well as the osmotic pressure model, predicts that, after the initial polarization period, flux remains constant with time.
However, a gradual, long-term decay in flux is noted
in many applications. This flux decline is due to
fouling. The causes of fouling are very disparate. It is
thus difficult to derive a general theoretical expression for the flux-time relationship.
A simple relation between flux and time is the
empirical relationship
J = Jot

(18)

where JO is the initial flux and n is an exponent less


than zero. Equation (18) has been much used to
predict flux decline in reverse osmosis systems [37].
Equation ( 18) gives, however, no information about
the influence of the operational parameters. Nor is
the influence of the properties of the solution taken
into account.
In the remaining part of this paper we will discuss
the influence of the nature of the solutes, the membrane material, pH and ionic strength on fouling.
We will also discuss how fouling can be controlled.
Fouling
It is very risky to make general statements about
the influence of different parameters on fouling. The

many exceptions to the general rules reflect the complexity of the fouling phenomenon. (One sometimes
has the feeling that there are more exceptions than
rules.) Comprehensive information may, however, be
found in a number of review articles treating this
subject (see, for example, refs. 31 and 38-41).
The fouling process has variously been ascribed to
the formation of a slowly consolidating gel layer and
to membrane pore plugging. The former event may
occur if the solute molecules are large enough to be
retained by the membrane. This is illustrated in Fig.
1 l(a). As the gel layer is consolidated the hydraulic
resistance Rg increases continuously with time.
If, on the other hand, the solute molecules are
small enough to enter the pores they may be adsorbed
onto the pore walls, as can be seen in Fig. 1 i(b). The
adsorbed molecules can then restrict the effective pore
diameter and the membrane resistance R,,, increases
as a consequence of the pore blocking.
Retention

characteristics

The adsorption of solute molecules affects not only


the flux, but also the retention characteristics of the
membrane. For example, the albumin transport drops
to exceedingly low values within minutes for membranes which at the start of ultrafiltration are quite
leaky to serum albumin [38].
Similar behaviour has been observed for membranes partially permeable to protein [42]. The increase in protein retention with time was attributed to
gradual pore blocking caused by the adsorption of
proteins on the inner wall of the pores of the membrane.
The reduction in effective pore diameter for a
membrane contacted with ovalbumin has been determined by measuring the retention of PEG. During
ultrafiltration the retention of PEG increased from
20% to 95% [43].
The pore size distribution of a polysulphone
membrane, before and after treatment of red grape
must, was determined by a method based on combined bubble pressure and solvent permeability measurements [44]. The characteristics of the membrane
were changed in two respects: the number of small
pores increased and pores with a smaller pore diameter than in the initial state of the membrane were
detected.

Characteristic
pore sizes were determined
for
clean and fouled membranes
by Hanemaaijer
et al.
[45]. The pore size changes caused by solute adsorption were derived from saccharide retention data. It
was shown that for a hydrophilic
low protein adsorbing membrane,
the calculated pore size was not
affected by protein adsorption,
whereas the pore size
of hydrophobic
membranes
was reduced.
Adsorption
of one of the solutes in a mixture may
thus also affect the retention
of other compounds.
Solutes that are not retained by the membrane when
tested alone may very well be retained due to solutemembrane
and solute-solute
interactions
of other
compounds
in the solution.
It is thus advisable to
confirm the expected retention
characteristics
of a
membrane by tests with real solutions and not base
predictions
of membrane performance
on tests with
idealized solutions.
But even predictions
based on
tests with real solutions
may be unreliable
as the
composition
of many process streams may occasionally differ.
Influence

of membrane

material

It is commonly
recognized
that hydrophobic
membranes
have a larger fouling tendency than hydrophilic membranes.
Even the pure water flux may
be affected by the nature of the membrane material
as absolutely
pure water is very hard to find (a
well-known
problem
for anyone who works with
membranes).
Investigations
[ 3 1,46,47]
have shown that the
pure water flux of hydrophobic
membranes decreases
with time, while the pure water flux of hydrophilic
membranes is less time dependent. This phenomenon
has been attributed
to contamination
of the pure
water by bacteria and trace colloids [31] and to trace
amounts of waste products of micro-organisms
[46]
present in the pure water.
Infruence

of membrane

pore size

Membrane
performance
cannot, however, be related simply to the membrane material. For example,
the flux decline of three membranes,
all made of
polysulphone,
was noticeably different when the pH
of a BSA solution was altered [48].
The same disparate behaviour was found for three
membranes
with varying pore sizes used for the
treatment
of caustic bleach plant effluent [49]. The
effect on the flux of the three membranes
when the
pH was lowered differed considerably,
as can be seen
in Fig. 12.
At the higher pH the flux of all three membranes
was almost identical, while when the pH was lowered
to below the isoelectric
pH of the solution,
the
magnitude
of the flux followed the cut-off of the
membranes,
that is, the densest membrane
experienced the largest flux decline, while the flux of the
membrane with the largest pores was unchanged.
It was thus the membrane with the smallest pores
that exhibited the greatest flux decline in this case.

