Process Biochemistry 39 (2004) 599–613

Biosorption of phenol by immobilized activated sludge in a

continuous packed bed: prediction of breakthrough curves
Zümriye Aksu∗ , Ferda Gönen
Chemical Engineering Department, Hacettepe University, 06532 Beytepe, Ankara, Turkey

Received 14 February 2003; accepted 6 April 2003

Abstract

A continuous fixed bed study was carried out by using Mowital® B30H resin immobilized dried activated sludge as a biosorbent for the
removal of phenol from aqueous solution. The effect of flow rate and inlet phenol concentration on the sorption characteristics of sorbent was
investigated at pH 1.0. Data confirmed that the total amount of sorbed phenol and equilibrium phenol uptake decreased with increasing flow
rate and increased with increasing inlet phenol concentration. Freundlich and Langmuir adsorption models have been used to represent the
column equilibrium data. The results showed that the equilibrium data fitted both models within the concentration range studied. Four kinetic
models; Adams–Bohart, Thomas, Clark and Yoon–Nelson models were applied to experimental data to predict the breakthrough curves and
to determine the characteristic parameters of the column useful for process design. All models were found suitable for describing the whole
or a definite part of the dynamic behavior of the column with respect to flow rate and inlet phenol concentration.
© 2003 Elsevier Ltd. All rights reserved.

Keywords: Biosorption; Phenol; Immobilized activated sludge; Packed bed column; Breakthrough curve

1. Introduction chemicals, which becomes impracticable and uneconomi-

Phenolics are present in different concentrations in
wastewaters of industries such as coal conversion, coke
preparation, synthetic rubber, pesticide, insecticide,
petroleum refineries, pulp and paper, plastic, textile, dye,
polymeric resin, pharmaceuticals, wood, etc. [1]. Phenol and
phenolic compounds are among the most common organic
pollutants of wastewaters that require careful treatment be-
fore being discharged into the receiving body of waters. It
should be noted that the contamination of drinking water
by phenolics at even a concentration of 1 mg l−1 could
bring about significant taste and odor problems making it
unfit for use. Phenol becomes chlorophenols if chlorination
is used to disinfect phenol-containing waters. Traditionally,
biological degradation, activated carbon adsorption, solvent
extraction and chemical oxidation are the most widely used
methods for removing phenols and its derivatives from
wastewaters [2–5]. Application of such traditional treatment
techniques needs enormous cost and continuous input of
∗ Corresponding author. Tel.: +90-312-297-7434;
fax: +90-312-299-2124.
E-mail address: zaksu@hacettepe.edu.tr (Z. Aksu).
cal and causes further environment damage. Hence, easy,
effective, economic and ecofriendly techniques are required
for fine tuning of effluent/wastewater treatment.
The search for a low cost and easily available adsorbent
has led to the investigation of materials of agricultural and
biological origin, along with industrial by-products, as ad-
sorbents. Microorganisms such as bacteria, fungi, yeast and
algae can remove some pollutants from aqueous solutions
and this biological phenomenon is called biosorption. This
term is used to indicate a number of metabolism-independent
processes (physical and chemical adsorption, ion exchange,
complexation, chelation and microprecipitation) taking
place essentially in the cell wall. The main attraction of
biosorption are cost effectiveness and good removal perfor-
mance; raw materials which are either abundant (sea weeds)
or wastes from other industrial operations (fermentation
wastes, activated sludge process wastes) can be used as
biosorbents presenting performances often comparable with
those of ion exchange resins. The mechanism of binding by
inactivated biomass may depend on the chemical nature of
pollutant (species, size, ionic charge), type of biomass, its
preparation and its specific surface properties and environ-
mental conditions (pH, temperature, ionic strength, existence

0032-9592/$ – see front matter © 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S0032-9592(03)00132-8
600 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613

Nomenclature
A constant in the Clark model
B Langmuir adsorption constant (l mg−1 )
Cb bulk phenol concentration in the solution in the column (mg l−1 )
Co inlet (feed) or initial phenol concentration (mg l−1 )
C effluent phenol concentration (mg l−1 )
Cad ( = Co −C) adsorbed phenol concentration in the column (mg l−1 )
Cbreak outlet phenol concentration at breakthrough (or limit effluent concentration) (mg l−1 )
Ceq nonadsorbed phenol concentration at equilibrium in the column (mg l−1 )
Cs phenol concentration at the solid/liquid interface in the column (mg l−1 )
D, E axial diffusion or dispersion coefficient (cm2 min−1 )
kAB kinetic constant in the Adams–Bohart model (l mg−1 min−1 )
kTh kinetic constant in the Thomas model (ml mg−1 min−1 )
kYN kinetic constant in the Yoon and Nelson model (l min−1 )
K mass transfer coefficient in the Clark model (min−1 )
KF Freundlich adsorption constant [(mg g−1 )(mg l−1 )n ]
n Freundlich adsorption constant
No saturation concentration in the Adams–Bohart model (mg l−1 )
mtotal total amount of phenol sent to column (mg)
q phenol concentration in the solid phase in the column at any time (mg l−1 )
qeq equilibrium phenol uptake per g of biosorbent in the column or in the batch system (mg g−1 )
qtotal total adsorbed quantity of phenol in the column (mg)
qo ( = qeq ) constant in the Thomas model (mg g−1 )
Q flow rate (ml min−1 )
Q◦ Langmuir constant (mg g−1 )
r adsorption rate (mg l−1 min−1 )
R constant in the Clark model (min−1 )
t flow time (min)
tbreak time at breakthrough (min)
ttotal total flow time (min)
Uo superficial velocity (cm min−1 )
Veff effluent volume (ml)
X amount of sorbent in the column (g) or sorbent concentration in the batch system (g l−1 )
Z height of the column (cm)
␤a kinetic coefficient of the external mass transfer in the Wolborska model (min−1 )
ε void fraction in the bed
␯ migration rate (cm min−1 )
␶ time required for 50% adsorbate breakthrough (min)

