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Ceramic membranes for the filtration

of liquids: An actual overview
St. Duscher*

Since nearly one century, ceramic membranes are an established component for the separation of particles out of
liquids. Since the development and rollout of ceramic nanofiltration membranes, they also offered an additional method
in separating dissolved solids or ions out of liquids under rough conditions. Due to constant improvements in materials
and production methods, it is possible to replace established processes like e.g. evaporators by these membranes
with lower investment and running costs without any disadvantages in product quality or efficiency. The following article
gives an overview about the actual state of development of ceramic membranes with an emphasized focus on ceramic
nanofiltration membranes. The outlook of the article gives a rough overview about some actual fields of development
and optimization.
1. Development and design of
ceramic membranes

they were successfully used as membranes

for gas diffusion in the subproject of
the uranium concentration during the
Manhattan project. Shortly after, the
development and modification of these
membranes went on and membranes for
micro- and ultrafiltration have been developed, which consisted already of a porous
carrier and a thin ceramic membrane layer,
their shapes have already been in single
and multi-channel designs. Due to their
various advantages, which are for example
important for the treatment and filtration
of foods and beverages, most of the ceramic membranes were used for microfiltra-

1.1. Historical background of

ceramic membranes
While there is very diverse information
concerning the time of the first ceramic
membranes on a laboratory scale, the 40s
mark the birth of ceramic membranes
commercially produced on a large scale, as
* Dipl.-Ing. Stefan Duscher
Head of Sales, Inopor GmbH
Industriestrasse 1, 98669 Veilsdorf / Germany
www.inopor.de

tion of milk as well as (pre-)filtration of

wines and juices.
Next to the development of ceramic
membranes for food and beverages,
after the end of the second world war,
companies like Carbone Lorraine and
Desmarquest did a lot of research and
development in ceramic micro- and ultrafiltration membranes for the enrichment of
uranium. At the same time, also the development and optimization of polymeric
membranes went on; the specific pricing
of polymeric membranes (price per membrane area) was significantly below the
pricing of ceramic membranes, but the

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Fig. 2: Ceramic multi-channel membrane

Table 1: Properties of ceramic membranes

applications were limited due to the chemical and mechanical properties of polymeric membranes. Until the beginning of the
second millennium, microfiltration and
ultrafiltration was available as polymeric
or ceramic membranes, but nanofiltration
and reverse osmosis were still technologies which were covered exclusively by
polymeric membranes. Things changed
significantly, when a new ceramic nanofiltration membrane with a cut-off of 450
Dalton was developed by Hermsdorfer
Institut fr technische Keramik (H.I.T.K.) ,
which is now known as Fraunhofer IKTS
and located at Dresden. While the method
of reverse osmosis certainly will be operated indefinitely only with polymer membranes, a patent-protected ceramic nanofiltration membrane based on the results of
Fraunhofer IKTS - has been available
since 2004 and is being sold on an industrial scale by Inopor GmbH.
1.2. Geometry of ceramic
membrane carriers
As mentioned at the beginning, ceramic
membranes consist of a carrier - mostly
also ceramic - on which the actual membrane layer is fixed. In terms of the shape
and design of these carriers, there are different approaches on the market, like e.g.
flat-sheet membranes, tubular membranes,
capillaries and some further special
designs. Next to Inopor GmbH, typical
supplier of ceramic membranes on the

European market are companies like

Kerafol GmbH, Tami GmbH or Atech
Innovations GmbH. Because tubular
geometries dominate on the market, they
will be discussed primarily in the further
article.
Tubular ceramic membranes are
made of an extruded carrier (so-called
Support) which has one or more channels on which the membrane layers are
fixed on the cannel surface by some intermediate layers. Typically, the support is
also made of a ceramic material, but there
are also some technical alternatives available. Fig. 1 shows some typical single- and
multi-channel geometries of ceramic
membranes. Today a huge number of
material and membrane combinations are
available on the market, like for example
SiC, Al2O3, ZrO2 and TiO2.
Fig. 2 shows the design of a typical
multi-channel membrane, including the
front-side sealing. During operation, the
membrane is installed in a housing and the
feed flow / raw medium flows through the
channels of the ceramic carrier. The surface of the channels are coated with a
ceramic membrane layer. The filtration
process is done by leading liquid through
the membrane layer and separating the
components out of the feed medium which
are not able to pass the membrane layer.
Liquids and components which can pass
through the membrane layer are called
permeate, while the remaining particles,