-0

20

40

80

100

TIME (h)

(a)

200

150

zj

100

ii

50
0

20

40

80

100

TIME (:;

(b)

Fig. 12. Flux of three membranes with varying cut-off at different


values of pH: (a) pH 11 and (b) pH 4.6. Two membranes were
made of polysulphone, PU120 with a cut-off of 20 000 and PU608
with a cut-off of 8000, and one was made of polyethersulphone,
ES404 with a cut-off of 4000. All three membranes were manufactured by PC1 Membrane Systems. The operating pressure was
0.8 MPa and the temperature 55 C. (Data from ref. 49.)

Usually, however, the relative flux decline is greatest


for the membrane
with the highest pure water flux
(which is often the membrane with the largest pores).
Influence

of surfactants

Surface chemical phenomena


play an important
role in the fouling of membranes.
It is well known,
for example, that hydrophobic
solutes (e.g. BSA) are
more readily adsorbed onto the membrane
surface
than hydrophilic
solutes (e.g. dextran).
Antifoams used in fermentation
can cause considerable fouling of membranes
during downstream
processing [50-541. The membranes
in some commercial membrane
plants have even been destroyed
when an antifoam agent has been exchanged. In such
cases irreversible
adsorption
of the new antifoam
agent has caused a nearly zero flux and made it
necessary to replace all the membranes.
Despite some frightening
examples of the influence of surfactants,
as a class of materials they do
not lead to fouling problems. It has been shown, for
example, that the flux of ultrafiltration
membranes
can be enhanced
if the membranes
are pretreated
with non-ionic
surfactants
before use [55]. There is
also evidence that cleaning, due to the surfactants in
the cleaning solution, may not be considered merely
as a cleaning operation, but also as an in situ surface
modification
[49].
Some surfactants,
however, may interact with the
membrane
and cause an irreversible
flux decline.
Many parameters
may affect the flux decline of

76
surfactant solutions, for example, the membrane material, the pore size of the membrane and, of course,
the nature of the surfactant.
Surfactants

causing fouling problems

The flux of antifoams with cloud points has been


shown to be virtually zero for polysulphone membranes at, and above, the cloud-point temperature
[54]. When the temperature was lowered the flux
returned approximately to the original level. No flux
decrease was observed for a hydrophilic membrane.
This type of flux decline was not observed for noncloud-point antifoams.
Irreversible
fouling is often observed when
cationic polymers and surfactants are in contact with
negatively charged membranes. Cationic surfactants
do not always cause irreversible flux declines, however. The initial flux of cellulose acetate membranes
was restored when the membranes were flushed with
pure water after ultrafiltration of the cationic surfactant hexadecyl trimethylammonium bromide [47]. A
slight, irreversible flux decline was observed for
membranes of polysulphone and polyvinyldifluoride
when exposed to the same surfactant.
Critical micelle

concentration

The flux decline on the addition of a surfactant is


usually very fast, within minutes, and even small
amounts of surfactant are enough to cause a considerable drop in flux. At the critical micelle concentration (CMC) micelles are formed and the retention
then often increases as the micelles are too large to
pass freely through the membrane pores.
At CMC the flux often stabilizes at a constant
level, as can be seen in Fig. 13. The Figure shows the
influence of a non-ionic surfactant on the flux of a

600
506

polysulphone membrane, before and after cleaning


of the membrane. After cleaning, the pure water
flux of the membrane increased from 140 to
540 1 m- h-.
The tlux increase after cleaning, shown in Fig. 13,
makes it easy to understand why cleaning is such a
vital part of membrane operations. This will, however, be treated in more detail in a following section.
We will now take a look at two other properties that
may influence the fouling tendency of solutes,
namely the solution pH and the ionic strength.

