Separation and Purification Technology 25 (2001) 341 346

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Ozonewater contacting by ceramic membranes

P. Janknecht a,*, P.A. Wilderer a, C. Picard b, A. Larbot b
a

Technische Uni6ersitat Munchen Am Coulombwall, 85748 Garching, Germany

Institut Europeen des Membranes, CNRS, 1919 route de Monde, Montpellier, F-34293, France

Abstract
A common process in water treatment is the wet oxidation for the removal of certain organic and inorganic
pollutants. The strongest oxidant technically applied in this process is ozone, which is an unstable gas under normal
conditions, and therefore is produced from oxygen on site, usually by electrical discharge. After that the ozone has
to be transferred from that gas into the water to be treated. Conventionally ozone transfer is achieved by bringing
the gas and water in direct contact by means of bubble columns, injectors or other similar devices. Under unfavorable
conditions, however, these methods suffer from excessive formation of foam requiring an extra treatment and a
high-energy demand for pumping gas or water. This projects approach was to improve the transfer by better control
of gaseous and aqueous phases conditions at the contact surface. This was achieved by means of a membrane both
separating the two phases and allowing for an ozone transfer between them. Due to ozones high oxidation potential,
chemically inert ceramic membranes were chosen for that purpose. In experiments, it was found that the transfer of
the unstable ozone molecules is not obstructed by ceramic membrane material. Transfer rates between gaseous ozone
and model water were measured for conventional ceramic membranes, as well as specially designed ones. They are
comparable to conventional methods or better on the base of mass transfer per reactor volume. In conventional oxide
membranes, water enters the pores because of capillary effects in the hydrophilic material [Burggraaf, A.J. and Cot,
L., 1996, Fundamentals of inorganic Membrane Science and Technology Elsevier Science, The Netherlands]. The
water in the pores raises the diffusion resistance for the ozone thus decreasing the transfer itself. Consequently, the
modification of the hydrophilic material features into a hydrophobic behavior was one promising approach for the
optimization of the process. It was achieved through the application of a hydrophobic coating to the membrane
surface, which greatly improved the transfer efficiency. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Ceramic membranes; Ozonation; Gas contacting; Gas transfer; Mass transfer

1. Introduction
Common membrane processes are characterized by the feature of the utilized membrane to
* Corresponding author. Tel.: + 49-89-28913717; fax: + 4989-28913718.
E-mail address: janknecht@bv.tum.de (P. Janknecht).

hold back certain components of a fluid mixture,

while allowing others to pass through. In the most
common case of membrane filtration, the permeating component is the solvent of the mixture,
whereas the non-permeating components are pollutants that desirably should be removed from it.
Here the media that is to be purified is forced
through the membrane by application of pressure

1383-5866/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 1 3 8 3 - 5 8 6 6 ( 0 1 ) 0 0 0 6 1 - 2

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P. Janknecht et al. / Separation/Purification Technology 25 (2001) 341346

to the mixture. In other cases the purification

process involves the retaining of the fluid to be
purified, while the undesired pollutants pass
through the membrane and thus can be removed.
The driving force in these processes is a gradient
in partial pressure of the respective substance
from the mixture side of the membrane to the
receiving side. The medical application of membrane dialysis represents this kind, but similar
ones occur manifoldly in technical and natural
processes.
Respiration can also be regarded as a membrane process, the delivering fluid is air and the
permeation of oxygen through the membrane to
the liquid fluid on the other side constitutes the
aim of the process. While this concept has been
utilized and optimized for millions of years biologically and also technically ([1]), a similar variation of this process, which is the subject of this
work is much newer and still worked on. The
novelty is in the fact that ozone instead of oxygen
is transferred and the challenge is formed by the
peculiar features of this substance.

2. Ozone in water treatment

Ozone is one of the strongest oxidants technically applied. It is utilized in a variety of chemical
processes, as well as in the treatment of both
drinking and wastewater. The aims of ozonation
in water treatment include the removal of color
and smell and the disinfecting of biologically polluted water in order to destroy or inactivate microorganisms and even viruses. Furthermore, by
reacting with macromolecular organic pollutants
ozone can improve flocculation and successive
removal of these substances. It can also increase
the biological accessibility of organic pollutants
when toxic substances are present, which otherwise inhibit the activity of microorganisms ([2]).
In high doses ozone can even affect a complete
wet oxidation in which all present organic matter
is wholly mineralized. This process, however, due
to its high ozone demand usually is limited to
applications with low water volumes and difficult
pollutants.