of competing organic or inorganic ligands in solution). As
hydrophobic organic pollutants show a high tendency to
accumulate onto microbial cells or sludge, the microbial
biomass could be used as an adsorbent of biological origin
for the removal of very low concentration hazardous organics
from the wastewater. For all these reasons biosorption can be
considered a promising technology for phenol removal from
industrial waste streams and polluted natural waters [6–10].
Both living and dead biomass can be used to remove haz-
ardous organics, but maintaining a viable biomass during
adsorption is difficult, because it requires a continuous sup-
ply of nutrients and avoidance of organic toxicity to the mi-
croorganisms. The use of dead microbial cells in biosorption
is more advantageous for water treatment in that dead or-
ganisms are not affected by toxic wastes, they do not require
a continuous supply of nutrients and they can be regener-
ated and reused for many cycles. However, the use of dead
biomass in powdered form has some problems, such as dif-
ficulty in the separation of biomass after biosorption, mass
loss after regeneration and low strength and small particle
size, which make it difficult to use in column applications.
To solve these problems, dead biomass can be immobilized
in a biopolymeric or polymeric matrix used as a support-
ing material. Immobilization may improve biomass perfor-
mance, biosorption capacity, increase mechanical strength
and facilitate separation of biomass from pollutant-bearing
solution. Immobilization also allows higher biomass con-
centration, resistance to chemical environments and column
 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613
operations and immobilized systems may be well suited for
non-destructive recovery. Indeed, the use of immobilized
biomass has a number of major disadvantages. In addition
to increasing the cost of biomass pre-treatment, immobiliza-
tion adversely affects the mass transfer kinetics of phenol
uptake. When biomass is immobilized the number of bind-
ing sites easily accessible to pollutant in solution is greatly
reduced since the majority of sites will lie within the bead.
So a good support material used for immobilization should
be rigid, chemically inert and cheap, should bind cells firmly,
should have high loading capacity and should have a loose
structure for overcoming diffusion limitations [11,12].
For continuous operation with immobilized biomass, the
most convenient configuration is that of a packed column,
much like that used for ion exchange. A packed bed column
is an effective process for cyclic sorption/desorption, as it
makes the best use of the concentration difference known to
be a driving force for adsorption and allows more efficient
utilization of the sorbent capacity and results in a better qual-
ity of the effluent. Continuous packed bed sorption has also
a number of process engineering advantages including high
yield operations and relatively easy scaling up from a labo-
ratory scale procedure. The stages in the separation protocol
can also be automated and high degrees of purification can
often be achieved in a single step process. A large volume
of wastewater can be continuously treated using a defined
quantity of sorbent in the column. Reuse of microorganism
is also possible. After pollutant loading the pollutant may
be concentrated in a small volume of solid material or des-
orbed into a small volume of eluant for recovery, disposal
or containment [8,11,12].
Activated sludge is a well known biomass used for
the purification of some industrial effluents and domestic
wastes. Part of the microorganisms over grown in such
wastewater systems can be separated and utilized for re-
moval of phenol as an abundant and cheaper biosorbent.
Activated sludge from wastewater systems contains both
bacteria and protozoa. The cell wall of bacteria essentially
consists of various organic compounds such as carboxyl,
acidic polysaccharides, lipids, amino acids and other com-
ponents. The protozoa are unicellular, motile, relatively
large eucaryotic cells that lack cell walls. They can absorb
components through their outer membranes that contain
proteins and lipids [6,7,9,11].
Mowital® B30H resin (a polyvinyl butyral based polymer)
is a well known polymer used extensively in painting and
coating industries. While it is abundant, extremely cheap
than other immobilizing agents, non toxic and chemically
inert, more suitable for preparation of porous beads, the solid
and rigid support, showing little change in volume under any
conditions, with dimensional stability under pressure, pro-
duced in the desired size and thus highly competitive with
ion exchange resins and activated carbon so it can be used
for immobilization of microorganisms for biosorption [11].
Activated sludge has been immobilized in Mowital® B30H
resin in order to produce a biosorbent material with proper
601
characteristics for use in typical chemical engineering oper-
ations such as fixed beds. It has been used to demonstrate
the potential for removal of phenol from waste streams in
a continuous packed bed column as a function of flow rate
and inlet phenol concentration. The column phenol sorption
equilibrium has been described by the use of Langmuir and
Freundlich models. Several kinetic models are also applied
to experimental data to simulate the breakthrough curves in
order to predict the scale-up of a unit plant. To our knowl-
edge, this is the first attempt to immobilize a biomass in
Mowital® B30H resin in a fixed column and to test its use
as an biosorbent for the removal of phenol.
2. Mathematical description
The performance of packed beds is described through
the concept of the breakthrough curve. The time for break-
through appearance and the shape of the breakthrough curve
are very important characteristics for determining the opera-
tion and the dynamic response of a biosorption column. The
general position of the breakthrough curve along the volume
axis depends on the capacity of the column with respect to
the feed concentration and flow rate. The breakthrough curve
would be a step function for favorable separations, i.e. there
would be an instantaneous jump in the effluent concentra-
tion from zero to the feed concentration at the moment the
column capacity is reached [8,11–19].
The breakthrough curves show the loading behavior of
phenol to be removed from solution in a fixed bed and is
usually expressed in terms of adsorbed phenol concentration
(Cad = inlet phenol concentration(Co )−Outlet phenol con-
centration (C)) or normalized concentration defined as the
ratio of effluent phenol concentration to inlet phenol con-
centration (C/Co ) as a function of time or volume of effluent
for a given bed height [11]. Effluent volume (Veff ) can be
calculated from Eq. (1).
Veff = Qttotal (1)
where ttotal and Q are the total flow time (min) and volumet-
ric flow rate (ml min−1 ). The area under the breakthrough
curve (A) obtained by integrating the adsorbed concentra-
tion (Cad ; mg l−1 ) versus t (min) plot can be used to find the
total adsorbed phenol quantity (maximum column capacity).
Total adsorbed phenol quantity (qtotal ; mg) in the column for
a given feed concentration and flow rate is calculated from
Eq. (2):

t=ttotal
QA Q
qtotal = = Cad dt (2)
1000 1000 t=0
Total amount of phenol sent to column (mtotal ) is calcu-
lated from Eq. (3).
Co Qttotal
mtotal = (3)
1000
602 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613
Total removal percent of phenol (Column performance)
with respect to flow volume can be also found from the
ratio of total adsorbed quantity of phenol (qtotal ) to the total
amount of phenol sent to column (mtotal ) Eq. (4).
qtotal
Total removal % = × 100
mtotal
Adsorption is also a well-known equilibrium separation
process for wastewater treatment. Equilibrium studies on ad-
sorption give information about the capacity of the sorbent
or the amount required to remove a unit mass of pollutant
under the system conditions. As the adsorption isotherms
obtained from sorption data in a batch system are not able
to represent the column equilibrium, the experimental data
from the column experiments should be used to fit isotherm
models. Equilibrium phenol uptake (qeq ) (or maximum ca-
pacity of the column) in the column is defined by Eq. (5) as
the total amount of phenol sorbed (qtotal ) per g of sorbent
(X) at the end of total flow time.
qtotal
qeq = (5)
X
Unadsorbed phenol concentration at equilibrium in the
column (Ceq ; mg l−1 ) can be defined by Eq. (6):
mtotal − qtotal
Ceq = × 1000
Veff
The most widely used isotherm equation for modeling
the equilibrium is the Langmuir equation, which is, valid
for monolayer sorption on to a surface a finite number of
identical sites and is given by Eq. (7).
Q◦ bCeq
qeq =
1 + bCeq
where Q◦ is the maximum amount of the phenol per unit
weight of dried activated sludge to form a complete mono-
layer on the surface bound at high Ceq ; and b is a constant
related to the affinity of the binding sites. Q◦ represents a
practical limiting adsorption capacity when the surface is
fully covered with phenol and assists in the comparison of
adsorption performance, particularly in cases where the sor-
bent did not reach its full saturation in experiments. Q◦ and
b can be determined from the linear plot of Ceq /qeq versus
Ceq .
The empirical Freundlich equation based on sorption on
a heterogeneous surface is given below by Eq. (8).
qeq = KF Ceq
1/n
where KF and n are the Freundlich constants characteristic
on the system. KF and n are indicators of adsorption capacity
and adsorption intensity, respectively. Equation (8) can be
linearized in logarithmic form and Freundlich constants can
be determined. According to the Freundlich equation, the
amount adsorbed increases infinitely with increasing con-
centration. This equation is, therefore, satisfactory for low
concentrations. The Freundlich isotherm is also more widely
used but provides no information on the monolayer adsorp-
tion capacity, in contrast to the Langmuir model [11].
Succesful design of a column adsorption process requires
prediction of the concentration–time profile or breakthrough
curve for the effluent. Developing a model to accurately de-
(4) scribe the dynamic behavior of adsorption in a fixed bed
system is inherently difficult. Since the concentration of the
adsorbate as the feed moves through the bed, the process
does not operate at steady state. The fundamental transport
equations for a fixed bed are those of material balance be-
tween solid and fluid. These equations are usually written
in the following form.
     