Influence of pH and ionic strength


The solution pH and ionic strength affect the
charge, stability and tendency to aggregate of the
solute molecules and this influences, of course, the
membrane performance.
A reduction in the flux at the isoelectric pH has
been found for many solutes (BSA [20,31,56]
and
whey [57,58], for example). At the isoelectric pH the
net charge is zero. Thus, a solute which under normal conditions is not adsorbed onto the membrane
due to electrostatic repulsion (Fig. 14(a)) is no
longer repelled at the isoelectric pH (Fig. 14(b)).
Alteration of pH does not only influence the
solute-membrane
interaction, but also the solutesolute interaction. If the electrostatic repulsion between solute molecules ceases this may result in a
more closely packed and denser gel layer. The same
result may be obtained if salt is added to the solution.
It has been shown that the addition of salt to a
starch solution results in a drastic decrease in flux
[59]. It was suggested that the cations shielded the
charges of ionized carboxyl groups on the oxidized
starch chain. This shielding caused contraction of the
starch molecules which resulted in lower viscosity
and stability of starch in the solution. Densification
of the starch gel increased the hydraulic resistance of
the gel layer and the flux was thus decreased. No
interactions were observed for completely un-ionized
pearl starch.

406
300
266
160

100

200

300

400

500

TIME (h)
Fig. 13. Variation of flux during addition of the non-ionic surfactant Triton X-100. The polysulphone membrane, DDS GRIO, has
a nominal cut-off of 500 000. The line with the open circles shows
the Aux decline of a membrane that has only been conditioned
with pure water. The line with the solid dots shows the flux decline
of the same membrane, but after cleaning of the membrane with
a commercial alkaline cleaning agent, Ultrasil 10 from Henkel.
Surfactant was added stepwise, the concentration 0.1 CMC, for
example, indicates that the concentration was 10% of the critical
micelle concentration. The operating pressure was 0.1 MPa and
the temperature 30 C.

hydrophobic tall

(b)
Fig. 14. (a) A charged solute is repelled by a membrane of the
same charge. (b) At the isoelectric pH the solute is uncharged and
may be adsorbed onto the membrane.

77
During ultrafiltration of kraft black liquor it was
found that large molecules, that were able to permeate the membrane at a high ionic strength, were
almost completely retained at low ionic strength [60].
The influence of pH may be altered if salt is
present in the solution. This has been demonstrated
for BSA [LX]. In the absence of salt the flux was at its
minimum at the isoelectric pH. In the presence of
0.2 M NaCl the flux was lowest at pH 2 and increased monotonically with increasing pH.
The zeta potential

of the membrane

The pH may, however, affect not only the charge


of the solute, but also the net charge of the membrane, the zeta potential. It has been shown [61] that
a polycarbonate membrane has an isoelectric point
at pH 4. Above this pH the membrane had a slight
negative surface charge, which increased in magnitude with increasing pH. The surface was found to
be fully charged above a pH of about 6. The surface
was neutral below a pH of 3. The same dependence
on pH has been shown for membranes of polysulphone and polyamide [62].
Most natural substances are negatively charged.
The maximum flux of a negatively charged membrane ought then to be found at a high pH, where
the electrostatic repulsion is at its maximum. This
supposition has been confirmed in many investigations. For example, for bleach plant effluent [49] and
for BSA solutions with salt present [56].
The flux may, however, also be higher at a low
pH. This has been found, for example, during ultrafiltration of soybean extract [63] and for cheddar
cheese whey [64]. Of course, not only the pH may
change the charge of the membrane. If solutes are
adsorbed on the membrane this may change not only
the charge, but also the hydrophobic/hydrophilic
properties of the membrane.
Pretreatment
The fouling ability of a solution may be diminished by suitable pretreatment. The pretreatment can
be mechanical, thermal or chemical. Modifications to
the feed solution include adjustment of pH, removal
of fibres, fines, etc. and heat treatment of the feed
solution.
Mechanical pretreatment
is especially important
when using thin-channel membrane modules. The
danger of plugging the flow channels is greatest for
spiral, hollow-fibre and plate and frame modules.
Tubular modules also require some solution pretreatment. When treating effluents in the pulp and
paper industry a continuous sand filter is often used
as a prefilter for plate and frame modules [65], while
for tubular membranes a 1 mm screen is sufficient

t(351.

