DESALINATION

ELSEVIER Desalination 146 (2002) 141-147

www.elsevier.com/locate/desal

Characterisation and modelling of fouling

in membrane bioreactors

S. Ognier*, C. Wisniewski, A. Grasmick

Laborutoire Genie des Procedes de Montpellier 2, CC 024, Place Eugene Bataillon 34095 Montpellier Cedex 05 France
Tel. +33 (4) 67 14 48 54; Fax +33 (4) 67 14 48 54; emails: ognier@crit.univ-montp2.fn
wisniews@crit.univ-montp2.fr grasmick@crit.univ-montp2.fr

Received 7 February 2002; accepted 6 March 2002

Abstract

A membrane bioreactor used for denitrification of a synthetic substrate was studied in term of membrane fouling.
For standard pH and temperature conditions, subcritical conditions were defined to ensure the process stability. The
stepwise method was used to determine the critical flux for the deposition of colloidal particles. Under standard
physicochemical conditions, only a low and constant fouling resistance was observed if the permeate flux was
maintained below the critical flux. The influence of physicochemical variations was then investigated by varying pH
and temperature in the biological reactor. It was observed that, when the pH value was higher than a critical one, the
membrane was rapidly fouled. This maximum admissible pH value decreased when the temperature increased. On
analysing the reversible nature of fouling and the variations of ionic concentrations with the pH, the role of carbonate
calcium precipitation was pointed out. By using classical filtration models, it was shown that the fouling mechanism
could be the deposition of CaCO, particles formed in the bulk suspension by bulk crystallisation.

Keywords: Membrane bioreactor; Membrane fouling; Subcritical regime; Precipitation

1. Introduction deposits from building up on the membrane

surface [ 11. However, the membrane permeability
Critical flux is an interesting notion to define
can decrease during the operation due to the
optimal hydrodynamic conditions; subcritical
interactions between soluble compounds and
conditions can be defined to avoid macroscopic
membrane material, which do not depend on
*Corresponding author. hydrodynamic conditions. Therefore, the stability

Presented ut the International Congress on Membranes and Membrane Processes (ICOM), Toulouse, France,
July 7-l 2, 2002.

001 l-91 64/02/$- See front matter 0 2002 Elsevier Science B.V. All rights reserved
PII: SO0 II-9 164(02)00508-8
142 S. Ognier et al. /Desalination
of the system depends not only on hydrodynamic
conditions but also on biological and physico-
chemical suspension properties, and it is of
utmost importance to define subcritical hydro-
dynamic conditions as well as physico-chemical
and biological conditions to obtain a stable filtration
regime. In these conditions, long filtration periods
without having to use chemical cleaning pro-
cedures can be obtained. Fan et al. [2] showed
that a membrane bioreactor (MBR) system for
the treatment of raw municipal wastewater can
be run continually over 70 d with a stable trans-
membrane pressure.
However, the biological and physico-chemical
properties of the suspension are not always stable
due to influent composition or temperature changes.
As these variations are weak, they are not always
taken into account when defining the operating
conditions. Therefore, subcritical conditions are
generally defined experimentally in fixed biological
and physicochemical conditions. Based on these
considerations, the objective of this work was (i)
to ensure that stable filtration conditions could
be obtained in an MBR under constant hydro-
dynamic, biological and physico-chemical con-
ditions and (ii) to study the influence of weak
variations of two physicochemical parameters
(pH and temperature) on process stability. The
fouling phenomena were analysed by using classical
filtration models.
2. Experimental
2.1. Membrane bioreactor
Experiments were conducted on a pilot MBR,
which consisted of a 20-l bioreactor tank and a
ceramic ultrafiltration membrane module
(Membralox@) having a 0.24-m* surface area and
a mean pore size of 0.05 pm and a resistance of
5x10” m-l. The recirculated pump integrated to
the system ensured the perfect mixing of the
reactor and made the retentate circulate with a
I .6 m/s tangential velocity in the membrane
module, corresponding to a wall shear stress of
146 (2002) 141-147
13 Pa. A cooling system kept the whole system
at a constant temperature of 25?1 “C. A constant
permeation flux was maintained by using a
suction pump (Watson-Marlow 505 RS).
2.2. Denitrifcation process
The system worked in denitrification of a
synthetic substrate. The biodenitrification was
realised by an activated sludge, mixed culture,
taken from the aeration tank from the municipal
wastewater treatment plant in Montpellier
(France) and acclimated to the synthetic substrate
used in the experiments. The synthetic substrate
was prepared by diluting potassium nitrate and
ethanol in tap water so that the concentrations
were 200 mg,,,/l and 1000 mg,n/l, respectively.
In these conditions, the ratio COD/N was equal
to 5. (NH,),HPO, was also added so that COD/P
= 150.
The reaction of denitrification can be written
as follows:
SCH,CH,OH + 12 NO;+ 10 HCO,- + 6 N,
+ 9 H,O + 2 CO,
Hydroxide and hydrogenocarbonate ions are
metabolically produced by the reaction of
denitrification. In theory, the increase of alkalinity
is equal to 3.6 mg CaCO3/mg N-NO,--N denitrified.
The bioreactor pH value could increase to 8.5 or
more when no acidic solution was added to the
substrate (consequently, chlorydic acid was added
to the substrate to maintain the pH value between
7.5 and 8).
By keeping the biological parameters (hydraulic
retention time, sludge retention time, organic
loading) constant, the biomass concentration was
stable, equal to a constant value of 1.5 g&l. Table 1
presents the main biological characteristics of the
system.
2.3. Fouling characterisation
TMP evolution was monitored in the MBR
by recording data of pressure transducers P,, P,
 S. Ognier et al. /Desalination 146 (2002) 141-147 143