∂Cb ∂Cb ∂q ∂2 Cb
ε + Uo + (1 − ε) =E (9)
∂t ∂Z ∂t ∂2 Z
where q is the phenol concentration in the sorbent at t (mg
l−1 ); Cb , the phenol concentration in solution (mg l−1 ); Z,
the column depth (cm); ε, the void fraction in the bed; Uo ,
the superficial velocity (cm min−1 ); and E is a dispersion
coefficient (cm2 min−1 ).
The second key equation is a mass balance on the adsorbed
solute:
 
∂q
(1 − ε) =r (10)
(6) ∂t
As before, the adsorption rate r (mg l−1 min−1 ) depends
on the mechanism responsible for adsorption. This mech-
anism may be controlled by mass transfer from the bulk
solution to the surface of the adsorbent. Alternatively, it may
be controlled by diffusion and reaction within the adsorbent
particles. So the mathematical description of adsorption rate
(7)
must be added to these transport equations given for the fixed
bed. The adsorption isotherm equation is the fourth and final
key equation for the mathematical modeling of a fixed bed.
All these equations derived to model the system with the-
oretical rigor are differential in nature and usually require
complex numerical methods to solve. Such a numerical
solution is not usually difficult, but often does not fit ex-
perimental results especially well. Some solutions for very
limiting cases have been reported, but in general, complete
time-dependent analytical solutions to differential equation
based models of the proposed rate mechanisms are not avail-
able. Because of this, various simple mathematical models
have been developed to predict the dynamic behavior of the
column and the following models characterizing fixed bed
(8) performance are discussed in detail here [8,15,19].
2.1. The Adams–Bohart model
The fundamental equations describing the relationship
between C/Co and t in a flowing system were established
by Adams and Bohart (1920) for the adsorption of chlorine
on charcoal. Although the original work by Adams–Bohart
was done for the gas–charcoal adsorption system, its over-
all approach can be applied successfully in quantitative
 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613 603

description of other systems. This model assumes that the that in short beds or at high flow rates of solution through
adsorption rate is proportional to both the residual capacity the bed, the axial diffusion is negligible and ␤a = ␤o . The
of the activated carbon and the concentration of the sorbing migration velocity of the steady-state front satisfies the re-
species. The Adams–Bohart model is used for the descrip- lation, known as Wicke’s law:
tion of the initial part of the breakthrough curve. The mass Uo Co
transfer rates obey the following equations: ␯= (18)
No + C o
∂q
= −kAB qCb (11) The expression of the Wolborska solution is equivalent to
∂t
the Adams–Bohart relation if the coefficient kAB is equal to
∂Cb kAB ␤a /No . So the drawing of ln C/Co versus t would also give
=− qCb (12)
∂Z Uo information on this model [14,15].
where kAB is the kinetic constant (l mg−1 min−1 ). Some
2.3. The Thomas model
assumptions are made for the solution of these differential
equation systems: (i) the concentration field is considered to
Successful design of a column adsorption process requires
be low, e.g. effluent concentration C<0.15Co ; (ii) for t→∞,
prediction of the concentration–time profile or breakthrough
q→No , (where No is the saturation concentration (mg l−1 ).
curve for the effluent. The maximum adsorption capacity
When the differential equation systems solved, the following
of an adsorbent is also needed in design. Traditionally, the
equation is obtained with parameters kAB and No :
Thomas model is used to fulfil the purpose. The model has
C Z the following form:
ln = kAB Co t − kAB No (13)
Co Uo
C 1
where Co and C are the inlet and effluent phenol concen- =   (19)
Co k
1 + exp QTh (qo X − Co Veff )
trations (mg l−1 ), respectively. From this equation values
describing the characteristic operational parameters of the
column can be determined from a plot of ln C/Co against t where kTh is the Thomas rate constant (ml min−1 mg−1 ) and
at a given bed height and flow rate [12–15]. qo is the maximum solid-phase concentration of the solute
(mg g−1 ). The linearized form of the Thomas model is as
2.2. The Wolborska model follows:
 
Co kTh qo X kTh Co
ln −1 = − Veff (20)
The Wolborska model is also used for the description of C Q Q
adsorption dynamics using mass transfer equations for dif-
fusion mechanisms in the range of the low-concentration The kinetic coefficient kTh and the adsorption capacity of
breakthrough curve. The mass transfer in the fixed bed sorp- the bed qo can be determined from a plot of ln[(Co /C]−1]
tion is described by the following equations: against t at a given flow rate.
     2  The Thomas solution is one of the most general and
∂Cb ∂Cb ∂q ∂ Cb widely used methods in column performance theory. The
+ Uo + =D (14)
∂t ∂Z ∂t ∂2 Z Thomas or reaction model, which assumes Langmuir kinet-
  ics of adsorption–desorption and no axial dispersion is de-
∂q ∂q
= −␯ = ␤a (Cb − Cs ) (15) rived with the adsorption that the rate driving force obeys
∂t ∂Z second-order reversible reaction kinetics. Thomas’ solution
where Cs is the phenol concentration at the solid/liquid inter- also assumes a constant separation factor but it is applicable
face (mg l−1 ); D, the axial diffusion coefficient (cm2 min−1 ); to either favorable or unfavorable isotherms. The primary
␯, the migration rate (cm min−1 ); and ␤a is the kinetic co- weakness of the Thomas solution is that its derivation is
efficient of the external mass transfer (min−1 ). With some based on second order reaction kinetics. Adsorption is usu-
assumptions previously described by Wolborska: Cs Cb , ally not limited by chemical reaction kinetics but is often
␯ Uo and axial diffusion negligible D → 0 as t → 0, the controlled by interphase mass transfer. This discrepancy can
solution can be approximated to: lead some error when this method is used to model adsorp-
C ␤ Co ␤ Z tion process [8,18].
ln = a t− a (16)
Co No Uo
2.4. The Clark model
with
 
