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Separation and Purification Technology 26 (2002) 19–31


www.elsevier.com/locate/seppur

Crossflow microfiltration – state of the art


Siegfried Ripperger*, Justus Altmann
Technische Uniersita¨t Dresden, Lehrstuhl fu¨r Mechanische Verfahrenstechnik, 01062 Dresden, Germany

Abstract

Microfiltration is the oldest membrane process and shows up to now the largest market for technical membranes
and membrane modules. In technical applications crossflow microfiltration is an established process for the separation
of microparticles, bacteria and emulsion droplets. The following article describes the development and the state of the
art. It makes a contribution to understand the mechanisms of crossflow filtration. © 2002 Elsevier Science BV All rights
reserved.

Keywords : Microfiltration; Microparticles; Bacterium; Droplet emulsion; Crossflow filtration

1.Introduction Filter medium is blocked due to a compact layer


formation. This was the invention of crossflow
Microfiltration (MF) is a pressure-driven microfiltration (CMF). Bechhold used a stirred
membrane brane process for the separation of filtration cell to create the shear flow across the
fine particles, microorganisms and emulsion filter media.
droplets. The mem branes used have a In CMF, the fluid to be filtered flows parallel to
microporous structure which separates fine the membrane surface and permeates through
particles with a size in the range of 0.02–20 m. the membrane due to a pressure difference. The
Therefore, MF is placed between ultrafiltration and crossflow reduces the formation of a filter cake
coarse filtration, which is not a membrane operation. and keeps it at a low level. So it is possible to get
MF is the oldest membrane technology. It a quasi-steady filter flow for a long time (Fig.
started at the beginning of this century with the 1). Today this operation mode is a standard
preparation of synthetic microporous membranes operation in many medical and technical
based on cellulose. In 1907, Bechhold [1] found membrane applications. This mode of operation
by experiments, that in the filtration of colloidal is sometimes also called tangential or dynamic filtration.
and very fine suspensions a flow parallel to the CMF is used for the production of pure liquids,
filter medium increases the filtrate volume before the the concentration of suspensions in order to
recover valuable products, and the regeneration
*
of process liquids. CMF has become an established
Corresponding author. Phone: +49-351-4635182; fax: +49-
351-4637058.
process for the separation of microparticles,
E-mail address : mechanvt@rcs.urz.tu-dresden.de (S. Rip bacteria and emulsion droplets in a variety of
perger). industrial applications. Often a high concentration

1383-5866/02/$ - see front matter © 2002 Elsevier Science BV All rights reserved.
PII: S 1 3 8 3 - 5 8 6 6 ( 0 1 ) 0 0 1 1 3 - 7
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S. Ripperger, J. Altmann / Separation/ Purification Technology 26 (2002) 19–31

Fig. 1. Principle of crossflow filtration.

slurry should be reached, therefore CMF is mostly


used in combination with other separation processes.

The following chapters will give an overview over


the development in the last years and describe the
state of the art of CMF and make a contribution to
understand the mechanisms of crossflow filtration
of suspensions with fine particles.

. . Market size olume


eleven

A market research gives a rough idea about sales Fig. 2. Principle of a laser triangulometer.
volumes, market potentials and technical importance
of a technology. This is even truer when dealing
with an expanding business like membranes. The
membrane market, defined by membrane and
module sales, had estimated sales of over US$1.5
billion in the year 1999.
According to different market research results, the
average annual growth rate is about 10%. The
largest market for membranes and membrane units
(membrane cartridges and membrane mod ules) is
still in MF. This area is responsible for approximately
40% of the current sales, and is growing at an
annual growth rate of 8–10%. It can be estimated
that 70–80% of these sales are membranes and
membrane units for dead-end filtration. The market
for membrane modules for CMF has a size in the
range of about US$150 million worldwide. The
annual growth rate of this part of the market is Fig. 3. Filtration curve of diatomaceous earth at constant
expected to be over 10%. transmembrane pressure.
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Table 1
Equations of the calculation of the diffusion coefficient D of particles
in the crossflow filtration

kBT
D=
3x
two

eckstein w
=0,…,0.2 D=0.1x
two two

w
=0.2,…,0.5 D0.025x
two

Leighton and =0,…,0.2 x two

w
D=0.5
assets
x
two two

=0.2,…,0.5 w
D0.335 (1
two

+0.5 exp(8.8))
two

Geissler w
D=x (A exp(ÿB)+C)
(0.005) two

Fig. 4. Categorization of physical models of the CMF.

