MEMBRANE HYBRID PROCESSES IN WATER TREATMENT – THE STATE OF ART

Michał Bodzek, Krystyna Konieczny

The progress in the development of microfiltration (MF) and ultrafiltration (UF) resulted in the
90’s of the previous century caused rather intensive its application in the water treatment. A general
application of UF/MF processes is hampered by the contamination and fouling of the membranes by
soluble and colloidal organic substances in raw water. The proper application of UF/MF processes
requires strictly defined and adequate methods of controlling and minimizing the fouling and the
operating costs, as both these factors continuously restricts the application of membrane filtration in
practice. Fouling influences directly not only the maximum value of the permeate flux, and thus the
installed surface of the membrane, but also affects the conditions of its regeneration, influencing the
membrane life-time. A proper way of controlling an irreversible fouling is a preliminary treatment of
raw water before it is introduced to the membrane. For this purpose the following process systems
have been suggested: coagulation - UF/MF, adsorption on activated carbon – UF/MF, biological
filtration – UF/MF, oxidation – UF/MF and membrane bio-reactors (e.g. for the removal of nitrates).
Combined membrane systems are particularly useful for the treatment of surface water, which in
contrast to underground water is often characterized by the presence of large amounts of
contaminations.

1. Hybrid process coagulation – UF/MF

The addition of a coagulant (aluminum or ferric salts and also poly(aluminum chloride) [1])
preceding MF or UF can increase the extent of the removal of natural and anthropogenic organic
substances, including the precursors of the disinfection byproducts. Such a procedure improves also
efficiency of the membranes, both polymeric and ceramic [2]. UF permeate flux being the most
favorable, when the condition of coagulation lead to the formation of floccules with a zeta potential
close to zero. There are three mechanisms of the increasing the permeate flux thanks to the application
of preliminary coagulation of the water preceding UF/MF [1]: reducing the penetration of substances
which cause fouling inside the membrane structure, forming a filter cake on the surface of the
membrane with a smaller porosity and improving the condition of transporting the particles (lift
forces).
Hybrid systems of the treatment of natural water basing on the process of coagulation and UF/MF
are usually run in three fundamental system solutions [1,2]:
 coagulation of water in a separate tank with a fast and slow mixing, sedimentation and
UF/MF,
 “in-line” coagulation (adding the coagulant before the membrane filtration, i.e. without
sedimentation), followed by UF/MF of the suspension of the post-coagulation floccules,
 hybrid process with an immersed membrane – the separation takes place in the same
tank as the coagulation.

Authors were carried out the investigations concerning the effectiveness of the hybrid system
coagulation-sedimentation-UF/MF [3]. Filtration in the hybrid system improves considerably the
efficiency of the membrane, deviating only slightly from the flux for deionized water, as has been
proved by calculations of the values of the relative permeability of the membrane, which values

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amount in the hybrid system to 0.98 for simulated water containing organic carbon (TOC). Table 1
presents the retention coefficients of the respective contaminants of water for ceramic membranes (0,1
m) and ferric chloride (III) as coagulants. Water treatment in the hybrid system coagulation-
sedimentation-MF allows to attain a constant and high efficiency of the membrane and also to
eliminate organic compounds in contrast to unit process coagulation and MF.
Table 1. Retention coefficients (%) of some water pollution indices; water 7 and 10 mg TOC/l
Parameter Coagulation Hybrid process MF
turbidity 9.86 51.1 97.2 94.9 100 99.0
absorbance 78.7 94.4 99.2 99.3 99.4 97.7
TOC 66.8 89.7 100 100 100 100