Fig. 3: Separation principle of a multi-channel membrane

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which cannot pass through the membrane

layer, are called concentrate. For a maximum efficiency, it has to be avoided, that
feed liquid gets on the permeate side without passing through the membrane layer;
otherwise, this would mean a contamination of the permeate flow. So, also a frontside sealing is necessary to avoid that feed
medium flows directly through the porous
membrane carrier to the permeate side. As
shown in Fig. 3, the filtration process is
regulated by a concentrate valve, which
creates a ram pressure by throttling the
diameter and creating a transmembrane
pressure (TMP). Concerning the porosity
of the materials, the membrane layers have
much smaller pores than the intermediate
layers and the membrane carriers, so that
nearly all of the hydraulic resistance of the
flow through the membrane element is
generated by the membrane layer(s) but
not by the support material. Mathematically, the transport mechanism
through porous membranes can be
described by pore models, depending on
pore sizes, driving forces and transport
conditions. Nanofiltration with polymeric
membranes can be described pretty good
by some solution-diffusion-models which
are suitable for tight membranes. Ceramic
membranes even if they are in a range of
a nanofiltration membrane are still
porous membranes, so the transport mechanism cannot be described by the laws for
tight membranes, but by a modification of
the Nernst-Planck-Equation (NPE), which
combines the effects of transport through
porous media with the electrical surface
effects and potentials.
1.3. Materials of ceramic membranes
As already mentioned, the development
of ceramic membranes partly took place at
the same time in different applications, so
that also different developments in materials and shapes were made with similar
properties. In general ceramic membranes
are distinguished by the following features:
Never-the-less, also ceramic membranes are only suitable within defined
ranges of chemical and physical condi-

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tions. A fact, which becomes more and

more important for decreasing pore sizes
of the membranes, because decreasing
pore sizes mean also decreasing resistance. Generally, micro- and ultrafiltration
membrane layers are formed by filling the
channels of the membrane carrier with a
slurry, drain the channels and sinter the
carriers to make the slurry film becoming
a membrane layer. During this production
process, the average pore size of the membrane layer is related with the sinter temperature: So, higher sinter temperatures
mean coarser pore sizes. Typically, a
ceramic filter element does not consist of
only one membrane layer but of several
layers, while the first layers are intermediate layers to fix the membrane layers on
the carrier. Then, one membrane layer
after the other is sintered on the existing
layers with decreasing pore sizes. This
means, that during this production process,
the sinter temperature decreases during
each coating process because pore sizes
become smaller. This means also a
decreasing of the maximum operating
temperature, because the operating temperature must not be higher than the sinter
temperature of the top membrane layer.
While ceramic micro- and ultrafiltration
layers are sintered by a standard slurry

Tab. 1: Properties of ceramic membranes

process, ceramic nanofiltration membranes are manufactured by a polymeric

sol-gel process, which means even lower
max. operating temperatures and a lower
chemical resistance because of a significantly increased membrane surface
because of a multitude of small pores. In
the end, the thermal and chemical resistance of ceramic membranes is still higher
than polymeric membranes, but decreasing pore sizes mean decreasing chemical
and thermal resistance.