Fig. 6. Acting forces on a single particle.

Fig. 5. Particle concentration in the vicinity of the membrane at the


CMF.

1.2 . Membranes for microfiltration

In MF the membrane has a microporous structure and


separates particles according to the size of pore, from a
liquid or a gas phase. The separation is based on the sieve
effect. Therefore, the separation effect is mostly limited to
the outer surface of the membrane. The microporous
structure of the membrane should have a narrow pore size
distribution in order to ensure the quantitative retention of
particles of a given size and type. Another important feature
is the high porosity of membranes which leads to high
filtration rates at small pressure differences. Further
Fig. 7. Particle deposition on a microporous 0.2 m membrane brane.
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Requirements of membranes are high strength as well


as chemical and thermal stability.
The properties of microporous membranes are
largely determined by the production process and the
materials used. The commonly used types are the
polymer membranes. These membranes, while fulfilling
the requirements mentioned above, are favorable in
terms of cost/benefit ratio. MF membranes based on
inorganic materials like ceramic, metal and carbon are
available and are used when specific advantages, for
example, the high thermal stability, are required.

Fig. 8. Estimation of the lift force and the drag of the filtrate flow. 2. New methods for the investigation of the layer
formation in crossflow microfiltration

The processes of the crossflow filtration are mainly


determined by the formation of a cake layer on the
membrane. A better understanding of the layer
formation and the particle deposition on the membrane
could result in a more economical use of the crossflow
filtration in many technical applications. Therefore,
recent investigations were focused on this point.

In some investigations [2–4], the layer thickness and


layer structure was measured after the filtration process.
Other authors tried to get on-line information about the
layer formation.
Leighton and Acrivos [5] and Wakemann [6] used
an experimental setup with a video camera to visualize
the growth of the layer. Huismann et al. [7] calculated
Fig. 9. Filtration rate vs. particle size.
indirectly the deposited mass of particles on the
membrane by the measurement of the concentration of
particles in the circulating feed. Because of the
deposition of particles on the membrane the
concentration in the feed decreases continuously. By
consideration of the balance of the particle mass in the
whole system it was possible to calculate the amount
of deposited
mass.
The following three methods of the in situ
measurement of the layer thickness were introduced
by the authors of this article in Ref. [8]:
change of the electrical capacitance due to a particle
layer, change of the electrical conductivity due to a
Fig. 10. Mass transport at the membrane. particle layer, and
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S. Ripperger, J. Altmann / Separation/ Purification Technology 26 (2002) 19–31 23

direct measurement of the layer thickness with


a laser triangulometer.
The use of a laser triangulometer showed the
best stability and flexibility in practical use. The
principle of the laser triangulometer is shown in
Fig. 2.
Fig. 3 shows a typical curve for the filtration of
diatomaceous earth at constant transmembrane
pressure. The high flux at the beginning of the
filtration in Fig. 3 is only influenced by the mem
brane resistance. As the layer grows flux de

Fig. 13. Layer resistance vs. layer height.

you created The layer height reaches the steady


state very quickly, while the filtrate flow has a
longer start-up time.

3. Modeling the particle deposition and


layer formation

The crossflow filtration is influenced by a great


number of parameters, eg crossflow velocity,
transmembrane pressure, membrane resistance,
layer resistance, size distribution of the suspended
particles, particle form, agglomeration behavior
Fig. 11. Principle of layer growth. and surface effects of the particles etc. A lot of
models have been developed to describe the
processes of the CMF, but only a few are sufficient
to describe the real processes and explain the
differing between experimental and practical results.
Models for the description of the CMF can be
distinguished into empirical and physical models.
In the following the focus is on the physical models,
because the empirical consideration is useful in
practice, but is not helpful for under standing the
processes of crossflow filtration. A further distinction
of the physical models into macroscopic and
microscopic models according to the scheme
shown in Fig. 4 is practical, because the
macroscopic approach considers the particle
system as a continuum while the microscopic
Fig. 12. Comparison of the theoretical and experimental results. models consider the behavior of a single particle
during the filtration. Both approaches reduce the
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large number of influence parameters to the


following three basic physical mechanisms:
hydrodynamics of the particles; particle
diffusion; and particle interaction and surface
effects Fig. 4 shows the suggested division of
the models and accompanying references.
Because of the large amount of publications on
this topic, the list of references cannot claim to be
complete.