Centrifugation is often used, for instance to remove fines from whey and fibres from starch processing waters. Another example is centrifugation of

blood for the fractionation of red blood cells from


blood serum proteins.
Thermal pretreatment is often necessary in order
to avoid undesirable changes, especially when processing biological materials which are sensitive to
biodegradation, such as liquid foods, food waste
waters and fermentation broths. The pH of whey, for
instance, decreases rapidly without heat pretreatment.
Calcium phosphate is known to cause a flux decline during the ultrafiltration of milk and whey
when the temperature and pH are not carefully
controlled [39]. Milk and whey are therefore normally heated to 55-60 C and held at this temperature for up to half an hour before ultrafiltration at
50-55 C. As the solubility of calcium phosphate
decreases with increasing temperature the salt precipitates during the preheating operation. If the milk, or
whey, is not preheated, calcium phosphate may precipitate at the membrane surface and in the pores.
This phenomenon, known as scaling, can also occur
in the porous support. The deposited salt is very
difficult to remove. However, no significant flux decline is observed when the salt is precipitated before
the ultrafiltration.
Chemical pretreatment,
can, in many cases, improve flux. The reduction of flux of protein solutions
at the isoelectric pH has already been discussed in
this paper. This reduction is avoided if the pH is
adjusted before the protein solution is concentrated.
Cleaning
Cleaning and disinfection of the membrane plant
are very important operations, especially in food
processing. Fouling of the equipment, as well as the
presence and growth of micro-organisms, necessitates regular cleaning and disinfection cycles. Membranes used in food plants are generally cleaned at
least once a day, while those used for the treatment
of electrodeposition paints, or for the production of
desalinated water, need to be cleaned less frequently,
usually no more than twice a year.
A cleaning cycle generally includes the following
stages: removal of product from the system, followed
by rinsing the system with water; cleaning in one or
several steps, followed by rinsing the system with
water; disinfection of the system.
The product should be removed at the same temperature as that used in the process. This is important, for instance, when dealing with products which
tend to form gels at low temperatures.
Both retentate and permeate should be discharged
when the system is rinsed. Rinsing should continue
until both the retentate and permeate streams are
totally clear and neutral.
Cleaning solutions
A large number of cleaning recommendations
are reported in the literature. Cleaning studies are

usually trial and error investigations, whereas systematic studies are very rare. Temperature, time,
concentration and type of surface active agent are
important cleaning parameters that vary with foulants and membrane material.
As a rule, mineral deposits are removed by acids
and proteins by alkaline solutions. For some products, it is necessary to use different chemicals in
succession to obtain a satisfactory cleaning result.
For milk, where protein deposits dominate, an alkaline formulation is used first, sometimes followed by
acid treatment to remove mineral deposits. If polysulphone membranes are used, a final alkaline cleaning is often carried out in order to improve the flux.
For whey, where mineral deposits dominate, acid
cleaning is often performed first, and is then followed by alkaline cleaning.
Some care is recommended when selecting a
cleaning procedure since an injudicious choice could
be catastrophic. As an example, in ref. 67 it is shown
that pectine, present in fruit juices, presents difficult
fouling problems. Especially alkaline detergents, and
also unsuitable acid products, may lead to complete
clogging of the membranes.
In order to obtain a good mechanical cleaning
effect, the cross-flow rate is often higher and the
pressure lower during cleaning than during normal
operating conditions.
Cleaning solutions are often a mixture of chemicals. Alkaline cleaning solutions usually contain
sodium hydroxide, phosphate, sequestering agents
and surface active agents. Examples of some cleaning
chemicals and the concentrations used are given in
Table 1.
The choice of surface active agent is very important, since some types may be adsorbed onto the
membrane surface, resulting in a flux reduction. On
the other hand, with a suitable choice of surfactant
in the cleaning solution considerably enhanced fluxes
may be obtained. Thus, as stated previously, it has
been suggested [49] that cleaning may be considered
not merely as a cleaning operation, but also as an in
situ surface modification.
The influence of the surfactant on the flux was
demonstrated in an investigation where membranes
fouled during ultrafiltration of whey were cleaned
with different types of surfactants [68]. Considerably
improved whey fluxes were experienced after cleaning with a solution containing an anionic surfactant,

TABLE
I. Examples of concentrations
cleaning and disinfection solutions
Cleaning/disinfecting
Caustic soda
EDTA-Na,
Nitric acid
Chlorine
Hydrogen peroxide
Sodium bisulphite

agent

of chemicals

Concentration
0.5-1.0
0.5-1.0
0.3-0.5
0.002-0.02
0.1
0.25

used in

for example. Another example of the positive effect


of cleaning is demonstrated in Fig. 13.
Disinfection
A diluted solution of hypochlorite, hydrogen peroxide or sodium bisulphite is often used for disinfection. It is important to clean and disinfect not only
the active side of the membrane, but also the permeate side. This fact has to be considered especially for
reverse osmosis membranes, since these dense membranes retain the cleaning and disinfecting agents.
Membrane plants are often run discontinuously.
When idle, the modules should be preserved in a
diluted disinfection solution, for example sodium
bisulphite, in order to prevent microbial growth in
the membrane and/or membrane support.
Means of facilitating