Ceramic membranes have in common,

that they are inorganic membranes, but
never the less, depending on the production process and application, the ceramic
materials have different physical and
chemical properties. Sometimes, it is said
about ceramic membranes, that they are
resistant against acids and basics through
the whole pH-range; unfortunately, this is
not the whole truth, because different
ceramic materials have different chemical
properties, depending for example on the

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Fig. 4: Overview of the material resistance properties /1/

Fig. 5: Structure of a ceramic membrane support with membrane layer

range. In case of a phase transformation,

the risk of stress cracks is very high; also
the risk of cracks is given when different
materials with different transformation
properties are coated on each other. This
risk of cracks is given during operation at
high temperatures as well as during the
production process. Fig. 5 shows a crosssection through channel of a ceramic
membrane element taken with a SEM,
including the support, the intermediate
layer and the membrane layer. Depending
on the different thermal and chemical
properties of these different materials, the
mechanical junction between the different
layers has to compensate different expansions and structure conversions. While
Al2O3 and SiO2 appear here to be very stable, tetragonal zirconium oxide and titanium oxide, on account of their relatively
low phase transition temperature, have
only a limited thermal resistance. For the
selection of the suitable ceramic material,
it is hence not enough to know only the
medium to be filtered, also the temperature
and the pH value must be taken into
account. Although the prevailing proportion in ceramic tubular membranes is covered with the materials aluminium oxide
and titanium oxide, reference should be
made at this point also to the very good
chemical resistance of zirconium oxide; as
an example here, reference should be
made to the work of van Gestel /2/, who
succeeded in making ceramic nanofiltration membranes on the basis of ZrO2.
2. Operation of ceramic
membranes

Fig. 6: Schematic structure of a system with ceramic membranes (including CIP cycles)

type of atomic bonding. Last but not least,

it must not be forgotten, that the ceramic
membrane layer is only one part of the
membrane element or the filtration stage:
To make the whole plant run properly, all
materials have to resist the media, incl. the
front-side sealing, the housing and the orings.
Generally, metal oxids are more resistant against acids if their chemical bonding
is more acidic; an increasing resistance
against acids also means a decreasing
resistance against basics. Fig. 4 shows his
properties for some typical ceramic materials. So, for example with SiO2, this is a
significant behaviour, which reduces the

16

hydro-thermal resistance of SiO2 significantly, because of its high affinity for

water. Next to the material itself, also the
allotrophy / crystal structure of the material plays an important role: For example,
for example, -Al2O3 has a good resistance against acids and basics, while Al2O3 with tetragonal crystal structure has
a worse chemical resistance, especially
against basics. Next to the chemical resistance, the lattice structure of the material
also influences the thermal resistance of
the membrane carrier and membrane layer.
A maximum thermal resistance means no
changing of pore sizes, atomic matrix and
chemical reactions in defined temperature

2.1. Construction and incoming flow

Ceramic membranes are primarily used
in the cross flow operation; time by time,
there are applications mainly in the pharmaceutical and chemical processes
where ceramic membranes are operated in
Dead end mode, but the flow rates are
very low and this are not typical installations.
As far as the fundamental construction
of a membrane system with ceramic membranes is concerned, this differs only
slightly from the structure of a plant with
polymer membranes (see Fig. 6).
However, ceramic membranes require
higher cross-flow velocities and larger
cross-flows, compared to polymeric membranes. The practice showed and shows
that especially with applications in the
field of wastewater treatment, as well as
the filtration of chemicals and pharmaceuticals, a cross flow of 4 m/s for ceramic
membranes is an acceptable minimum
cross-flow. The processes of the separation
of micro-organisms (for example from fermentation broths) in this case form an
exception here, since, in addition, the cross