3 .1 . Macroscopic models

First models of the crossflow filtration in the


seventies based on the diffusion and concentration
polarization on the membrane [9–11]. These mod
els consider the parameters affecting the flux in
the case of suspended solids with the mathematical
cal models based on diffusion. The diffusive
movement of the particles causes a particle
transport port opposite to the convective transport
of the filtrate flow. This behavior is well described
in the so-called film model [9]. In the stationary
state both transport mechanisms are in balance. In
that case the filtration rate Fcan be calculated as
follows:

cMÿcP cMÿcP =k ln cFÿcP


F=D ln . (3.1)
cFÿcP

The mass-transfer coefficient k is the ratio of the


diffusion coefficient D and the thickness of the
concentration boundary layer. Very often this
coefficient is given in a dimensionless form as a
Sherwood number Sh=kd/ D. The concentration of
the component to be separated in the permeate
cP is given by the characteristics of the membrane.
cF is the concentration in the feed. The
concentration on the membrane surface cM is the
maximum concentration of a flowable particle
system. The balance of convective and diffusive
mass flow in the immediate vicinity of the membrane
is outlined in Fig. 5.
The macroscopic diffusion models are often a
borderline case to semi-empiric and empirical mod
Fig. 14. Cross-section of a layer. (a) Constant transmembrane els, because they do not consider only effects of
pressure. (b) Variable process parameters. thermal and turbulent diffusion. These models
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The cake layer in Fig. 7 was prepared with the help of a


cryo-transfer device of a SEM.
A quantitative evaluation of the acting hydrodynamic forces
shows that especially the drag of the filtration flow and the lift
force of the particle influence primarily the deposition of particles
on the membrane. The lift force FL is caused by the shear flow.
This effect was investigated eg by Rubin [14], Saffmann [15] and
McLaughlin [16,17]. The results of these investigations are
similar. According to McLaughlin the lift force of a deposited
particle can be calculated as follows 1.5x3 0.5 J() with = xw

two
w
FL=0.358 .
Fig. 15. Flux of Titan(IV) oxide suspension vs. the-potential.
(3.2)

The deposition of the particles depends decisively on the


integrate all effects of particle interaction, hydrodynamics hydrodynamic forces in the immediate vicinity of the
and diffusion into the diffusion coefficient D. Table 1 membrane. An estimate of the acting hydrodynamic
contains different approaches to this coefficient. forces is shown in Fig. 8.
The calculation is based on the following parameters:
=0.001 Pa, =1000 kg/m3 , w=50 Pa, s= 0.001.
3 .2 . Microscopic models
Fig. 8 shows that the balance between the lift force
The starting point of microscopic models is the and the drag force of the filtrate flow is responsible for
consideration of the forces acting on the single particle. the transport of particles to the layer. At high filtration
Fig. 6 shows a simplified scheme of a deposited particle rates the drag force is higher than the lift force in a wide
on the membrane. As the elec tron microscopical image particle range.
of a cake layer in the vicinity of the membrane in Fig. 7 That means, that the particles will be transported to the
shows it is thoroughly justified to consider the acting layer and will be deposited there. Large particles have a
forces in such a simplified manner as shown in Fig. 6. higher lift force so they will not touch the layer. With
decreasing filtration rate the

Fig. 16. Layer structure at the filtration of a stabilized Titan(IV)oxide suspension (a) and an agglomerated suspension (b) at the same magnification.
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Fig. 17. Layer structure at the filtration of a stabilized Geltech 500 (monodisperse) suspension (a) and an agglomerated suspension (b) at the
same magnification.