cleaning

Generally, the effect of the cleaning operation is


checked by measuring the water flux after cleaning at
a defined pressure, temperature and cross-flow velocity. This is not a reliable measure, however. A high
water flux does not guarantee a good product flux,
whereas a low water flux indicates that the cleaning
is not sufficient. The product flux in the following
run is a better indication of whether the membranes
have been cleaned satisfactorily [69].
The cleaning operation is facilitated if the membrane fouling is reduced as much as possible. Factors
which must then be considered are:
_ membrane properties (choose the most suitable
type of membrane and module for each application);
_ solution pretreatment (before ultrafiltration, remove salts that can cause severe scaling, for example) ;
- flow velocity (try to keep the cross-flow velocity at
such a level that gel formation is avoided);
_ rinsing water quality (be aware of the quality of
the rinsing water).
The presence of iron, silica, calcium and other
inorganic ions in the rinsing water can cause precipitation of salts which are difficult, or impossible, to
remove. The rinsing water quality required is as
follows [ 701:
Iron
Manganese
Silicate ( SiOz)
Hardness
Particles
Total plate count
E. coli count

< 0.05 ppm


< 0.02 ppm
<5 ppm
t20 German degrees
<25pm
-z 1000 per ml
Oper 1OOml

(%)

Concluding remarks
Our understanding of the fundamental principles
of ultrafiltration is becoming better and better. But
there is still a long way to go before the complex
mechanisms of the ultrafiltration process are fully

79
understood. A vast number of empirical investigations show that it is very hazardous to make general
statements, especially about the influence of different
parameters on fouling.
Experience indicates that if we are to be able
to describe the dynamics of ultrafiltration it will
be necessary to combine knowledge from different
areas. The theoretical models must combine knowledge and experience of fluid mechanics, mass transfer and surface chemistry phenomena.

Nomenclature

A*
A
a

a
b
c
cb

57
CP
:

4
4
J

JO
K

Kg

KO

k
L
AL
AL,
AP
PWF
PWP
n
n
R
&I
4
&
RS

Re
rP
SP
SC

Sh
t
u
0:
&
L-I
mv
d

proportionality constant in eqn. (13)


constant in eqn. ( 17)
solution-dependent constant in eqn. (4), Pa
constant in eqn. (17)
constant in eqn. (17)
constant in eqn. (17)
bulk concentration, wt. %
gel concentration, wt.%
permeate concentration, wt.%
concentration at membrane wall, wt.%
diffusivity, m2 s-
hydraulic diameter of flow channel, m
diameter of solute molecules, m
permeate flux, 1 m-* h-
initial flux, 1 m-* h-
specific permeability, mz
permeability of a gel layer, m*
specific permeability at zero pressure, m*
mass transfer coefficient, m s-l
length of flow channel, m
thickness, m
thickness of gel layer, m
pressure difference across membrane, Pa
pure water flux, 1 mm* h
pure water permeability, 1 m-* hh Pa-
solution-dependent constant in eqn. (4)
exponent in eqn. ( 18)
adsorbed layer hydraulic resistance, m ~
boundary layer hydraulic resistance, m-
gel layer hydraulic resistance, m -
membrane hydraulic resistance, m ~
solute hydraulic resistance, m-
Reynolds number
pore radius, m
membrane surface porosity
Schmidt number
Sherwood number
time, s
cross-flow velocity, m s-
compaction constant in eqn. (1 l), Paa
porosity of gel
viscosity, Pa s
osmotic pressure difference across membrane, Pa
osmotic pressure at membrane wall, Pa
reflection coefficient