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flow is to be selected before the background that the organisms are not
destroyed by the appearing shear rates.
Because the necessary cross flow for
ceramic membranes is clearly higher than
that of polymer membranes, the higher
energy entry associated with this is an
argument against ceramic membranes, but
only in case of that the process can also be
operated with polymeric membranes.
Thats why manufacturers of ceramic
membranes also continuously work on
reducing this disadvantage, something
that, in the end, means to find a geometry
where the pressure loss, the necessary
oncoming flow, membrane surface and not
least the manufacturability are in an optimal relationship with each other. Fig. 7
shows the cross section of such a carrier
geometry.
2.2. Geometries of ceramic
membrane elements
Ceramic membranes are available in
various geometries and shapes with various numbers of channels and channel
diameter. Next to tubular membranes, also
flat-sheet membranes are available with a
shape of a disc and diameters between
25mm and 90mm, while diameters of
25mm, 47mm and 76mm define an internal standard, because the usual test cells
for flat-sheet membranes are manufactured for discs with these diameters. One
side of the disc is coated with a ceramic
membrane while the carrier is made out of
the same materials like tubular ceramic
membranes. The advantage of test cells for
flat-sheet membranes is, that initial tests
can be done with a small amount of liquid:
The membrane disc is installed in a housing and a liquid column is filled above the
membrane. Then, the liquid column is
pressed in Dead end mode through the
membrane by filling compressed air or gas
between the column and the housing of the
test cell. Typically, maximum transmembrane pressures up to 6 bar / 85 PSI can be

Fig. 7: Optimized geometry of a ceramic

membrane /1/

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Table 2: Parameter overview of membranes commonly available on the market

realized with standard test-cells. To

homogenize the boundary layer on the
membrane surface, a magnetic stirrer can
be used. Filtration processes with flatsheet test cells are only suitable for small
amounts of liquids or for initial trials; the
operating pressures of flat-sheet cells are
typically lower than operating pressures of
processes with tubular membranes. Neverthe less, flat-sheet test cells are invaluable
for trials because they are easy to do and
can be done with a minimum amount of
liquid. Next to test cells for flat-sheet
membranes, depending on the application
chemically high resistant materials are
needed which means for example metalfree housings, made of PTFE or PVDF.
Fig. 8 shows an overview of lab scale
equipment, incl. metal-free housings for
the filtration of high-corrosive liquids.
Regarding tubular geometries, the single-channel tube (EKR) forms the smallest
unit, while depending on the applications the number of channels can be
more than hundred per ceramic element.
Table 2 shows an overview about typical
geometries available on the market and the
technical requirements to design a membrane plant with this membranes.

Similar to polymeric membrane elements, ceramic membrane elements can be

installed in series or in parallel with the
same advantages and disadvantages like
installing polymeric membranes. While
pressure vessels for polymeric membranes
can capture spiral-wound elements in
series installation, housings for ceramic
membranes cannot capture ceramic membranes in series; to install ceramic membranes in series, housings have to be
installed after each other and be coupled
by piping. On the other hand, housings for
ceramic membranes are available to install
ceramic membranes in parallel, while spiral-wound elements cannot be installed in
parallel in one pressure vessel. By
installing membranes in parallel, the
required cross-flow and the size of the circulation pumps grows linearly to the number of elements. Fig. 9 shows a housing for
up to seven tubular ceramic membranes,
while the first membrane is already
installed and sealed with an o-ring against
the housing. Fig. 10 shows a general cut
through a membrane housing for ceramic
membranes. Each membrane has to be
sealed against the housing by an o-ring
and a stopper plate is necessary to avoid

Fig. 8: Flat-sheet test cell and further lab equipment for

ceramic membranes /1/

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Tab. 3: Typical permeate performance with ceramic membrane processes