In chemical view the ozone molecule (O3) consists of three oxygen atoms and is considerably
unstable. This instability accounts for two peculiarities that make technical ozone applications
special: first ozone can not be stored or transported like other gases, since when filled into
containers it continuously decays until only oxygen is left. Therefore, it can only be produced at
the place and the time of consumption from oxygen or oxygen containing gases like air. The production consists of applying energy to molecular
oxygen (O2), either as ultraviolet radiation or as
an electrical discharge, through which by splitting
and recombination three oxygen molecules can be
transformed into two ozone molecules. This process, however, is subject to a thermodynamical
equilibrium that only allows for a comparatively
small portion of the oxygen to be transformed to
ozone. Thus, the second peculiarity of ozone in
technical application is the fact that it cannot be
applied as a pure gas, but is always mixed with
oxygen and possibly other gases that usually
make up more than 90% by mass of the mixture.
Thus, if ozone is to be applied to water it needs
to be transferred from the gas phase mixture into
the liquid phase. The necessary condition for that
is a surface between the two phases to enable the
phase transfer, usually prepared by the formation
of gas bubbles within the water. Transport within
the two phases generally can be accomplished by
diffusion, since the ozone will be readily consumed in the water, creating the necessary drop in
partial pressure from the gas to the liquid phase.
Since the diffusion coefficient of ozone in water is
relatively low, however, the transfer performance
can be and in technical application often is considerably increased by mechanical agitation creating shear forces on the liquid boundary layer close
to the surface, thus overlaying a fast convectional
transport to the slow diffusion.
Conventional ozone contacting methods include bubble columns, impellers, injectors, and
others. The shear forces in the water boundary
layer are engendered either within the resting liquid by the floating of the bubbles as in bubble
columns, or by additional agitation of the liquid
performed by mechanical stirring that also keeps
the bubbles from coalescing.

P. Janknecht et al. / Separation/Purification Technology 25 (2001) 341346

While the creation of bubbles is the simplest

method to create a contact surface between the
two phases it also displays a few drawbacks. The
generation and continuation of bubbles constantly
consumes energy, and the surface itself is subject
to many factors, which thus indirectly influence
the gas transfer. One example for the latter problem is the ozonation of water containing surfactants ([3]).
Surfactants are substances that due to the inherent force of attraction between the dipolar
water molecules tend to accumulate near the inter-phase surfaces. This accumulation in turn disturbs the forces between the dipoles of the water
molecules at the surface and can reduce the surface tension considerably, which leads to a drastically decreased size of bubbles within the water
and stabilizes the bubbles after reaching the surface, so that a layer of foam develops. This foam
can complicate the control of process parameters
by consuming reactor space and in the extreme
even prevent the whole ozonation process from
working.
Triggered by difficulties in a research project
dealing with such surfactant-loaded wastewater,
and with the concept of a respiration-like membrane process, an approach was made to achieve
better control over the inter-phase surface by
means of membranes. Ceramic membranes were
selected for that purpose, since most polymer
materials are not suited for application with
ozone.

pump, a side stream of the circulating flow passed

through a photometer cuvette for aqueous ozone
determination. The gas was also pumped in a
circuit from the electrical discharge ozone generator (Anseros COM) through the module and by
way of a silica gel exsiccator back to the generator. Technical oxygen was used in this circuit, gas
tubing consisted of stainless steel (1.4571 standard), borosilicate glass, Polytetrafluorethylene
(PTFE), and a stainless steel metal bellows
compressor.
Ozone measurement and regulation in the gas
phase were carried out in a side stream by direct
UV absorption at a wavelength of 253.7 nm
(ANSEROS Model GM-6000-OEM). The
aqueous ozone measurement represented a special
difficulty, because the characteristical decay of
ozone in the gas phase corresponds to an even
faster decay of dissolved ozone in the aqueous
phase. Since in the laboratory scale experiments
only small membrane samples could be applied,
the ozone transfer was limited and demanded for
an especially adapted method. After a series of
tests with different techniques ([4]), a process developed by Hoigne and Bader and described by
Langlais [5] and in the German Standard Method
DIN 38 408-G3-3 was successfully modified and
adopted a model water with a defined concentration of dissolved indigo trisulfonate (a strong
blue dye) is prepared to serve as the receiving
aqueous phase. During circulation in the setup,
this dye is readily oxidized by the ozone transferred through the membrane, which leads to a