Refereoces
1 I. Zahka and L. Mir, Ultratiltration of cathodic electrodeposition paints, Pluring Surj: Fiairhing, (Nov.) (1979) 34-39.
2 B. R. Breslau, A. J. Testa, B. A. Milnes and G. Medjanis,
Hollow fiber ultrafihration technology,Iti. WurerEng., 17
(1980) 20-26.
3 I. H. Hanemaaijer, Toepassing van membranfdtratie in de
zuivelindustrie, Voedingsmiddelen Technol., I8 (4) (1985) 2629.
4 V. Gekas, B. Hallstrom and G. Tr&$rdh, Food and dairy
applications: the state of the art, Desalinufion, 53 (1985)
95-127.
5 J.-L. Maubois, Recent developments of ultra8ltration in dairy
industries, in E. Drioli and M. Nakagaki (eds.), Membranes
and Membrane Processes, Plenum Press, New York, 1986, pp.
255-262.
6 R. M. Hedges and P. Pepper, Reverse osmosis and ultraliltration-advances
in the fruit and vegetable juice industries,
Proc. Symp. on Fruit juices for Europe, Den Haag, The
Netherhzndv, Int. Fed. Fruit Juice Producers, 1986, pp. 253260.
7 I. R. Wahl, R. C. Hayes, M. H. Kleper and S. D. Pinto,
Ultrafiltration for todays oily wastewaters: a survey of current ultrafiltration systems, Proc. Conf: on Industrial Wusfe,
1980, pp. 719-729.
8 A.-S. Jdnsson and R. Wimmerstedt, The application of membrane technology in the pulp and paper industry, Desalinarion, 53 (1985) 181-196.
9 H. P. G. Darcy, Les Fontaines Publiques de la Ville de Duon,
Victor Dalmont, Paris, 1856.
10 0. Kedem and A. Katchalsky, Thermodynamic
analysis of
the permeability of biological membranes to non-electrolytes,
J. Chromatogr., 27 (1958) 229-246.
11 K. S. Spiegler and 0. Kedem, Thermodynamics
of hyperf%ltration (reverse osmosis): criteria for efficient membranes,
Desalination, I (1966) 31 l-326.
12 G. Jonsson, Boundary layer phenomena during ultrafiltration
of dextran and whey protein solutions,
Desalination,
51
(1984) 61-77.
13 J. G. Wijmans, S. Nakao and C. A. Smolders, Flux limitation
in ultrafiltration: osmotic pressure model and gel layer model,
J. Membr. Sci., 20 (1984) 115-124.
14. G. Jonsson, Characterization
of uhrafiltration membranes:
the osmotic pressure model, in G. Trlg&rdh (ed.), Proc. Conf.
on Characterization
of Ultrafiltration
Membranes,
&en&
Sforr, Sweden, Studentlitteratur, Lund, 1988, pp. 125- 140.
15 W. F. Blatt, A. Dravid, A. S. Michaels and L. Nelsen, Solute
polarization and cake formation in membrane ultrafiltration:
causes, consequences, and control techniques, in J. E. Flinn
(ed.), Membrane Science and Technology, Plenum Press, New
York, 1970, pp. 47-97.
16 M. C. Porter, Concentration polarization with membrane ultrafiltration, Ind. Eng. Chem., Prod. Res. Dev., II (1972)
234-248.
17 A. G. Fane, C. J. D. Fell and A. G. Waters, The relationship between membrane surface pore characteristics and flux
for ultrafiltration membranes, J. Membr. Sci., 9 (1981) 245262.
18 M. W. Chudacek and A. G. Fane, The dynamics of polarisation in unstirred and stirred ultrafiltration, J. Membr. Sci., 22
(1984) 145-160.
19 P. De.jmek, Concentration
polarization
in ultrafiltration of
macromolecules, Ph.D. Thesis, Dept. Food Engineering, Lund
Univ., 1975.
20 S. I. Nakao, T. Nomura and S. Kimura, Characteristics of
macromolecular
gel layer formed on ultrafiltration tubular
membrane, AIChE J., 25 (1979) 615-622.