that membranes are shot out of the housing in case of a pressure hammer.
Typically, screwed flange connections are
used to connect the housing with the piping, but in pharmaceutical or food and
beverages applications, also tri-clamp connections are used.
2.3. Permeate volume and
transmembrane pressure
Due to its properties as a pore membrane, the permeate performance of
ceramic membranes within a determined
window obeys quasi-linear laws, which is
why the specific permeate performance of
a process with ceramic membranes is often
described also in the dimension, which
expresses the fact that a duplication of the
permeate performance entails the duplication of the transmembrane pressure.
Within certain windows this can be confirmed from practise; however, it must not
be concluded therefrom that, for example,
the transmembrane pressure can be multiplied arbitrarily without consequences,
since, the laws of transportation through
the membrane and the behaviour in forming a surface layer will become more and
more important with increasing pressures
and potentials. Although ceramic nanofiltration will be discussed more extensively
in the following chapters, it must already
be mentioned that nanofiltration is especially a process that yields no satisfactory
permeate qualities in the case of low transmembrane pressure, even if some scientific works argued that ceramic nanofiltration
only follows the laws of porous membranes.
Because the optimum working point
depends in the end on a huge number of
factors, such as for example viscosity,

Fig. 9: Membrane housing for up to seven ceramic

membrane elements with one element installed /1/

18

temperature, solids cargo, particle size

etc., a blanket statement about the optimum operating point to be selected is not
possible. The values listed in Table 3 show
some data typical from practice.
In this case, it must be mentioned that,
for example, an increase of the temperature of the inflow medium leads to an
increase of the permeate performance with
a concurrent drop of the permeate quality,
while a reduction of the media temperature
leads to the fact that the transmembrane
pressure must be raised in order to keep
the permeate flow constant.
3. Ceramic nanofiltration
membranes
3.1 Membrane construction and
characteristic variables
With development and market launch of
ceramic nanofiltration membranes with a
separation limit below 1 kDa, a totally new
product branch of ceramic membranes hit
the market which differs in several aspects
from ceramic micro and ultrafiltration
membranes. Ceramic nanofiltration membranes - like ceramic micro and ultrafiltration membranes - are built up in layers, i.e.
on a very porous carrier (called
Support), separation-active membrane
layers are applied in several process steps
and these layers have a finer separation
limit with every process step, so that at the
end of the manufacturing process, the
finest membrane layer - which also defines
the separation limit of the ceramic membrane tube - is applied and this is also the
layer that during operation receives the
oncoming flow from the feed medium. An
example construction is shown in Fig. 5.

It is obvious that maximum membrane

permeability is to be aimed without a loss
of selectivity and without using a manufacturing method that would make commercialisation impossible for cost reasons.
Concerning the membrane permeability L,
the law from Hagen-Poiseuille for a
porous structure is:

In detail, there are the porosity of the

membrane, the pore diameter, the dynamic viscosity of the medium and the membrane thickness. Essential problems
already become obvious here, which one is
confronted with due to increasingly smaller pore sizes. Because the pore size
squarely enters in the permeability of the
membrane, an increasing reduction of the
pores means a disproportionate loss of permeability that one must counteract:
remaining here as possible manipulated
variables are the porosity and the thickness
of the membrane layer, i.e. it is always
aimed for that a membrane layer is very
thin and has very high porosity.
Unfortunately, increasing porosity goes
hand in hand with a loss of chemical resistance, since increasing porosity means a
surface enlargement that offers a bigger
attack area for the respective chemicals.
This circumstance, in turn, can be counteracted only by having starting materials as
pure as possible and the cleanest production conditions. Besides the application of
additional membrane layers, these requirements for cleanliness in the manufacturing
process and the purities of the starting
materials constitute the essential influence
on the cost structure of ceramic nanofiltration membranes. In practice the law of
Hagen-Poiseuille also means, for example,
that the membrane layer should be very
thin, but still mechanically stable enough
to resist the forces occurring - for example,
through incident flow of solids loaded
inflow media. At the same time it can also
be recognized from the law of Hagen-