U2 4␤o D Clark (1987) defined a new simulation of breakthrough
␤a = o 1+ −1 (17) curves. This model combines the Freundlich equation and
2D Uo2
the mass transfer concept according to Eqs. (8) and (21):
where ␤o is the external mass transfer coefficient with a neg- dCb
ligible axial dispersion coefficient D. Wolbraska observed Uo = K(Cb − Ceq ) (21)
dZ
604 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613
where K is the mass transfer coefficient (min−1 ). Clark re-
solved this system and obtained the following solution:
 1/n−1
Con−1
=C (22)
1 + [(Cn−1 −rt
o /Cbreak − 1)e break ]e
n−1 rt
or
 1/n−1
C 1
= (23)
Co 1 + Ae−rt
with
 
Cn−1
A= o
− 1 ertbreak (24)
Cn−1
break
and
kCl
R(n − 1) = r and R= ␯ (25)
Uo
Eq. (23) is the generalized logistic function where n;
Cbreak and tbreak are the Freundlich constant, the outlet con-
centration at breakthrough (or limit effluent concentration),
and the time at breakthrough, respectively. For a particular
adsorption process on a fixed bed and a chosen treatment
objective, values of A and r can be determined by using
Eq. (23) by non-linear regression analysis, enabling the pre-
diction of the breakthrough curve according to the relation-
ship between C/Co and t in Eq. (23), [15–17].
2.5. The Yoon and Nelson model
Yoon and Nelson (1984) have developed a relatively sim-
ple model addressing the adsorption and breakthrough of
adsorbate vapors or gases with respect to activated charcoal.
This model is based on the assumption that the rate of de-
crease in the probability of adsorption for each adsorbate
molecule is proportional to the probability of adsorbate ad-
sorption and the probability of adsorbate breakthrough on
the adsorbent. The Yoon and Nelson model not only is less
complicated than other models, but also requires no detailed
data concerning the characteristics of adsorbate, the type of
adsorbent, and the physical properties of adsorption bed.
The Yoon and Nelson equation regarding to a single-
component system is expressed as:
C diluted and concentrated H2 SO4 and NaOH solutions.
ln = kYN t − ␶k YN (26)
Co − C
where kYN is the rate constant (min−1 ); ␶, the time re-
quired for 50% adsorbate breakthrough (min) and t is the
breakthrough (sampling) time (min). The calculation of the-
oretical breakthrough curves for a single-component system
requires the determination of the parameters kYN and ␶ for
the adsorbate of interest. These values may be determined
from available experimental data. The approach involves a
plot of ln C/(Co −C) versus sampling time (t) according to
Eq. (26). If the theoretical model accurately characterizes
the experimental data, this plot will result in a straight line
with slope of kYN and intercept ␶kYN [19,20].
3. Experimental
3.1. Microorganism
The waste activated sludge collected from wastewater
treatment system of Meteksan Company-Ankara Paper and
Board Mill, Turkey was used in this study. The harvested
cells were washed thoroughly with sterile distilled water,
centrifuged at 5000 rpm for 5 min, dried at 60 ◦ C for 24 h to
constant weight and then powdered before immobilization.
3.2. Preparation of Mowital® B30H resin immobilized
activated sludge
The method used for the immobilization is based on
solvent evaporation. For each batch immobilization, 1 g
Mowital® B30H (Hoechst) was dissolved in 8 ml of chloro-
form (Merck). When Mowital® B30H resin was completely
dissolved in this solution, 1 g of dried and powdered ac-
tivated sludge biomass was added to this medium mixed
continuously by means of an agitator. 4 g of polyvinyl al-
cohol (Sigma) used as the stabilizator was solved in 500
ml of distilled water. After that, 0.3 g of sodium dodecyl
sulfate (Sigma) used as the emulsifier was added to this
mixture and mixed thoroughly. At the last step, the first
prepared mixture was added to this mixture. The mixing
operation was continued for 6 h at 750 rpm to obtain the
porous, uniform and spherical immobilized particles and to
evaporate chloroform. Finally, the particles were removed
from the immobilization medium and washed with distilled
water. These particles had 1.0 mm of mean diameter and
contained 50% dried activated sludge by weight [11].
3.3. Preparation of phenol solutions
Phenol solutions were prepared by diluting 1 g l−1 of stock
phenol solution, which was obtained by dissolving exact
quantity of phenol (Merck) in double distilled and de-ionized
water. The range in concentrations of phenol prepared from
stock solution varied between 50 and 500 mg l−1 . Before
the biosorption in the continuous column system, the pH of
each test solution was adjusted to the required value with
3.4. Sorption studies in the batch and column systems
The effect of initial pH on phenol biosorption by
Mowital® B30H resin immobilized activated sludge was
examined in a batch system. For the batch system studies,
immobilized particles containing 0.05 g of dried activated
sludge were contacted with the known concentration of
100 ml phenol-bearing solution in Erlenmayer flasks at
the desired pH. The flasks were agitated on a shaker for
120 h, which is more than ample time for sorption equi-
librium. Three milliliter samples of solution were taken in
definite intervals and analyzed for the residual phenol. The
 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613
equilibrium phenol uptake value (qeq ) was determined as
mg of sorbed phenol per g of sorbent.
Continuous fixed bed column studies were performed in
a fixed bed mini column reactor with an inside diameter of
0.96 cm, a bed depth of 6 cm and 3 g of immobilized cells
containing 1.5 g of dried activated sludge biomass. The col-
umn was preconditioned to pH 1.0 for phenol (by eluting the
column with 1 M H2 SO4 ). The phenol solution at a known
concentration and flow rate was passed continuously through
the stationary bed of sorbent. The flow rate was regulated
with a variable speed pump by a Masterflex L/S digital drive
and easy-load pump head. Samples were taken from the ef-
fluent at timed intervals and analyzed for phenol as described
below. The experiment was continued until a constant con-
centration of phenol was obtained. The experiments showed
that no phenol was taken up by Mowital® B30H beads in the
absence of entrapped biomass.
The studies were performed at a constant temperature of
25 ◦ C to be representative of environmentally relevant con-
ditions. All the experiments were carried out in duplicates
and the average values were used for further calculations.
3.5. Analysis of phenol
The concentration of phenol in the effluent was de-
termined spectrophotometrically. The absorbance of the
coloured complex of phenol with p-nitroaniline was read at
470 nm after [21].
4. Results and discussion
4.1. Effect of initial pH
The most important single parameter influencing the sorp-
tion capacity is the pH of adsorption medium. The initial
pH of adsorption medium is related to the adsorption mech-
anisms onto the adsorbent surface from water and reflects
the nature of the physicochemical interaction of the species
in solution and the adsorptive sites of adsorbent. The vari-
ation of equilibrium phenol uptake with initial pH obtained
from batch system studies was given in Fig. 1. The removal
of phenol from aqueous solution was more efficient with de-
creasing pH and was the greatest at pH 1.0. The equilibrium
phenol uptake was 55.6 mg g−1 at this pH value. Packed
bed column studies were also performed at the same pH.
pH primarily affects the surface properties of the acti-
vated sludge biomass, i.e. surface charge of the cells used as
biosorbent. The surface charge of biomass is predominantly
negative over the pH range of 3.0–10.0. Phenol could be ex-
pected to become negatively charged phenoxide ion above a
pH of 9.0 as pKa for phenol molecules at 25 ◦ C is 9.99. Be-
low a pH of 3.0, the overall surface charge on cells becomes
positive due to isoelectric point of activated sludge so the
electrostatic attraction between phenol and activated sludge
biomass will be insignificant. The hydrogen binding between
605
Fig. 1. The effect of initial pH on the equilibrium phenol uptake in the
batch system (temperature, 25 ◦ C; initial pH, 1.0; Co , 100 mg l−1 ; X, 0.5
g l−1 ; agitating rate, 150 rpm).
the hydroxyl group of phenol and the functional groups on
cell surface like carboxylic may play a certain role in phenol
adsorption at very low pH values. Moreover donor–acceptor
interactions between the aromatic ring of phenol activated
by the OH− , and the groups of the biosorbent surface may
be also important in this case. At very low pH values, the
surface of sorbent would also be surrounded by the hydro-
nium ions which enhance the unionized phenol molecules
interaction with binding sites of the biosorbent by greater
attractive forces. As the pH increased, however, the overall
surface charge on the cells became negative and biosorp-
tion decreased. Because phenol exhibit significant binding
at higher pHs, there must be some additional types of reten-
tion mechanisms, including alterations in cell surface prop-
erties and interactions of phenols with the cells by complex
formation or electron share or membrane transport [6,8–10].
4.2. Effect of flow rate
In the first stage of removal studies in the continuous-flow
fixed column with Mowital® B30H resin immobilized acti-
vated sludge, the flow rate was changed from 0.8 to 3.2 ml
min−1 while the inlet phenol concentration in the feed was
held constant at 100 mg l−1 at pH 1.0. The plots of compar-
ative normalized phenol concentration versus effluent vol-
ume at different flow rates are given in Fig. 6. As indicated
in Fig. 6, at the lowest flow rate of 0.8 ml min−1 , relatively
higher uptake values were observed for phenol biosorption
to immobilized activated sludge at the beginning of column
operation. But, as solution continued to flow, the concentra-
tion of phenol in the effluent rapidly increased, the bed be-
came saturated with phenol and the concentration of solute
in the effluent suddenly rose to inlet phenol concentration.
Much sharper breakthrough curves were obtained by immo-
bilized activated sludge at higher flow rates. The breakpoint
time and total adsorbed phenol quantity also decreased with
606 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613