Table I l Acidic cleaning. Last, the membrane was

Biological conditions chemically cleaned with a slightly diluted
solution of nitric acid (HNO,) at room temp-
Volumetric loading rate, gcoD/lld 3
erature.
Hydraulic retention time, h 8
Sludge retention time, d 3.5
l Complete chemical cleaning. To restore the
Specific denitrification rate, gNlgv&d 0.4 initial permeability of the membrane, a
0.2 complete chemical cleaning was done. An
Yield, g&gco,
Biomass concentration, g&l 1.5 alkaline solution (diluted hydroxide sodium
solution) and then an acid solution (diluted
nitric acid solution) were filtered at 60°C.

and P,. P, and P, are the pressures of the retentate

measured at the input and the output of the
membrane module and P, is the pressure on the
permeate side. During the filtration operation, P,
and P, are constant and P, decreases due to mem-
brane fouling. TMP was calculated by the relation:
To characterise the nature of the fouling,
several cleaning methods were tested: intermittent
filtration, forward flush with water, back flush
with water and slight acid cleaning. Except for
the intermittent filtration, the membrane resistance
to a water permeation was determined after each
cleaning method. TMP was measured when
filtering pure water at lo,20 and 30 l.m-*.h-‘.The
tangential velocity was the one used during the
filtration operation. Details of the different methods
in chronological order of their applications are
as follows:
l Intermittent filtration. The suction pump was
switched off for approximately 10 min, then
the filtration operation was reinitiated. During
the intermittent filtration, the recirculation
pump continued to make the retentate circulate.
l Forward flush. The filtration ws stopped
when the reactor was filled up with pure water.
Then, the water was recirculated for 10 min
without filtering.
l Back flush. Pure water was filtered in the
opposite direction of the normal filtration
operation with a TMP of 0.5 bar.
3. Results and discussion
3. I. Definition of operating conditions ensuring
process stability
The operating conditions of the MBR were
defined under “standard” conditions of pH and
temperature, that is to say, a pH value between
7.5 and 8 and a temperature equal to 25kl”C. The
objective of this preliminary study was to define
hydro-dynamic conditions where no deposition
of colloidal particles on the membrane occurred.
Therefore, the increase of membrane resistance
is controlled and a stable regime should be
obtained. In theory, such conditions are possible
when the permeate flux is inferior to the critical
flux value.
To determinate the critical flux value in the MBR,
the stepwise method was used. The permeate flux
was stepwise increased with a step length of
30 min. Below the critical flux value, the TMP
stabilised rapidly after each flux increase, and the
stabilised value of TMP increased linearly with
the flux imposed. Above the critical flux value,
this linear relationship did not apply any more due
to a deposition phenomenon. Fig. 1 shows the TMP
measured for each flux value. The subcritical regime
corresponds to the first part of the curve where the
resistance stays constant (2x10’* m-l) for permeate
flux values below 38 l.m-*.h-‘. This resistance
differed from the clean membrane one due to an
instantaneous fouling phenomenon taking place
at the very beginning of the filtration. Above
38 l.m-2.h-‘, the fouling resistance increased
 S. Ognier et al. /Desalination 146 (2002) 141-147
Fig. I. Flux of permeate vs. TMI?
dramatically, indicating that the filtration regime
was supracritical.
Considering these results, it could be concluded
that a 10 l.m-*.h-’ value for the permeate flux, less
than the critical value, would ensure the process
stability. However, the results obtained with the
stepwise method did not mean that there was no
membrane fouling when the flux of permeate was
below the critical value. Actually, a slow fouling
phenomenon could not necessarily be observed
with the stepwise method due to the relatively
short duration of the steps and the precision of
the measurements.
To ensure that the conditions were stable under
standard conditions of pH and temperature, long-
term experiments were conducted. During the
whole filtration run (5 weeks), the fouling rate was
very low, with an increasing rate of the resistance
below 10” m-‘.d-’ (less than 0.003 bar/d). But this
resistance proved to be irreversible as neither a
forward flush, nor a back flush were efficient.
So, a permeate flux value of 10 l.m-2.h-1 allowed
a stable fouling regime.
3.2. Analysis of the influence of physicochemical
conditions on process stability
In the range of pH values tested, it is reported
in literature that the biological activity does not
undergo significant changes [3]. Similar results
were obtained in the present srudy since VSS
concentration, soluble COD concentration and
removal efficiencies stayed almost constant for
all the physicochemical conditions tested.
To study the influence of pH on process stability,
the pH value in the bioreactor was allowed to vary
between 7.5 and 9. This was done by adjusting
the substrate pH value to different values (the
added volume of chlorydric acid changed). It was
observed that, when the value of the pH increased
too much, a continuous increase of the TMP could
be observed. This phenomenon is illustrated in
Fig. 2 where the TMP evolution is shown with time
and with pH variations. In this experiment, the
temperature was equal to 25kl”C. Continuous
increases of the TMP can be observed; these are
numbered on the graph from 1 to 4. These TMP
always increases corresponded to pH values
greater than 8.5. However, if the suspension pH
was decreased by acidifying the substrate, the
system could become stable again and the fouling
was partly removed.
Additional experiments were conducted to
study the effect of temperature that was varied
from 22 to 32°C by adjusting the cooling system.
As mentioned previously, TMP increases were
observed when the pH values were shown to depend
on temperature (Fig. 3): for high temperatures,
the fouling occurred for pH values inferior to
those for low temperatures.
To chatacterise the phenomenon leading to these
rapid TMP increase, the nature of the fouling
resistance was investigated by testing several
-9
I,
8
Fig. 2. Influence of pH increases on TARPevolution.
 S. Ognier et al. /Desalination 146 (2002) 141-147 145