Fig. 10: Membrane housing for ceramic membrane

elements /1/

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Tab. 4: Isoelectric points of different oxide

ceramics

Fig. 11: Extrusion of ceramic membrane carriers /1/

Poiseuille that the hydraulic resistance of

the ceramic support plays a minor part,
since its pore size - as a function of the
material and production process - is usually in the range of 3 - 5 m, while the pore
sizes of ceramic microfiltration membranes can lie approx. in the ranges 100 800 nm and the pore sizes of ceramic
nanofiltration membranes can be less than
1 nm.
3.2 Manufacture of ceramic
nanofiltration membranes
As shown in Fig. 11, the supports of
ceramic nanofiltration membranes are
extruded - just like the supports of ceramic micro and ultrafiltration membranes - in
order to implement tubular geometry. In
this case, different oxide ceramics are used
as a material, which in each case, on
account of their physical and chemical
properties, are of advantage or disadvantage for corresponding applications.
Typical materials are, for example, aluminium oxide (Al2O3), titanium oxide
(TiO2) and zirconium oxide (ZrO2), and
here, aluminium oxide is used nearly
exclusively as -Al2O3, since -Al2O3 is
not stable at the temperatures at which the
respective membrane layers are sintered.
The influencing of the pore size of ceramic supports is a subject of a huge number
of publications and, hence, should not be
discussed at this point in depth. Typically
the pore size of ceramic supports can be
influenced by admixing of excipients that
incinerate during the combustion process
and then leave behind respective pores in
the matrix. A typical excipients for this is
starch and also here, as a function of the
starch, the pore size varies: While with
potato starch pore sizes of up to 50 m can
be achieved, the pore sizes when using
wheat starch lie in the range of 20 m and
with rice starch in the range of 15 m. In
addition, a crucial role is also played by
the combustion temperature and burning
period: While burning for too short a time
or burning at too low a temperature entail
an inadequate formation of the ceramic
structure and therefore a poor mechanical

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stability, too much time or overheating

causes the loss of porosity and a decrease
of the number of pores.
While ceramic micro and ultrafiltration
membranes are usually applied and sintered in layers with a slurry method, pore
sizes for nanofiltration in a range of a pore
diameter of 1 nm cannot be realized with
these processes anymore. Here, a Sol gel
process is used, in which either a coarseporous carrier, or a carrier that has been
initially pre-coated with an ultrafiltration
membrane, is coated with liquid Sol. This
method - in connection with polymeric
Sols - was particularly promoted by
Puhlfr et al. and optimised from the
point of view that it can be used beyond
just on laboratory scales /3/. The coating
of the carrier can be done in different
ways, for example, by means of SprayCoating (spraying on) or Dip-Coating
(immersion), wherein Spray-Coating is
suitable primarily for flat structures and,
hence, is not applicable for using with a
tubular geometry. The liquid gel is transferred into a solid gel when the gel point is
exceeded. In general with this Sol-gel
process there are two different methods
that differ in the kind of the Sol. The prevailing part of the ceramic membranes
available on the market that are produced
by means of the Sol gel process are produced by means of a colloidal sol in which
a metal alkoxide is hydrolyzed in an environment with a surplus of water; in this
case nanodisperse particles are then
formed, which can be peptized by treatment with respective electrolytes. These
aqueous suspensions - which either consist
of colloidal or aqueous sols - are admixed
with corresponding substances which
implement mechanical bonding on the surface and then are applied directly to a
coarse-porous support. The adjustment of
the pore size occurs during hydrolysis by
varying the temperature and concentration
accordingly.
Because with a colloidal sol no pores
can be mapped that are smaller than 2 nm,
these pore sizes are implemented by