Table 1 to the column was adsorbed by Mowital® B30H resin immo-

The effect of flow rate and inlet phenol concentration on the total adsorbed
quantity of phenol (qtotal ), equilibrium phenol uptake (qeq ) and total
bilized activated sludge beads, respectively. The maximum
removal percentage of phenol for phenol adsorption to Mowital®B30H biosorption capacity of immobilized cells was 9.0 mg g−1 at
resin immobilized activated sludge an inlet phenol concentration of 502.3 mg l−1 .The driving
Co (mg l−1 ) Q (ml min−1 ) qtotal (mg) qeq (mg g−1 ) Total phenol
force for adsorption is the concentration difference between
removal (%) the solute on the sorbent and the solute in the solution. A high
52.3 0.8 9.0 6.0 14.8 concentration difference provides a high driving force for the
102.3 0.8 10.2 6.8 13.0 adsorption process and this may explain why higher adsorp-
1.6 5.0 3.4 8.6 tion capacities were achieved in the column fed with a higher
3.2 2.3 1.5 5.8 phenol concentration. The relatively low phenol retention
251.1 0.8 12.3 8.2 11.3
for immobilized activated sludge can be attributed to the dif-
502.3 0.8 13.5 9.0 9.3
ference in the surface morphology. Immobilized activated
sludge particles do not have many micro or macropores, so
its low surface area also results in lower sorption capacity.
increasing flow rate. This behavior can be explained that
phenol biosorption by activated sludge biomass is affected
4.4. Application of the Langmuir and Freundlich models
by insufficient residence time of the solute in the column, the
diffusion of the solute into the pores of biosorbent and lim-
Adsorption isotherms show the distribution of solute be-
ited number of active sites and ionic groups of biomass for
tween the liquid and solid phases and can be described
biosorption in the matrix. The sorption data were evaluated
by several mathematical relationships such as the standard
and the total sorbed quantities, maximum phenol uptakes
Langmuir and Freundlich models. The linearized Freundlich
and removal percents with respect to flow rate are presented
and Langmuir adsorption isotherms of phenol obtained at
in Table 1. In general the total sorbed phenol quantity, max-
25 ◦ C were shown in Figs. 2 and 3 with the correlation co-
imum phenol uptake and phenol removal percentage values
efficients. In view of the values of linear regression coeffi-
decreased with increasing flow rate and maximum values of
cients, both the models fitted very well to the sorption data
total sorbed phenol quantity, maximum phenol uptake and
in the studied concentration range.
phenol removal percentage were obtained as 10.2 mg, 6.8
An adsorption isotherm is characterized by certain con-
mg g−1 and 13.0, respectively, at 0.8 ml min−1 flow rate.
stants the values of which express the surface properties and
affinity of the sorbent and can also be used to compare the
4.3. Effect of inlet phenol concentration sorptive capacity of sorbent for the phenol in the fixed col-
umn. KF and n, the Freundlich constants, are indicators of
The adsorption performance of Mowital® B30H resin im- adsorption capacity and adsorption intensity, respectively.
mobilized activated sludge was tested at various phenol inlet The closer the n value of Freundlich is to zero the more
concentrations. The sorption breakthrough curves obtained heterogeneous is the system. From Fig. 3, KF and n val-
by changing inlet phenol concentration from 50 to 500 mg ues were determined as 3.1 and 5.6, respectively. The high
l−1 at 0.8 ml min−1 flow rate are given in Fig. 7. As ex- values of KF showed easy uptake of phenol from wastew-
pected, a decreased inlet concentration gave a later break- ater with high adsorptive capacity of sorbent. Table 3 also
through curve and the treated volume was the greatest at
the lowest inlet concentration since the lower concentration
gradient caused a slower transport due to a decreased diffu-
sion coefficient or decreased mass transfer coefficient. The
breakpoint time decreased with increasing inlet phenol con-
centration as the binding sites became more quickly satu-
rated in the system. Breakthrough (C/Co = 0.05) occurred
after 30 min (corresponding to 24 ml of effluent solution)
at 50 mg l−1 phenol inlet concentration while as breakpoint
time appeared after 15 min (corresponding to 12 ml of ef-
fluent solution) at an inlet phenol concentration of 100 mg
l−1 . The total sorbed phenol quantities, equilibrium phenol
uptakes and phenol removal percentages related to the feed
phenol concentration are also compared in Table 1. Although
the equilibrium phenol uptake and amount of total sorbed
phenol increased with increasing inlet phenol concentration
from 50 to 500 mg l−1 , the total phenol removal percentages
showed opposite trend. For the inlet phenol concentrations Fig. 2. The linearized Langmuir adsorption isotherm for phenol biosorption
of 50 and 500 mg l−1 , 14.8 and 9.3% of total phenol applied to Mowital® B30H resin immobilized activated sludge.
 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613 607