obtained after acid cleaning: in both cases, acid

cleaning proved to be very efficient in removing
the fouling resistance that remained after the
forward flush.
The irreversible fouling can be of organic (bio-
film, metabolites, etc.) or inorganic (precipitated
salts) nature. Alkaline cleaners are generally
considered as the most effective against biofilms
and organic foulants whereas acidic cleaning is
I

required to ensure the removal of inorganic preci-

15 17 19 21 23 25 27 29 31 33 35

Temperature
Fig. 3. Influence of temperature on critical pH value.
cleaning methods. Two experiments were con-
ducted: (1) Case A was initiated during an intensive
fouling phase, (2) Case B was done at the end of
the filtration run presented in Fig. 2, when the
process was stabilised again (t = 575 h). The results
are presented in Table 2.
As shown by these results, filtration resting is
totally ineffective in removing the fouling
resistance in both cases. This result signifies that
the fouling mechanism is not the formation of a
reversible deposit on the membrane surface.
However, in the first case, half of the fouling
resistance can be eliminated by the forward flush.
As the cleaning methods of filtration resting and
forward flush differ only in the use of water (the
hydrodynamic conditions are identical), the
cleaning efficiency of the forward flush points
out once again the crucial role of physicochemical
conditions. The forward flush effectiveness could
be due to the use of water with a neutral pH value.
The importance of the pH value in fouling removal
had been already noticed during the experiments.
This result was confirmed by the resistance values
(“C)
pitants [4]. Therefore, the effectiveness of the
acidic cleaning indicates that the fouling could
be mainly due to precipitation phenomena. The
continuous fouling increase observed is not in
disagreement with this hypothesis. Actually, if
precipitation can be instantaneous, the continuous
feed of hard tap water and the biological reaction
can induce continuously a salt precipitation as long
as the suspension pH is beyond the critical value
for precipitation.
To determine the nature of the precipitants,
the influence of pH on the suspension composition
was analysed. When the pH was increased, only
hydroxide ions (OH-) and carbonate ions (CO:-)
concentrations were increased. Therefore, the pre-
cipitation was supposed to depend on the concen-
trations of hydroxide and/or carbonate ions. As the
substrate was prepared with hard tap water (Ca2+=
120 mg/l and Mg*+ = 8 mg/l), the reaction quotient
was compared with the solubility product for the
main hydroxide and carbonate precipitates involving
calcium and magnesium ions. Table 3 presents
the solubility product at 25°C the reaction quotient
calculated at pH 9 with the calcium and magnesium
concentrations in the tap water used for the substrate.
These calculations indicate that two inorganic
crystals, CaCO, and Mg(OH),, can precipitate

Table 2
Membrane resistance values obtained after the different cleaning methods tested (m-l)