80
21 J. Cl. Wijmans,
S. Nakao, J. W. A. van den Berg, F. R.
Troelstra
and C. A. Smolders, Hydrodynamic
resistance of
concentration
polarization
boundary layers in ultrafiltration,
J.
Me&r.
Sci., 22 (1985) 117-135.
22 E. Matthiasson,
Macromolecular
adsorption
and fouling in
ultrafiltration
and their relationships
to concentration
polarization, Ph.D. Thesis, Dept. Food Engineering,
Lund Univ.,
1984.
23 S. Sourirajan
and T. Matsuura,
Reverse osmosis/ultrafiltration
process principles, NRCC Rep. No. 24188, Nat. Res. Council of
Canada,
1985.
24 R. B. Bird, W. E. Steward and E. N. Lightfoot,
Transport
Phenomena, Wiley, New York, 1960, Chap. 3.
25 V. Gekas and B. Hallstrom,
Mass transfer in the membrane
concentration
polarization
layer under turbulent cross flow. I.
Critical literature review and adaption
of existing Sherwood
correlations
to membrane operations, J. Me&r. Sci., 3O( 1987)
153-170.
26 M. Lopez-Leiva,
Ultrafiltration
in rotary annular flow, Ph.D.
Thesis, Dept. Food Engineering,
Lund Univ., 1979.
27 M. Lopez-Leiva, Ultrafiltration
at low degrees of concentration
polarization:
technical
possibilities,
Desalination,
35 (1980)
115-128.
28 F. Vigo, C. Uliana and P. Lupino, The performance
of a
rotating
module in oily emulsions
ultrafiltration,
Sep. Sci.
Tech&.,
20 (1985) 213-230.
29 I. G. R&z, J. G. Wassink and R. Klaassen, Mass transfer, fluid
flow and membrane
properties
in flat and corrugated
plate
hyperfiltration
modules, Desalination, 60 (1986) 213-222.
30 V. Gekas and K. Olund, Mass transfer
in the membrane
concentration
polarization
layer under turbulent cross flow. II.
Application
to the characterization
of ultrafiltration
membranes, J. Membr. Sci., 37( 1988) 145-163.
31 A. G. Fane, Ultrafiltration:
factors influencing flux and rejection, in R. J. Wakeman
(ed.), Progress in Filtration and
Separation, Elsevier, Amsterdam,
1986, pp. 101-179.
32 A. G. Fane, C. J. D. Fell and M. T. Nor, Ultrafiltration
in the
presence of suspended matter, Inst. Chem. Eng. Symp. Ser. No.
73, (1982) Cl -ClZ.
33 R. L. Goldsmith,
R. P. de Filippi and S. Hossain,
New
membrane process applications,
AIChE Symp. Ser. No. 120, 68
(1972) 7-14.
34 H. Reihanian,
C. R. Robertson
and A. S. Michaels, Mechanisms of polarization
and fouling of ultrafiltration
membranes
by proteins, J. Membr. Sci., 16 (1983) 237-258.
35 P. DeJardin,
C. Toledo, E. Pefferkorn and R. Varoqui, Flow
rates of solutions through ultrafiltration
membranes monitored
by the structure of adsorbed flexible polymers, in A. R. Cooper
(ed.), Ultrajiltrotion
Membranes and Applications,
Plenum
Press, New York, 1980, pp. 203-247.
36 V. L. Vilker, C. K. Colton and K. A. Smith, Concentration
polarization
in protein ultrafiltration.
Part 1: An optical shadowgraph
technique
for measuring
concentration
profiles
near a solution-membrane
interface,
AIChE J., 27 (1981)
632-645.
37 D. G. Thomas and W. R. Mixon, Effect of axial velocity and
initial flux on flux decline of cellulose acetate membranes
in
hyperfiltration
of primary sewage eflhients, Ind. Eng. Chem.,
Process Des. Dev., II (1972) 339-343.
38 A. S. Michaels,
Ultrafiltration:
an adolescent
technology,
CHEMTECH,
(Jan.) (1981) 36-43.
39 G. B. van den Berg and C. A. Smolders,
Flux decline in
membrane processes, Filtr. Sep., 25 (1988) 115-121.
40 E. Matthiasson
and B. Sivik, Concentration
polarization
and
fouling, Desalination, 35 (1980) 59- 103.
41 G. Trlgardh
(ed.), Proc. Corzf. on Characterization of Ultrofiltration Membranes, &etis
Slott, Sweden, Studentlitteratur,
Lund, 1988.