4.5. Estimation of breakthrough curves and determination

of kinetic constants

The dynamic behavior of the column was predicted with

the Adams–Bohart, Thomas, Clark and Yoon–Nelson mod-
els. The breakthrough curves showed the superposition of
experimental results (points) and the theoretical calculated
points (lines). Linear regression coefficients (R2 ) showed
the fit between experimental data and linearized forms of
Adams–Bohart, Thomas and Yoon–Nelson equations while
the average percentage errors (ε%) calculated according to
Eq. (27) indicated the fit between the experimental and pre-
dicted values of C/Co used for plotting breakthrough curves.
N

(C/Co )exp −(C/Co )theo

i=1
(C/Co )exp

Fig. 3. The linearized Freundlich adsorption isotherm for phenol biosorp-
tion to Mowital®B30H resin immobilized activated sludge.
indicates that n is greater than unity, indicating that phenol
are favorably adsorbed by the sorbent.
The Langmuir constants of Q◦ and b were determined
from Ceq /qeq versus Ceq plot as 9.6 and 0.03. The Q◦ defines
the total capacity of biosorbent for phenol.
The Langmuir model makes several assumptions, such
as monolayer coverage and constant adsorption energy
while the Freundlich equation deals with heterogeneous
surface adsorption. The applicability of both Langmuir and
Freundlich isotherms to the immobilized activated sludge
system implies that both monolayer adsorption and het-
erogeneous surface conditions exist under the experimental
conditions used.
In general as expected, the values of isotherm constants
obtained in a batch system show the maximum values of
these constants and are considerably higher than those ob-
tained in a fixed bed as flow rate of solution is zero in batch
system, that is, the contact time between sorbate solution and
adsorbent approximates infinite. These experimental data are
generally used in further studies concerning the dynamic
adsorption of solute in column studies for the prediction of
breakthrough curves. However, it is important to note that
adsorption isotherms and constants determined in a fixed bed
should be used for evaluating the breakthrough curves and
kinetic constants to model such a system mathematically.
ε% = × 100 (27)
N
where the subscripts ‘exp’ and ‘calc’ show the experimental
and calculated values and N the number of measurements.
4.6. Application of the Adams–Bohart and
the Wolborska models
The Adams–Bohart (or Wolborska) sorption model was
applied to experimental data for the description of the initial
part of the breakthrough curve. This approach was focused
on the estimation of characteristic parameters, such as max-
imum adsorption capacity (No ) and kinetic constant (kAB )
from Adams–Bohart model and kinetic coefficient of the
external mass transfer (␤a ) from Wolbraska model. After
applying Eq. (13) (or Eq. (16)) to the experimental data
for varying flow rates and inlet phenol concentrations, a
linear relationship between ln C/Co and t was obtained for
the relative concentration region up to 0.5, i.e. up to 50%
breakthrough, for all breakthrough curves (R2 > 0.900). Re-
spective values of No , kAB and ␤a were calculated from the
ln C/Co versus t plots at all flow rates and inlet phenol con-
centrations studied are presented in Table 2 together with
the correlation coefficients. The values of kinetic constant
was influenced by flow rate and increased with increasing
flow rate. This showed that the overall system kinetics is
dominated by external mass transfer in the initial part of
biosorption in the column. ␤a is also an effective coefficient
which reflects the effect of both mass transfer in liquid

Table 2
Parameters predicted from the Adams–Bohart and Wolborska models and model deviations for phenol biosorption to Mowital®B30H resin immobilized
activated sludge at different inlet phenol concentrations and flow rates
Co (mg l−1 ) Q (ml min−1 ) Adams–Bohart model Wolborska model ␤a (min−1 ) R2 ε%

kAB (l mg−1 min−1 ) No (mg l−1 )

52.3 0.8 0.0026 498.1 1.30 0.984 16.3

102.3 0.8 0.0014 726.3 1.02 0.900 22.1
102.4 1.6 0.0032 551.3 1.76 0.977 14.7
103.5 3.2 0.0036 519.0 1.87 0.999 0.3
251.1 0.8 0.0008 1310.4 1.05 0.941 22.4
502.3 0.8 0.0001 3225.9 0.32 0.942 6.1
608 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613

Fig. 4. Comparison of the experimental and predicted breakthrough curves obtained at different flow rates according to the Adams–Bohart (or Wolbraska)
model (temperature, 25 ◦ C; initial pH, 1.0; Co , 100 mg l−1 ).

phase and axial dispersion. Wolborska observed that in short
beds or at high flow rates of solution through the bed, the
axial diffusion is negligible and ␤a = ␤o , the external mass
transfer coefficient. Increasing flow rate from 0.8 to 3.2 ml
min−1 increased the ␤a value since increased turbulence re-
duces the film boundary layer surrounding the immobilized
particle. As expected, maximum adsorption capacity (No )
increased with increasing inlet phenol concentration. Pre-
dicted and experimental breakthrough curves with respect to
flow rate and inlet phenol concentration are shown in Figs. 4
and 5. It is clear from figures and average percentage errors
(<22.4%) in Table 2 that there is a good agreement between
the experimental and predicted values, suggesting that the
Adams–Bohart (or Wolbraska) model is valid for the relative
concentration region up to 0.5 where as large discrepancies
were found between the experimental and predicted curves
above this level for the phenol adsorption in immobilized cell
column.
Although the Adams–Bohart (or Wolbraska) model pro-
vides a simple and comprehensive approach to running and
evaluating sorption-column tests, its validity is limited to the
range of conditions used.
4.7. Application of the Thomas model
The column data were fitted to the Thomas model to
determine the Thomas rate constant (kTh ) and maximum
solid-phase concentration (qo ). Application of Thomas
model to the data at C/Co ratios higher than 0.08 and lower
than 0.97 with respect to flow rate and inlet phenol concen-
trations enabled the determination of the kinetic coefficients
in this system. A linear regression was then performed on