Before intermittent After intermittent After forward flush After back flush After acidic
filtration filtration cleaning
Case A 20x10” 20x10” 10x10’* 8.6x10’* 1.9x10’*
Case B 9x1012 9x1012 6.5. lOI 6.5~10’~ 1.8x1o’2
146 S. Ognier et al. /Desalination 146 (2002) 141-147

Table 3
Solubility products at 25°C and reaction quotient calculated at pH 9

Before intermittent After intermittent After forward flush After back flush After acidic
filtration filtration cleaning
Case A 20x1 012 2ox10’2 1ox1o’2 86x10’* 1.9x10t2
Case B 9x1012 9x1012 6.5.10’* 6.5~10’~ 1.8~10’~

when the pH value exceedes 9. In the case of of a deposition due to bulk crystallisation cannot
CaCO, precipitation, the theoretical “critical” pH be eliminated. Actually, heterogeneous crystal-
value is given by the relation where KS is the lisation could take place on the mineral deposit
solubility product of CaCO, and K3 the constant present on the membrane and therefore induce
. .
dissociation of HCO,-: chemical binding between particles. It was reported
elsewhere that a cake of CaCO, particles can be
pH,,.,, = -log [[ Ca ‘+]x [HCO;]x+‘j irreversible due to the cohesive properties of the
s particles [5].
To further investigate the fouling mechanism,
Contrary to other common precipitates, CaCO,
the intensive fouling phases numbered 1,2,3 and
is characterised by the decrease of its solubility
4 were analysed by using usual filtration models:
when the temperature is increased. So, in the case
standard blocking law, complete blocking law,
of CaCO,, the value of pHc,,, decreases when the
intermediate blocking law and cake filtration law
temperature is increased. This decrease of pHo,,
[6]. At first, these models have been developed
related with the temperature could not be observed
for frontal filtration mode: back-transport forces
with the other salts present in the suspension. It
are not taken into consideration. The results
can be therefore concluded that the decrease of
obtained for the first fouling phase are presented
the pH value corresponding to the strong increase
in Table 4.
of TMP when the temperature is increased, is in
Except for the complete blocking law (the
favour of CaCO, precipitation.
hypothesis of this mode1 are generally reported
There are two ways to explain the resistance
as too restrictive), it is shown that the models fit
increase due to the CaCO, formation: (i) the
the experimental data quite well. This result is
crystal particles are formed in the bulk phase (bulk
coherent with the building up of an irreversible
crystallisation) and deposit on the membrane or
deposit: no particles back-transport is possible
(ii) the crystal grows on the surface of the membrane
due to the severe particles adhesion, so the models
material (heterogeneous crystallisation). Even if
apply satisfactorily. However, one can note that
the hydrodynamic cleaning methods of intermittent
the agreement is much better when the cake
filtration and back flush proved to be inefficient
filtration and the intermediate blocking law are
to remove the fouling resistance, the hypothesis

Table 4
Analysis of 1st fouling phase by using usual filtration laws

Standard blocking Complete blocking Intermediate blocking Cake filtration

law law law law
Linear relation Rm”*vs. V R-’ vs. V InR vs. v R vs. V
Correlation coefficient 0.963 0.918 0.990 0.983
 S. Ognier et al. /Desalination
considered. Considering that better fittings are
obtained with models describing an external
fouling mechanism, the fouling would be located
at the pore entrance or on the membrane surface
rather than in the whole membrane matrix. This
result allows one to think that the fouling could
be caused by the deposition of CaCO, particles
formed in the bulk suspension (bulk crystallisation)
on the membrane surface. Actually, a pore con-
striction mechanism should have been obtained
with heterogeneous crystallisation. However, it
is of course difficult to base conclusions on the
only use of the models and further research would
be necessary to confirm this hypothesis.
4. Conclusions
An MBR for denitrification was studied in
terms of process stability. Unusual membrane
fouling in an MBR system was investigated. The
following conclusions could be drawn:
l In an MBR for denitrification, the great alkalinity
of the suspension can cause the precipitation
of calcium carbonate for pH values between
8 and 9.
l The role of precipitation can be pointed out as a
cause of system instability, even if the system
works in subcritical conditions.
146 (2002) 141-147 147
l The fouling mechanism could be the deposition
of CaCO, particles formed in the bulk suspension
by bulk crystallisation. Further research would
be necessary to confirm this hypothesis.
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Grasmick and C. Gavach, Denitrification of drinking
water by the association of an electrodialysis and a
membrane bioreactor: feasability and application,
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[3] X.-J. Fan, V. Urbain, Y. Qian and J. Manem, Ultra-
filtration of activated sludge with ceramic membranes
in a cross-flow membrane bioreactor process, Water
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