3. Materials and methods

A flow scheme of the experimental setup is
given in Fig. 1. The membrane type was a single
channel tubular ceramic membrane with fine layer
on the inner surface. The dimensions were 9 or 10
mm outer diameter, 5 or 7 mm inner diameter,
and a length of 200 or 400 mm, respectively. A
special module was designed to allow for a turbulent water flow through the inner membrane volume, while the ozone containing gas was applied
to the space formed by the outer membrane surface and an enveloping glass tube. The water was
circulated within PVC tubing by means of a radial

343

Fig. 1. Flow scheme of the experimental setup.

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P. Janknecht et al. / Separation/Purification Technology 25 (2001) 341346

bleaching effect on the blue color. Indigo trisulfonate concentration is monitored colorimetrically
by ultraviolet absorption at a wavelength of 605
nm and from its decrease the stoichiometrical
ozone consumption is calculated. Due to a limited
absorption linearity the measurement range of
this method is moderate, but precise and reproducible measurements of ozone transfer rates
could be carried out with it.

4. Results with hydrophilic membranes

In the first experiments, conventional alumina
membranes were used. The transfer rates obtained
with those were satisfying in that they proved that
ozone transfer through ceramic membranes is
possible and is not obstructed by the porous
ceramic material through which the ozone must
pass. The transfer rate displayed a strong dependency on the conditioning of the membrane during experiment startup, once the water circuit was
started and water touched the fine layer of the
membrane, the capillary effects of the hydrophilic
material caused a penetration of water into the
pores. If no pressure was applied to the surrounding gas phase, the membrane was completely penetrated within seconds and no ozone transfer was
observed later. Therefore, the membrane was
dried before the experiment and a gas pressure of
50 kPa was applied before the water circuit was
started. This gas pressure is higher than the capillary pressure of the support material and thus
allowed the water only to penetrate the fine layers.
Under these conditions and in relation to the
required membrane surface a transfer of 0.35 g of
ozone per square meter and hour was observed
reproducibly (Fig. 2).
If a partially wet membrane was utilized or the
conditioning procedure was not observed, the
transfer rates decreased considerably. In successive trials the drying time of a wet membrane
before an experiment was correlated to the respective transfer rates during the experiment. The
result indicates that residual water within the
pores constitutes a major limiting factor to the
transfer (Fig. 3).

Fig. 2. Accumulation of transferred ozone within the liquid

phase during contacting with a hydrophilic alumina membrane. Inner diameter 7 mm, effective length 390 mm, ozone
concentration in the gas 100 g m 3, liquid flow velocity 2.2 m
s 1.

5. Results with hydrophobic membranes

It became obvious from these findings, that the
penetration of the fine layers, though only covering a distance of a few micrometers, represented a
considerable obstacle for a fast ozone transfer
through the membrane. Thus keeping the liquid
phase from entering the pores appeared as a
promising approach for increasing the transfer
performance. It was engendered by application of
a thin hydrophobic layer to the ceramic surface by
means of a so-called grafting process.
The modification resulted in a surprisingly
strong transfer improvement, though no direct
comparison was possible since the membrane geometry also had to be modified. The transfer
performance measured under similar conditions
was 12 g ozone per membrane square meter and
hour and higher (Fig. 4).

Fig. 3. Correlation between membrane drying time and ozone

transfer.

P. Janknecht et al. / Separation/Purification Technology 25 (2001) 341346

Fig. 4. Accumulation of transferred ozone within the liquid

phase during contacting with a hydrophobic membrane. Inner
diameter 5.2 mm, effective length 190 mm ozone concentration
in the gas 100 g m 3, liquid flow velocity 3 m s 1.

6. Comparison to conventional contacting methods

The advantage that originally was expected
from the new contacting process was the avoidance of bubble and foam formation in the ozonation process. In this respect the method fulfilled
the expectations, high ozone doses were transferred to surfactant loaded wastewater without
any foam problems.
During the development it was found, however,
that it also displays other benefits: with hydrophobic membranes the transfer rate is almost
linearly related to the liquid flow speed within a
wide range, thus a constant ozone dosage even
with unsteady flow rates is easily secured (Fig. 5).
Due to the utilization of a statically fixed phase
border, the liquid flow velocity can be accelerated
and the turbulence increased far beyond the values practicable with open surfaces such as bub-

Fig. 5. Correlation of liquid flow velocity and ozone transfer

in a hydrophobic tubular membrane.