Fig. 5. Comparison of the experimental and predicted breakthrough curves obtained at different inlet phenol concentrations according to the Adams–Bohart
model (temperature, 25 ◦ C; initial pH, 1.0; Q, 0.8 ml min−1 ).
 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613 609

Table 3
Parameters predicted from the Thomas model and model deviations for phenol biosorption to Mowital®B30H resin immobilized activated sludge at
different inlet phenol concentrations and flow rates
Co (mg l−1 ) Q (ml min−1 ) kTh (ml mg−1 min−1 ) qo,cal (mg g−1 ) qo,exp (mg g−1 ) R2 ε%

52.3 0.8 0.119 6.4 6.0 0.989 16.3

102.3 0.8 0.073 7.1 6.8 0.968 14.2
102.4 1.6 0.228 2.9 3.4 0.942 16.7
103.5 3.2 0.654 0.9 1.5 0.836 36.5
251.1 0.8 0.054 8.8 8.2 0.879 21.5
502.3 0.8 0.050 9.2 9.0 0.935 18.8

each set of transformed data to determine the coefficients
from slope and intercept. Inspection of each of the regressed
lines indicated that they were all acceptable fits with linear
regression coefficients ranging from 0.935 to 0.989 except
the regressed lines obtained for 250 mg l−1 inlet phenol
concentration and 1.6 ml min−1 flow rate. The values of
kTh and qo are presented in Table 3. As flow rate increased,
the values of kTh increased and the values of qo decreased.
The bed capacity qo increased and the coefficient kTh de-
creased with increasing inlet phenol concentration. The
data in Table 3 also showed a negligible difference between
the experimental and predicted values of the bed capacity
(qo ) obtained at all inlet phenol concentrations studied al-
though the deviations of experimental data from predicted
values were evident at 1.6 and 3.2 ml min−1 flow rates. It
is clear from Figs. 6 and 7 that although the model gave a
poor fit of the experimental data at higher flow rates, there
was a good agreement between the experimental and pre-
dicted normalized concentration values at all phenol inlet
concentrations.
The Thomas model is suitable for adsorption processes
where the external and internal diffusions will not be the
limiting step.
4.8. Application of the Clark model
In a part of study, it was found that the Freundlich model
was approximately valid for the adsorption of phenol on
the immobilized activated sludge in the fixed bed column
so the Freundlich constant n obtained were used to cal-
culate the parameters in the Clark model. The adsorption
breakthrough could be well described by Clark model at
the ratios of C/Co higher than 0.08 with respect to flow
rate and inlet phenol concentration. Below these levels the
model could not applied to experimental data. The values
of A and r in the Clark equation were determined using
Eq. (23) by non-linear regression analysis and are shown
in Table 4. The non-linearized regression analysis provided
the deviation values changing between 3.7 and 13.6% for
the model fit. From Table 4 as both flow rate and inlet
phenol concentration increased, the values of r increased.
Plotting C/Co against t according to this equation also gives
the breakthrough curves predicted by the Clark model.
Figs. 8 and 9 showed the experimental and model-calculated
breakthrough curves obtained at different flow rates and
at different inlet phenol concentrations. It appears that the
simulation of the whole breakthrough curve is effective

Fig. 6. Comparison of the experimental and predicted breakthrough curves obtained at different flow rates according to the Thomas model (temperature,
25 ◦ C; initial pH, 1.0; Co , 100 mg l−1 ).
610 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613

Fig. 7. Comparison of the experimental and predicted breakthrough curves obtained at different inlet phenol concentrations according to the Thomas
model (temperature, 25 ◦ C; initial pH, 1.0; Q, 0.8 ml min−1 ).

Table 4 4.9. Application of the Yoon and Nelson model

Parameters obtained from the Clark model and model deviations for
phenol biosorption to Mowital®B30H resin immobilized activated sludge A simple theoretical model developed by Yoon–Nelson
at different inlet phenol concentrations and flow rates was applied to investigate the breakthrough behavior of
Co (mg l−1 ) Q (ml min−1 ) A r (min−1 ) ε% phenol on immobilized activated sludge. The values of kYN
52.3 0.8 9209.0 0.021 7.7 (a rate constant) and ␶ (the time required for 50% adsor-
102.3 0.8 3094.0 0.034 7.0 bate breakthrough) were determined from ln[C/(Co −C)]
102.4 1.6 888.3 0.124 3.7 against t plots at different flow rates varied between 0.8
103.5 3.2 3138.4 0.776 6.1 and 3.2 ml min−1 and at different inlet phenol concen-
251.1 0.8 1753.5 0.044 13.6
trations varied between 50 and 500 mg l−1 . These values
502.3 0.8 4678.1 0.126 9.9
were used to calculate the breakthrough curve. The values
of kYN and ␶ are also listed in Table 5. From Table 5 the
with the Clark model at higher flow rates and at higher inlet rate constant kYN increased and the 50% breakthrough
phenol concentrations. For lower flow rates and inlet phenol time ␶ decreased with both increasing flow rate and phe-
concentrations the correlation between the experimental and nol inlet concentration. The data in Table 5 also indicated
predicted values using this model deviated significantly. that ␶ values are very similar to experimental results. The

Fig. 8. Comparison of the experimental and predicted breakthrough curves obtained at different flow rates according to the Clark model (temperature,
25 ◦ C; initial pH, 1.0; Co , 100 mg l−1 ).
 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613 611

Fig. 9. Comparison of the experimental and predicted breakthrough curves obtained at different inlet phenol concentrations according to the Clark model
(temperature, 25 ◦ C; initial pH, 1.0; Q, 0.8 ml min−1 ).

Table 5
Parameters predicted from the Yoon–Nelson model and model deviations for phenol biosorption to Mowital®B30H resin immobilized activated sludge
at different inlet phenol concentrations and flow rates
Co (mg l−1 ) Q (ml min−1 ) kYN (l min−1 ) ␶theo (min) ␶exp (min) R2 ε%

52.3 0.8 0.0065 264.9 240 0.987 12.4

102.3 0.8 0.0074 131.6 120 0.970 14.3
102.4 1.6 0.0245 34.5 30 0.929 25.8
103.5 3.2 0.0678 3.2 6 0.832 36.5
251.1 0.8 0.0136 65.4 60 0.924 18.8
502.3 0.8 0.0210 26.0 30 0.927 16.4

theoretical curves are compared with the corresponding 0.99. From the experimental results and data regression, the
experimental data in Figs. 10 and 11. The experimental model proposed by Yoon–Nelson provided a good corre-
breakthrough curves were very close to those predicted by lation of the effects of inlet phenol concentration and flow
the Yoon–Nelson model in the C/Co region from 0.08 up to rate.