balance between the lift force and the drag force


of the filtrate flow shifts to smaller particle sizes.
Therefore, only small particles can be deposited
on the layer at low filtration rates. In the case of a
balance of the drag and lift force the maximum
possible filtration rate in the stationary state can be
calculated as follows
FL 1.5x2
F= 3x =0.038
w
0.5 J(). (3.3)
two
(x,K)
This equation considers only hydrodynamic
effects. At submicron particle sizes, a further
consideration of diffusion and particle interaction
forces is absolutely necessary. The additive super
position of hydrodynamic effects (Eq. (3.3)) and
the Brownian diffusion (Eq. (3.1)) for a typical case Fig. 18. Flux of agglomerated and stable suspensions.
of a crossflow filtration (crossflow velocity – 1.5 m/
s, solid concentration – 0.3 vol.%, hy draulic
diameter of the filtration channel – 5.7 mm,
maximum concentration on the membrane 50 vol.
%) are plotted in comparison with experimental
results in Fig. 9.
The calculations verify that in the particle size
range less than 100 nm, the filtration process is
determined only by the diffusion, while at particle
size larger than 1 m, the filtration is mainly
controlled by the hydrodynamics. Further a mini
mum of the filtration rate exists in the range
between 50 and 500 nm. This points to minimal
effective back transport mechanisms in this particle
size range. In the case of distributed particle
systems the filtration rate in the steady state will Fig. 19. Flux vs. -potential of stable suspensions [22].
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Fig. 22. Removal of large fragment from the cake layer.

dm
=m tÿm backÿm p. (3.4)
dt
Fig. 20. Comparison of lift force and attractive force of a deposited
particle. The penetrating mass flow depends on pthe characteristics of
the membrane and of the particle system. The mass flow
towards the membrane can be calculated as a convective
be determined by the particles in this size range. mt transport of the filtrate flow (Fig. 10). For the estimation of
In the shown calculation this filtration rate is caused by
the back transport from the membrane m back different model
particles of about 200 nm and amount to about 20 l/(m2 h).
assumptions can be found in the literature. Ripperger [13] used
an empirical model with the assumption that the back transport
from the membrane is proportional to the wall shear stress at
3 .3 . Modeling unsteady filtration behavior
the membrane and proportional to the height of the cake layer.
The models from Geißler [12], Sethi and Wiesner [18], Lee
The starting point of modeling the unsteady filtration and Clark [19] based on the macroscopic shear-induced
behavior is in all known models the mass balance of the
diffusion models.
particles on the membrane.
The differential change of dm/dt is equal to the difference of
the mass flow to the membrane (m t ) and the mass flow from
the membrane (m p+ m back) Unsteady state models, which use microscopic consideration
of particle deposition were intro

Fig. 21. Filtration of 1.5 m monodisperse particles (crossflow velocity 2 m/s (w=15 Pa), pH 10.5, 270 s/cm).
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duced by Chang and Hwang [20], and Altmann and excludes the possibility of the deposition of fine particles
Ripperger [21]. According to Ref. [21], Fig. 11 shows into an existing particle structure.
the scheme of the calculation of the layer growth for the The asymmetrical layer structure at a filtration at
case of a filtration at with constant transmembrane constant transmembrane pressure could be proved by
pressure. electron microscopical images. Fig. 14(a) shows a cross-
At the beginning of the process the filtration is section of a layer of glass spheres.
rate sure
F determined
p and the membrane
by the transmembrane
resistance RM.pressure
The
filtrate flow causes a convective particle transport to the According to this theory, it is possible to generate
membrane. Because of the particle transport and the ate specific layer structures by varying the operating
particle deposition the layer grows. parameters during the filtration. The introduced model
can be applied for the prediction of such specific
In addition the layer resistance increases and the structures. Fig. 14(b) shows, as the result of an
filtration rate declines. The smaller filter flow has two
experiment, a double asymmetric ric structure. Near the
effects: first, the particle transport to the layer decreases membrane the layer with systems of fine particles, in
and second, the specific cake resistance RL increases middle layers of very large particles and on the top
because of the deposition of finer particles. This cycle again of fine particles.
continues until the filtration rate is so small, that the
This structure was generated by an alternating low–
particle transport to the layer becomes zero.
high–low filtration rate.