Lately UF with “in-line” coagulation is preferred as a method replacing the classical technique of
preliminary treatment [4,5], because it ensures a constant and high quality of the treated water,
independently of the way in which UF is being run, the kind of the applied membrane and the
composition of raw water, and because it also definitely improves the conditions of the membrane
process [4].
C.Guigui et al. [5] attained a better quality of the permeate than in the case of other solutions,
because the elimination of dissolved organic carbon (DOC) is connected with the coagulation. The
similar investigations have been carried out by Konieczny et.al. [6] using ceramic UF and MF
membranes. Comparing the efficiency of various coagulants one can state that “in- line” coagulation
and membrane filtration alone do not characterize the good results. MF i UF membranes remove
effectively organics at high permeate flux in hybrid process with „in-line” coagulation.
Very interesting comparative investigations on the classical coagulation with sedimentation and
“in-line” coagulation have been presented in Ref. [7], where the affectivity of eliminating DOC and the
absorbance of UV (254 nm) have been studied, using dead-end and cross-flow mode of membrane
filtration. The removal of compounds absorbing the radiation of UV (254 nm) is higher in the case of
classical coagulation than in the case of “in-line” conditions.
Immersed membrane systems constitute a proposition of water treatment on a large scale and
permit to modernize the conventional systems based on coagulation [2,4]. An advantage of these
systems lies in the fact that the stage of membrane filtration can be performed in the same container as
the coagulation [8,9]. Moreover, bubble-aeration applied in the vicinity of the membrane caused that
the particles are removed from the surface of the membrane, so that the fouling can be controlled.
Many authors [8,9] have proved the efficiency of water treatment in the hybrid system with an
immersed UF/MF membrane. P. Choksuchart [8] has proved that in such a conditions coagulation also
brings about an increase of the size of the floccules and increases the rate of sedimentation; it also
stabilizes the permeate flux of the UF. The quality of the permeate depend on the dose of the
coagulant, and the elimination degree of the water impurities is definitely higher than those obtained
for of the coagulation alone [9].
Authors [10,11] have carried out investigations for comparison the efficiency of the hybrid
coagulation-UF process with UF alone in the treatment of water containing NOM with the immersed
capillary PVDF membranes ZeeWeed 10. Simulated water and natural surface water were used as a
feed. Analyzing the results for simulated water and UF alone, we found a high efficiency of turbidity
removal and a low removal efficiency of organic substances determined as oxidizability (COD) with
KMnO4. The application of the hybrid system results in a higher removal efficiency of organic
substances from water depending on the kind of the coagulant and the mode used for the coagulation
process (“in-line” or ordinary coagulation with sedimentation). The metals (Fe, Al) were efficiently

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removed to the level required by the Polish standards. For natural water (Czarna Przemsza in Upper
Silesia, Poland) UF aided by coagulation leads to an increase of the retention coefficient, particularly
in the case of organic substances designated as UV absorbance and oxygen consumption with KMnO4,
as well as to a higher turbidity and content of iron (Table 2).

Table 2. Comparison of the retention coefficients for water treatment by means of the UF method and hybrid system
Retention coefficient (%)
Parameter UF alone coagulation FeCl3 - UF coagulation - UF
Natural Simulated Natural Simulated Natural water Simulated water
water water water water Fe2(SO4)3 - UF Al2(SO4)3 - UF
Turbidity NTU 72.1 98.3 97.9 90.9 97.8
COD with KMnO4 34.2 43.3 42.2 56.6 49.8 52.1
UV 254 nm absorbance 34.3 75.4 74.8 66,5 69.0 71.1