means of a Sol gel method with a polymeric sol. In this case, pore sizes can be
mapped down to 0.9 nm. The method is
distinguished by the fact that they are
working with an alcoholic solution where
a partial hydrolysis of the metal alkoxides
is triggered by addition of water and the
metal alkoxides then polycondense in the
solution. If the dilution is corresponding,
the forming oligomers will remain in solution and are allowed to gel only when
applied to the membrane support, since
here, a suction effect results due to capillary forces. With this method, ceramic
nanofiltration membranes can be produced
from titanium dioxide, whose separation
limit in aqueous media is 450 Dalton.
Besides ceramic nanofiltration membranes from TiO2 /2/ ceramic nanofiltration membranes with a separation limit of
approx. 300 Dalton were implemented by
van Gestel on the basis of ZrO2 / TiO2; for
this purpose, the tetragonal zirconium
oxide was stabilised with yttrium. Agoudil
et al. /4/ have implemented ceramic
nanofiltration membranes from a mixture
of ZrO2 and SiO2 by using tetraethoxysilanes (Si(C2H5O)4) and zirconium tetrapropoxide (Zr(C3H7O)4); the transformation temperature of zirconia from the
tetragonal to the monoclinic phase was
able to be shifted to higher temperatures
by addition of SiO2.
In general, different materials and production approaches are currently to be
found on the market for ceramic nanofiltration membranes, which result in corresponding advantages and disadvantages;
for instance, the system SiO2 permits a
good monitoring of the pore size in the
manufacturing process, but at neutral and
alkaline pH values has detrimental properties in the stability. However, the system
aluminium oxide is at low pH values (pH
<2) only conditionally stable while the
systems ZrO2 and TiO2 have a good to
acceptable stability across the whole pH
value range.
3.3 Surface load of ceramic
membranes
Besides the pore size, the surface load
plays an important role with ceramic
membranes. In general the surface load
can form itself with ceramic membranes
on account of different mechanisms:

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3.4 Material transport through

ceramic nanofiltration
membranes

Fig. 12: Retention of a ceramic NF membrane as a function of pressure and pH value

Fig. 13: Retention of an improved NF membrane of Inopor GmbH

- Dissolution / absorption of ions into / from the surrounding liquid

- Dissociation of molecule groups on the surface
- Adsorption of ions / electrolytes on the surface
Because ceramic membranes typically have amphoteric behaviour, they can absorb and/or emit positive or negative ions / molecule groups as a function of the pH value. While ceramic membranes with low pH values have positive electric potential, it is
negative with high pH values. This electric potential is called Zeta
potential and can be measured by means of suitable measuring
cells and electrodes. The point at which the electric potential is
equal to zero is called isoelectric point. Typical values of oxide
ceramics for this are listed in Table 4.
As a function of the pH value of the medium to be filtered and
the isoelectric point of the membrane material used, the retention
of the membrane is also influenced and in general it has to be said
that the retention near the isoelectric points is worse because there,
the repulsion or attraction effects, which otherwise can influence
the separation process positively, cancel each other out. Fig. 12
shows how the retention of a ceramic nanofiltration membrane
with a pore size of 0.9 nm from TiO2 changes as a function of pressure and pH value.

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An essential difference between ceramic and polymeric nanofiltration membranes is that even the ceramic nanofiltration membrane like the micro and
ultrafiltration membranes - is a pore membrane while polymer membranes are
dense membranes. Therefore, the solution-diffusion model that is used in the
case of dense diffusion membranes, cannot be modified for ceramic nanofiltration
membranes. According to the solution-diffusion model, inter alia, it arises that with
rising water flow rate and/or pressure, the
retention increases and theoretically
approaches a value of 100%. This is
because the back diffusional proportion,
with rising water flow rate, has increasingly less influence on the deterioration of
the permeate; consequently it is not advisable to operate polymeric systems with
wound modules with insufficient pressure,
since the permeate quality noticeably
decreases. The higher the proportion of
the ingredients to be separated, the more
clearly this effect is detected.
However, with ceramic nanofiltration
membranes the substance transport can be
described sufficiently well for practice
with the expanded Nernst-Planck equation
according to Dresner. The expansion of
the Nernst Planck equation according to
Dresner consists of the fact that, beside the
solutes and the solvent, he also included
the membrane and its material in the thermodynamic consideration. To this end,
Dresner introduced an Interaction parameter /5/. The surface-related molar transport of a component j according to
Dresner consists of the following terms:

Convective Transport:
Diffusive Transport:

Electromigrative Transport:

Therefore the following equation arises for the surface-related

molar transport of a component:
.
In this case, cj,M is the concentration of the component j in the
membrane, vW is the velocity of the water, D(j,M) is the diffusion
coefficient of the component j in the membrane, zj is the ion valency
of the component j, F is the Faraday constant and
is the
displacement-dependent change in membrane potential. The introintroduction of the interaction parameter changes the convective
term to the effect that interactions with the solid ions in the matrix
of the membrane may be considered, similar to the interaction of

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Highlights 2013

solid ions in the matrix of an ion exchanger membrane. In particular, it is considered with this parameter that the convective ion
transport is not necessarily carried out with the speed of the convective transport of water. Dresner looks at the parameter , as well
as the diffusion coefficient of the water, as being independent of
the concentration. Tests with higher pressures and concentrations
have shown that the independence from the concentration is then
not totally present anymore, but for low and middle concentrations,
the equation according to Dresner has still proved to be very accurate. In particular, it applies also for ceramic nanofiltration membranes that a too low pressure and therefore a too low water flow
rate have a negative effect on the permeate quality.
3.5 The future of ceramic nanofiltration membranes
As already described, ceramic nanofiltration membranes with a
cut-off of 450 Dalton can be produced in large scale with process
reliability; in laboratory and prototype scales, membranes with significant lower cut-off rates were already able to be implemented.
An essential challenge will lie in the near future in also mapping
these membranes with a separation limit of 300 Dalton or less with
process reliability and in pipe geometry.
Fig. 13 shows an example of the retention characteristics of a
membrane prototype of the company Inopor GmbH, in which the
membrane potential was changed specifically by trying to map
electro-chemical mechanisms from ion exchangers with modified
ceramic membranes. In this case, a separation limit of smaller than
300 Dalton was able to be implemented with constant porosity and
constant flow rate, but currently, the long time stability of this
membrane is not optimized yet.
Alternatively to the optimisation of ceramic membranes, the
composite of ceramic and polymeric membranes will certainly
gain importance in the near future, since, here, the advantages of
both membrane models can be combined in one product. In the
ideal case a ceramic nanofiltration membrane would be conceivable on which there is a solidly bonded reverse osmosis membrane.
In spite of intensive researches in this area - in particular in the
USA - only prototypes on a laboratory scale are currently available.
Beside the optimisation and improvement of the ceramic membranes as a product looked at in isolation, the best possible placement and combination of appropriate products in increasingly
complex process and production chains will also increasingly be
gaining in importance. This assumes, for the design and implementation of a process, that knowledge about the most different
methods and products exists, in order to be able to select from
among them the optimum method with the best possible suitable
membranes. As an example for this, it should be mentioned that
Inopor GmbH, with acetic acid produced by fermentation, could
combine several methods in such a manner that the acetic acid was
initially purified and then, by means of a special membrane
process, was able to be concentrated to a concentration of 30-32%.
Literature:
/1/ Inopor GmbH, Veilsdorf
/2/ T. van Gestel, H. Kruidhof, D. H.A. Blank, H. J.M. Bouwmeester: ZrO2 and TiO2 membranes for nanofiltration and pervaporation: Part 1. Preparation and characterization of a
corrosion-resistant ZrO2 nanofiltration membrane with a MWCO<300. Journal of
Membrane Science 284 (2006) , No. 12, Pages 128-136
/3/ P. Puhlfr, A. Voigt, R. Weber, M. Morb: Microporous TiO2 membranes with a cut-off <
500 Da. Journal of Membrane Science 174 (2000), No. 1, Pages 123 133
/4/ N. Agoudjil, N. Benmouhoub, A. Larbot: Synthesis and characterization of inorganic membranes and applications. Desalination 184 (2005), No. 1-2, Pages 65 - 69
/5/ L, Dresner: Some remarks on the integration of the extended Nernst-Planck-Equations in
the hyperfiltration of multicomponent solutions. Desalination 10 (1972), No. 1, Pages
27 - 46

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