A result of a numerical calculation according to the


algorithm in Fig. 11 is shown in Fig. 12. It shows a good
4. Influence of interfacial phenomena
correspondence of the numerical calculated values with
the experiments. The cake porosity was assumed to be With the consideration of the influence of the particle
0.4. The typical be habit, that the layer height increases
interaction forces on the crossflow filtration process it is
faster than the filtration rate decreases, can be described
meaningful to decide two cases: influence on the particle
with this model very well.
system by agglomeration or flocculation, and
influence on the particle deposition behavior and
Another way to check the suitability of the model is
resuspensibility of particles from the layer .
the comparison of the structure. Since an independent
measurement of flux and layer height is possible, the
total layer resistance can be shown as a function of the Both effects can be described and explained by the
layer height (Fig. 13). The resistance is calculated Derjaguin–Landau–Verwey–Overbeek (DL VO) theory.
according to Eq. (3.5)
p 4 .1 . Agglomeration of the particle system
Rtotal=RM+RL= . (3.5)
F

Fig. 13 points to a strong asymmetrical layer structure. Agglomeration of a particle system occurs when the
The bottom layer near the membrane shows a low repulsive forces become small in comparison with the
resistance while the uppermost layer at the surface of attractive forces. An electrolytic agglomeration can be
the layer has a very high resistance. This high resistance realized by changing the -potential through the pH-
is caused by the fine particles in the upper layers. value. The agglomeration state has a direct influence
on the filtration rate.
The calculation describes the asymmetrical layer Fig. 15 shows the variation of the stationary filtration
structure with a good correspondence. The experimental rate of a crossflow filtration of Ti tan(IV)oxide (crossflow
values show a higher increase of the cake resistance in velocity – 1.5 m/s, solid concentration – 0.3 vol.%,
the upper layers than the calculation. The reason for hydraulic diameter of the filtration channel – 5.7 mm)
that is the assumption of a constant porosity in the vs. . the-potential.
layer. This assumption
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S. Ripperger, J. Altmann / Separation/ Purification Technology 26 (2002) 19–31 29

It can be seen that the agglomeration of the The irreversibility of the particle deposition could be
Titan(IV)oxide suspension causes a rapid increase of the observed in experiments with monodisperse silica
filtration rate at a -potential of about 25 mV because of particles. The particles were filtered at variable
the enlargement of the effective agglomerate size. The transmembrane pressures.
change in the particle system causes a change in the First, the transmembrane pressure was slowly in creased
cake layer structure. up to 3 bar and after that decreased back to zero. The
Fig. 16(a) shows the layer structure of a stable suspension changing of the transmembrane pressure sure was so
with a porosity of =0.45 and Fig. 16(b) shows the structure slow, that at any time a quasi-station ary layer height and
of an agglomerated system. The layer of the agglomerated filter flow was ensured. Fig. 21 shows the dependencies
suspension shows =0.74 a several times higher porosity. of the layer height and filtrate flow on the transmembrane
pressure.
The same behavior could also be observed with other The filtrate flow increased at low transmembrane
particle systems. Fig. 17 shows the structure of a layer pressures according to the membrane resistance. At
from a monodisperse silica suspension. higher transmembrane pressures only a very small
The steady state flux of an agglomerated parti cle increase of the filtrate flow could be observed, while the
system multiple higher than in the stabilized state. Fig. layer height increased linearly with the transmembrane
18 shows for several investigated parti cle systems a pressure. During the crease of the pressure, the layer
strong increase in the flux due to agglomeration.
height did not change significantly, the filtration rate
declined linearly to the transmembrane pressure. This
indicates that the layer structure and resistance was not
4 .2 . Influence of the interaction forces at
influenced by the decreasing pressure. Because of the
stabilized suspensions
irreversible attached particles a particle transport away
from the layer did not take place.
In suspensions with a high-potential the repulsive
forces between the particles dominate the particle
Other tests with monodisperse or narrow distributed
interaction and cause the stabilization of the suspension.
particle systems with a size of 1.0, 0.5 and 0.24 m also
Furthermore, the repulsion reduces the particle deposition
showed this behaviour.
on the layer, because the repulsive forces act opposite to
The force estimation has shown that particle attachment
the drag of the filtrate flow. Therefore, the stationary
to the layer is mostly an irreversible process. Adhesive
filtration rate in creases with the increasing -potential of
forces are dominating on a deposited particle. This effect
the par ticles. This effect is demonstrated by experiments
can be concluded from the experiments. The build-up of
in Ref. [22]. Fig. 19 shows the described behaviour.
the layer is a continuous process, while the removal of
the layer only takes place by removing large agglom
erates or large layer fragments as shown in Fig.
4 .3 . Reersibility of the layer formation
22. A removal of the layer in the form of a reverse
Particle interaction forces strongly influence the transport from single particles could not be observed.
reversibility of the layer formation. For example, the
calculation of the lift force and the attractive force
according to the DLVO theory of a de posited particle in
Fig. 20 shows that fine particles are irreversibly deposited 5. Applications of crossflow microfiltration
on the layer. The calculations based on the following
parameters: particle size – 600 nm, fluid – water at 20°C, CMF is widely used in different industries. The following
-potential – 40 mV, ion strength – 0.001 mol/l, Hammaker– overview demonstrates the scope of this separation
van-der-Waals-constant – 0.5× 10ÿ20 J, membrane- technique for fine particles, droplets and macromolecular
tube diameter – 5 mm, crossflow velocity – 2 m/s. substances:
clarification of fruit juice, wine, cider and vinegar;
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30 S. Ripperger, J. Altmann / Separation/ Purification Technology 26 (2002) 19–31