2. Hybrid process adsorption on active carbon – UF/MF

The application of the hybrid system combining adsorption on powdered activated carbon (PAC)
with UF/MF for the purpose of treatment natural waters is more efficient than the process of unit
membrane filtration. The addition of carbon increases the efficiency of the membranes and the
effectiveness of contaminations removal [12]. The membrane is a physical barrier preventing the
passage of PAC, and thus the organic compounds which have been adsorbed on PAC are retained. This
means that substance which lead to fouling are completely retained by the activated carbon and do not
deposit on the surface of the membrane. The efficiency of the process is affected by the frequency of
back-flushing, the size and shape of the reactor, the kind of filtration (dead-end or cross-flow) and the
way of dosing the carbon [12].
There are various configurations of the hybrid system with activated carbon. One part of the
system is usually the reactor, to which the activated carbon is introduced. The reactor may constitute
the recirculation mode or be preceded by the mixing and adsorption chamber (static or flow chamber)
[12], in which the process of adsorption takes place in batch or continuous mode. The second part of
the system is the membrane or a set of membranes, where the particles of activated carbon are
separated from the treated water. The activated carbon is drain off from the membrane module by
back-flushing and then removed or again recycled to the process [12].
The dose of activated carbon must be adapted to the concentration of contaminations in the raw
water and to the preset quality of the treated water. It has been found that in the case of ground water
with PAC concentration below 2 mg/l no PAC need be added to the membrane system [12]. Such water
may, however, contain seasonally micro-pollutants (e.g. pesticide) and also higher concentrations of
other impurities, and then only small doses of PAC may be applied [12]. In the case of surface waters
with a comparatively high concentration of organic compounds the addition of PAC will result in its
elimination. It has been found that the concentration of PAC in the recirculation node should not
exceed 600 mg/dm3, although other researchers in France indicated that higher concentrations might be
used [12]. The proper choice of the PAC particle size depends, first of all, on the effectiveness of
adsorption and the possibility of clogging the capillaries (not the pores) of the membrane, particularly
in the case of the module with a flow from the inside to the outside of the capillaries. The PAC
particles should not be too big, so that they would not plug the clearance of the capillaries; their
diameter should not exceed 1/5 of the diameter of the capillary [12].
The advantages of integrated PAC/UF processes comprise [12-14]:

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- a considerable reliability of the process, warranting the production of water of the required quality,
independently of change in the composition of raw water,
- the restriction of fouling of the membranes, because contaminations are adsorbed on PAC,
- more favorable conditions of operation than in the case of applying GAC filters.
The application of the PAC/UF process making use of capillary “Aquasource” modules is widely
known in the industry producing potable water under the name CRISTAL process [12-14]. A number
of installations for the treatment of underground and surface water with efficiency from 200 to 65000
m3/d have been operating since 1993. Such as process permits to eliminate from the treated water
chlorinated organic compounds, pesticides, turbidity, taste and smell (T&O), which the classical
method of water treatment, applied previous of modernization did not warrant.
Some other researches were carried out investigations for comparisons of hybrid systems
adsorption on PAC-UF/MF with UF/MF alone [15,16].

3. Hybrid process with biological filtration and UF/MF

A higher degree of eliminating organic substances in the production of potable water can be
achieved by combining the filtration on a biologically active bed with membrane filtration [17].
Principally, in this case two configurations are to be taken into account, differing from each other by
the sequence of both these processes. Table 3 presents the drawbacks and advantages of these
configurations of the process [17].

Table 3. Comparison of the advantages and disadvantages of hybrid biofiltration and membrane filtration processes
(TOC – total organic carbon, DOC – dissolved organic carbon)
Advantages of the process Restriction of the process
Biofiltration – membrane filtration
 Elimination of organic substances before  A biological filter requires frequent rinsing in
UF/MF minimizes the adsorption fouling of the the case of waters with a high turbidity and
membrane containing organics
 The membrane is a barrier for micro-  In water with a low content of TOC there
organisms occurring in raw water and in the may occur a deficiency of biogenic substances in
effluent from biological filtration the biological filter
Membrane filtration – biofiltration
 The membrane eliminates dispersed  A penetration of microorganisms into the
substances, turbidity and a part of TOC; biological treated water is possible
filtration removes DOC  The membrane must be frequently washing

4. Oxidation – ultrafiltration/microfiltration processes

Besides coagulation and adsorption on activated carbon, ozonization is applied for the treatment of
potable water. Therefore, investigation is being run concerning the influence of ozone onto
improvement of the efficiency of membrane processes [18-21]. The purpose of ozone is to decrease of
membrane fouling and life-time as well as quality of produced water [18,19]. If preliminary
ozonization is applied, the permeate flux increases from 20% to more than 90% depending on
membranes compactness, in comparison with the flux determined for deionized water [18]. Thus, a
continuous addition of ozone permits to control effectively the fouling of UF and MF membranes.
An interesting options of the application of ozone in membrane filtration is the washing the
capillary module with gaseous ozone in order to protect the membrane fouling [2,19]. The modules are
immersed in water, to which ozone is passed with a concentration of 0.043 mg O3/l [2] and 0.2-0.3 mg