Fig. 10. Comparison of the experimental and predicted breakthrough curves obtained at different flow rates according to the Yoon–Nelson model
(temperature, 25 ◦ C; initial pH, 1.0; Co , 100 mg l−1 ).
612 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613
Fig. 11. Comparison of the experimental and predicted breakthrough curves obtained at different inlet phenol concentrations according to the Yoon–Nelson
model (temperature, 25 ◦ C; initial pH, 1.0; Q, 0.8 ml min−1 ).
5. Conclusion
The biosorption of phenol from aqueous solution on
Mowital® B30H resin immobilized dried activated sludge
was investigated in a continuous packed bed column. The
breakthrough curves for column sorption of phenol from
dilute solutions to immobilized activated sludge have been
measured at various flow rates and inlet phenol concentra-
tions at 25 ◦ C. The results obtained showed that the sorption
of phenol is dependent on both the flow rate and the inlet
phenol concentration and the breakpoint time and phenol
removal yield decrease with increasing flow rate and phenol
concentration.
The Freundlich and Langmuir adsorption models were
used for the mathematical description of the biosorption
of phenol to MowItal® B30H resin immobilized activated
sludge in a continuous packed bed column and the isotherm
constants were determined. It was seen that the adsorption
equilibrium data fitted very well to the Langmuir adsorption
model.
The Adams–Bohart (or Wolborska), the Thomas, the
Clark and the Yoon–Nelson models were applied to ex-
perimental data obtained from dynamic studies performed
on fixed column to predict the breakthrough curves and to
determine the column kinetic parameters. The initial region
of breakthrough curve was defined by the Adams–Bohart
(or Wolborska) model at all flow rates and inlet phenol
concentrations studied while the full description of break-
through could be accomplished by all other models only
at higher flow rates and higher inlet phenol concentrations.
The model constants belonging to each model were deter-
mined by linear and non-linear regression techniques and
were proposed for the use in column design.
It seems that although the immobilization process de-
creased the phenol biosorption properties of the biomass,
dried activated sludge has a considerable potential for the
removal of phenol over a wide range of phenol concen-
tration. The results also indicated that the sorption process
could only deal with lower flow rates and lower concentra-
tions of phenol solutions if a high percentage removal was
required for extended periods. By adjusting the operating
characteristics of the packed column, for example the flow
rate, inlet phenol concentration, particle size, biomass quan-
tity very rapid and efficient phenol uptake can be achieved
for the system.
References
[1] Patterson JW. Wastewater treatment technology. USA: Ann Arbor
Science Pub. Inc, 1977.
[2] Mohan D, Chander S. Single component and multi-component ad-
sorption of phenols by activated carbons. Colloids Surf A: Physic-
ochem Eng Aspects 2001;177:183–96.
[3] Streat M, Patrick JW, Camporro-Perez MJ. Sorption of phenol and
p-chlorophenol from water using conventional and novel activated
carbons. Water Sci Res 1995;29:467–73.
[4] Aksu Z, Bülbül G. Investigation of the combined effects of external
mass transfer and biodegradation rates on phenol removal using
immobilized P. putida in a packed bed column reactor. Enzyme
Microb Technol 1998;22:397–403.
[5] Annadurai G, Juang R-S, Lee D-J. Microbial degradation of phenol
using mixed liquors of Pseudomonas putida and activated sludge.
Waste Manage 2002;22:703–10.
[6] Aksu Z, Yener J. Investigation of the biosorption of phenol and
monochlorinated phenols on the dried activated sludge. Process
Biochem 1998;33:649–55.
[7] Aksu Z, Akpinar D. Modelling of simultaneous biosorption of phenol
and nickel(II) onto dried aerobic activated sludge. Sep Pur Technol
2000;21:87–99.
[8] Rao JR, Viraraghavan T. Biosorption of phenol from a aqueous
solution by Aspergillus niger biomass. Bioresour Technol 2002;85:
165–71.
 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613
[9] Calace N, Nardi E, Petronio BM, Pietroletti M. Adsorption of phenols
by papermill sludges. Environ Pollut 2002;118:315–9.
[10] Garcia IG, Pena PRJ, Venceslada JLB, Martin AM, Santos MAM,
Gomez ER. Removal of phenol from olive mill wastewater using
Phanerochaete chrysosporium, Aspergillus niger, Aspergillus terreus
and Geotrichum candidum. Process Biochem 2000;35:751–8.
[11] Aksu Z, Gönen F, Demircan Z. Biosorption of chromium(VI) ions
by Mowital® B30H resin immobilized activated sludge in a packed
bed: comparison with granular activated carbon. Process Biochem
2002;38:175–86.
[12] Texier AC, Andres Y, Faur-Brasquet C, LeCloirec P. Fixed-bed study
for lanthanide (La, Eu, YB) ions removal from aqueous solutions
by immobilized Pseudomonas aeruginosa: experimental data and
modelization. Process Biochem 2002;47:333–42.
[13] Bohart G, Adams EQ. Some aspects of the behavior of charcoal
with respect to chlorine. J Am Chem Soc 1920;42:523–44.
[14] Wolborska A. Adsorption on activated carbon of p-nitrophenol from
aqueous solution. Water Res 1989;23:85–91.
613
[15] Guibal E, Lorenzelli R, Vincent T, Le Cloirec P. Application of silica
gel to metal ion sorption: static and dynamic removal of uranyl ions.
Environ Technol 1995;16:101–14.
[16] Clark RM. Evaluating the cost and performance of field-scale gran-
ular activated carbon systems. Environ Sci Technol 1987;21:573–80.
[17] Tran HH, Roddick FA. Comparison of chromatography and desiccant
silica gels for the adsorption of metal ions. Water Res 1999;33:3001–
11.
[18] Thomas HC. Heterogeneous ion exchange in a flowing system. J
Am Chem Soc 1944;66:1664–6.
[19] Yoon YH, Nelson JH. Aplication of gas adsorption kinetics. I. A
theoretical model for respirator cartridge service time. Am Ind Hyg
Assoc J 1984;45:509–16.
[20] Tsai WT, Chang CY, Ho CY, Chen LY. Adsorption properties and
breakthrough model of 1,1-dichloro-1-fluoroethane on activated car-
bons. J Hazard Mater 1999;69:53–66.
[21] Snell FD, Snell CT. Colorimetric methods of analysis, vol. 2, 3rd
ed. Toronto: D. Van Nostrand Company, 1959.