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filtration of of microbial
fermentation
upgrading
broths; load);
of cleaning
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wastewater treatment (CSB reduction, separation Fluid Mech. 22 (1965) 385–400 corrigendum 31(1968) 624.
of solid matter).
[16] JB McLaughlin, Inertial migration of a small sphere in linear shear
flows, J. Fluid Mech. 224 (1991) 261-274.
[17] JB McLaughlin, The lift on a small sphere in wall bounded linear
shear flows, J. Fluid Mech. (1993) 249–265.

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crossflow membrane filtration incorporating multiple transport
mechanisms, J. Memb. Sci. 136 (1997) 191–
205.
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ultrafiltration of colloidal suspensions, J.
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Further Reading
[7] I. Huisman, D. Elzo, E. Middelink, C. Tra¨gaÿrdh, Proper ties of
the cake layer formed during crossflow microfiltration, Colloids [1] AL Zydney, CK Colton, A concentration polarization model for
the filtrate flux in cross-flow microfiltration of particulate
Surf. A 138 (1998) 265-281.
[8] S. Ripperger, J. Altmann, Untersuchungsmethoden und suspensions, Chem. Eng. Commun. 47 (1986)
Ergebnisse zur Deckschichtbildung bei der Querstromfiltration, 1–21.
Filtrieren und Separieren 9 (1995) Heft 4, S. [2] L. Song, M. Elimelech, Particle deposition onto a permeable
149–155. surface in laminar flow, J. Colloid Interf. Sci. 173 (1995) 165–
[9] W. Blatt, A. Dravid, AS Michaels, L. Nelsen, Solute polarization 180.
and cake formation in membrane ultrafiltration: causes, [3] A. Fritz, Abscheidegesetz zur Querstromfiltration in tur bulent
consequences and control techniques, in: JE durchstro¨mten Rohrfiltern, Fortschr.-Ber. VDI Reihe 3, No. 412,
Flinn (Ed.), Membrane Science and Technology, Plenum, New VDI-Verlag, Duesseldorf, 1995.
York, 1970, pp. 47–91. [4] H. Ebner, Die kontinuierliche Mikrofiltration von Essig,
[10] MC Porter, Concentration polarization with membrane Chem. Eng. Tech. 53 (1981) 1.
ultrafiltration, Ind. Eng. Chem. Prod. Res. Develop. 11 (1972) 3. [5] H. Ebner, Die kontinuierliche Mikrofiltration von Essig, Chem.
Eng. Tech. 53 (1981) 25–31.
[11] MC Porter, Concentration polarization with membrane [6] E. Fischer, Untersuchungen zum Trennprozeß bei der
ultrafiltration, Ind. Eng. Chem. Prod. Res. Develop. 11 (1972) Querstromfiltration, Fortschr.-Ber. VDI-Reihe 3, No. 139, VDI-
234-248. Verlag, Duesseldorf, 1987.
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