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O3/l [19]. Ozone batched in small concentration of 0.2 to 0.3 mg/l forms microscopically charged
bubbles, which may play the role of coagulants for the hydrophobic organic substances contained in
the water. It is to be supposed that the destruction of microorganisms by the ozone and the prevention
of the development of bacteria are the main reason of the reduction of fouling. The decrease of the
amount of heterotrophic bacteria was found to drop from 3.5·103/100 ml in water without rinsing with
ozone to 5·10/100 ml in tests were ozone was applied [2].
Schlichter, Mavrov and Chmiel [20] carried out pilot investigations of a technology including
membrane filtration and adsorption on granulated activated carbon in order to obtain potable water
from rivers. During the first stage ozone was dosed in amounts of 1.7 – 2.8 and 4.5 mg O3/mg TOC,
followed by filtering through multi-channel ceramic MF (0.1 µm) and UF (20 kDa) membranes, and
the obtained permeate was passed to a column with activated carbon. The results proved that the
residual concentration of the ozone (about 0.05 mg O3/l ) in the permeate warrant a constant efficiency
of MF or UF processes, practically without having to apply back-flushing. Physicochemical analyses
have shown that in result of purification the concentration of organic compounds in the water may be
reduced to a level below that required by regulations.
Mozia, Tomaszewska and Morawski [21] investigated the influence of preliminary ozonization on
ultrafiltration process (UF) and UF aided by adsorption on PAC (PAC/UF). The poorest effect of
treatment was attained in the process of direct UF, because the concentration of TOC was reduced by
about 79 %, and the UV absorbance (254 nm) by about 91 % [21]. The introduction of PAC into the
system improved the effectiveness of purification, because TOC was decreased by about 98 % and the
UV absorbance (254 nm) in the permeate achieved a value equal to zero. Good effects have also been
obtained by combining UF with preliminary ozonization (TOC decreased by about 96 % and the
absorbance of UV 254 nm was also reduced to zero). The best effects were to be observed when
preliminary ozonization was applied in the PAC/UF system – both of the analyzed indices were equal
to zero.

5. Membrane bioreactors – removal of nitrates

For the purpose of potable water treatment it has been suggested to apply membrane bioreactors to
denitrify the water as an alternative of biodegradation and filtration on sand beds or adsorption on
activated carbon [2,22]. In the bioreactor an oxygen-free reduction of nitrates to gaseous nitrogen takes
place, and the UF/MF processes retain the biomass suspension as well as other contaminations. If the
pore sizes are adequately chosen and do not exceed the size of the bacteria cells, these latter can be
retained completely in the reactor. In result, the reactor can operate at a higher retention time without
washing out the cells [22] and thus permits to attain a considerable degree of elimination of the
nitrates.
Bohdziewicz and Wasik [23] investigated comprehensively the denitrification of underground
water in membrane bioreactors. A 60 % reduction of the permeate flux was observed when the volume
of the treated water was reduced tenfold and the obtained permeate was free of nitrates.
Microbiological and sanitary-epidemic tests of the permeate excluded the presence of bacteria
Escherichia coli, coli-like bacteria as well as pathogenetic bacteria. Therefore, treated water did not
have to be subjected to any further disinfection and could be used for alimentary and household
purposes [23].
New conceptions of biological denitrification in membrane bioreactors aim at extractive MBR
(membrane contactors), eliminating the restrictions of conventional systems [24,25]. Water polluted by
nitrates flows through tubular membranes, whereas the population of denitrified bacteria as well as the

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nutrient medium and the electron donor circulate outside the membrane providing appropriate biogenic
elements required for the development of microorganisms. Under such conditions NO3 is transported at
a high rate through the pores of the membrane; simultaneously, thanks to the presence of the porous
membrane, the microbiological process is separated from the water subjected to purification. Such a
solution prevents the danger of contaminating the water with microorganisms. In order to eliminate the
application of an organic substrate and the possibility of polluting the produced water, autotrophic
bacteria are employed in the process of denitrification [25]. The most popular autotrophic system is the
application of sulphur compounds or gaseous hydrogen as electron donors as well as carbonates (or
carbon dioxide)/ as sources of carbon [25].

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