42 A. G. Fane, C. J. D. Fell and A. G. Waters, Ultrafiltration


of
protein solutions through partially permeable membranes-the
effect of adsorption
and solution environment,
J. Membr. Sci.,
16 (1983) 21 l-224.
43 M. S. Lee, Membrane
Ultrafiltration
fouling and treatment,
Ph.D. Thesis, Univ. College of Swansea, Wales, 1982.
44 S. Munari, Characterization
of ultrafiltration
polymeric membranes, in G. Tragtirdh (ed.), Proc. Conf. on Characterization
of Ultrafiltration Membranes, &en& Slott, &e&n, Studentlitteratur, Lund, 1988, pp. 81- 114.
45 J. H. Hanemaaijer,
T. Robbertsen, Th. van den Boomgaard,
C.
Olieman, P. Both and D. G. Schmidt, Characterization
of clean
and fouled ultrafiltration
membranes,
Desalination, 68 (1988)
93-108.
46 L. A. Errede and P. D. Martinucci,
Flow rate of water through
porous membranes
as affected by surface modification
on the
lower-pressure
side of the membrane,
Ind. Eng. Chem., Prod.
Res. Dew., 19 (1980) 573-580.
47 A.-S. Jonsson, The influence of surfactants
on ultrafiltration
membranes,
in preparation.
48 A. Suki, A. G. Fane and C. J. D. Fell, Flux decline in protein
ultrafiltration,
J. Membr. Sci., 21 (1984) 269-283.
49 A.-S. Jiinsson, Y. Blomgren and E. Petersson, Influence of pH
and surfactants on ultrafiltration
membranes during treatment
of bleach plant effluent, Nordic Pulp Paper Res. J., 3 (1988)
159-165.
50 N. M. Fish and M. D. Lilly, The interactions
between fermentation and protein recovery, Biotechnology, 2 (1984) 623-627.
51 J. M. S. Cabral, B. Casale and C. L. Cooney,
Effect of
antifoam agents and efficiency of cleaning procedures
on the
cross-flow
filtration
of microbial
suspensions,
Biotechnol.
L&t., 7 (1985) 749-752.
52 K. H. Kroner, W. Hummel, J. Viilkel and M.-R. Kula, Effects
of antifoams on cross-flow filtration of microbial suspensions,
in E. Drioli and M. Nakagaki
(eds.), Membranes and Membrane Processes, Plenum Press, New York, 1986, pp. 223-232.
53 W. Han&h,
Cell harvesting
with membranes,
in W. C.
McGregor
(ed.), Membrane Separations in Biotechnology,
Marcel Dekker, New York, 1986, pp. 61-88.
54 W. C. McGregor,
J. F. Weaver and S. P. Tansey, Antifoam
effects on ultrafiltration,
Biotechnol. Bioeng., 31 (1988) 385389.
55 A. G. Fane, C. J. D. Fell and K. J. Kim, The effect
of surfactant
pretreatment
on the ultrafiltration
of proteins,
Desalination, 53 (1985) 37-55.
56 A. G. Fane, C. J. D. Fell and A. Suki, The effect of pH and
ionic environment
on the ultrafiltration
of protein solutions
with retentive membranes, J. Membr. Sci., 16( 1983) 195-210.
57 J. F. Hayes, J. A. Dunkerley,
L. L. Muller and A. T. Griffin,
Studies on whey processing by ultrafiltration.
II. Improving
permeation
rates by preventing fouling, Aust. J. Dairy Technol., (Sept.) (1974) 132-140.
58 F. Forbes, Considerations
in the optimisation
of ultrafiltration, Chem. Eng. (Lundon), (Jan.) (1972) 29-34.
59 H. B. Hopfenberg,
V. T. Stannet and M. W. Bailey, Solutesolute interactions
in ultrafiltration
treatment
of paper mill
wastes, AIChE Symp. Ser. No. 139, 70 (1974) 1- 10.
60 D. Woemer and J. L. McCarthy,
Ultrafiltration
of pulp mill
liquors, Tappi, 70 (1987) 126-129.
61 P. D. Bisio, J. G. Cartledge, W. H. Keesom and C. J. Radke,
Molecular orientation
of aqueous surfactants
on a hydrophobic solid, J. Colloid Interface Sci., 78 (1980) 225-234.
62 J. Nassauer,
Adsorption
und haftung
an oberIHchen
und
membranen,
Ph.D. Thesis, Inst. fiir Milchwissenschaft
und
Lebensmittelverfahrenstechnik,
Tech. Univ. Munich, 1985.
63 0. Omosaiye, M. Cheryan and M. E. Matthews, Removal of
oligosaccharides
from soybean water extracts by ultrafiltration, J. Food Sci., 43 (1978) 354-360.

81
64 L. L. Muller, J. F. Hayes and A. T. Griffin, Studies on whey
processing by ultrafiltration.
1. Comparative
performance
of
various ultrafiltration
modules on whey from hydrochloric
acid
casein and cheddar cheese, Aust. .l. Dairy Technol., (June)
(1973) 70-77.
65 U. H. Haagensen, Case Sanyo Pulp, Iwakuni, Japan, 1924GE0482-50, De Danske Sukkerfabrikker,
1982.
66 Pulp deresination
by ultrafiltration
at MoDoCell,
Leaflet,
FCI Membrane
Systems,
Laverstoke
Mill, Whitchurch,

U.K., 1987.
67 S. Bragula and K. Litner, Cleaning and disinfection
of membrane plants: theory and practice, Abstr. Int. Congr. und Messe
Nahrungsmitteltechnik,
K&z, 1986.
68 G. Tragigirdh, in preparation.
69 G. Tr&$rdh,
Membrane
cleaning,
Desalination,
71 (1989)
325-335.
70 Manual
cleaning
and disinfection,
2181-CB-088523,
De
Danske Sukkerfabrikker,
1985.

Você também pode gostar