345

bles. Furthermore, since the recycling of the

carrier gas provides a constant high ozone concentration on the gas side the gradient in partial
pressure is considerably high, so that the ozone
transfer rate per time and per area is extremely
high. Values upto 16 g ozone per square meter
and hour have been measured in a tubular membrane with 5.2 mm inner diameter and a mean
liquid flow velocity of 4 ms 1. Assuming a
configuration of a number of these membranes
stacked closely together in a hexagonal arrangement with a small gap for gas circulation in
between, more than 1000 g ozone per hour could
be transferred in an installation volume of 1 m3.
In comparison the performance of a bubble
column as is commonly used for ozonation is
below 40 g h 1 m 3, that is by a factor of 25 less
(value calculated from [5]).
A second advantage of the high ozone transfer
performance is the reduction of moisture uptake
by the carrier gas. While the gas that is left over
in a conventional ozonation process usually is
disposed off, the gas phase in the membrane
process can be easily recycled back to the ozone
generator. Since pure or enriched oxygen gas is
often applied in ozonation processes in order to
reach higher ozone concentrations, the utilization
of this resource can be optimized considerably.
Another point of interest connected to ozonation systems is the energy demand. Since ozonation processes first were applied technically more
than 100 years ago, the efficiency of ozone production has been increased continuously and
nowadays seems to approach the thermodynamical limits. Today 1 g of ozone can be produced
from oxygen with an energy in the magnitude of
10 Watt-hours (Wh), depending on the technology and the desired ozone concentration. The
contacting process, however, can consume almost
the same amount for pumping and mixing performance, values between 2 and 10 Wh per g ozone
are found in literature ([2]).
In the membrane ozonation process, one of the
most important transfer parameters is the liquid
flow velocity along the membrane surface, as
mentioned above. Due to the turbulence, the flow
rates are related to the head loss and pumping
energy for the process, thus making up the bulk

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P. Janknecht et al. / Separation/Purification Technology 25 (2001) 341346

of its energy demand. Though the laboratory

scale of the experiments did not allow for a
hydrodynamic optimization so far, the energy loss
of water measured in an ozonation experiment
with a reverse membrane corresponded to a specific energy demand of only 7 Wh per g ozone,
which is well in the order of magnitude of conventional processes.

for the assistance of the staffs of Institute for

Water Quality Control and Waste Management,
Munich, and Laboratoire des Mate riaux et Proce de s Membranaires, Montpellier. The financial
support of Bayerisches Staatsministerium fu r Landesentwicklung und Umweltfragen and Centre
National de la Recherche Scientifique within the
framework of cooperation between Bavaria and
the French Region Languedoc-Roussillon is
gratefully acknowledged.

7. Conclusions
From the findings, it can be concluded that the
ozone contacting process with ceramic membranes has the potential to become a useful
method of treating wastewater. Several advantages in the process design speak in favor of this
approach as compared with conventional bubble
based contacting procedures, including a constant
ozone dosage independent of the liquid flow rate,
a potential to easily recycle the oxygen carrier gas
and the high transfer performance within a small
installation volume.

Acknowledgements
The authors wish to express their appreciation

References
[1] N. Mu ller, Berechnungsgrundlagen und Anwendungsbeispiele zum Sauerstoffeintrag in Wasser und Abwasser
u ber nichtporo se Polymermembranen (Technische Universita t Hamburg-Harburg, Hamburg, Germany), 1986.
[2] S. Pschera, Abwasserbehandlung mit Ozon (R. Oldenbourg Verlag, Mu nchen, Germany), 1997.
[3] J. Do llerer, Biologische Behandlung von Sickerwa ssern aus
Sonderabfalldeponien mittels schubweise beschickter, u berstauter
Festbettreaktoren
(Technische
Universita t
Mu nchen, Munich, Germany), 1998.
[4] P. Janknecht, P.A. Wilderer, C. Picard, A. Larbot, J.
Sarrazin, Blasenfreier Ozoneintrag durch keramische
Membranen zur naoxidativen Abwasserbehandlung,
Chem. Ing. Tech. 72 (2000) 122 126.
[5] B. Langlais, D.A. Reckhow, D.R. Brink, et al. (Eds.),
Ozone in Water Treatment: application and engineering,
Lewis, Chelsea, USA, 1991.