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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-


cal and causes further environment damage. Hence, easy,
Phenolics are present in different concentrations in effective, economic and ecofriendly techniques are required
wastewaters of industries such as coal conversion, coke for fine tuning of effluent/wastewater treatment.
preparation, synthetic rubber, pesticide, insecticide, The search for a low cost and easily available adsorbent
petroleum refineries, pulp and paper, plastic, textile, dye, has led to the investigation of materials of agricultural and
polymeric resin, pharmaceuticals, wood, etc. [1]. Phenol and biological origin, along with industrial by-products, as ad-
phenolic compounds are among the most common organic sorbents. Microorganisms such as bacteria, fungi, yeast and
pollutants of wastewaters that require careful treatment be- algae can remove some pollutants from aqueous solutions
fore being discharged into the receiving body of waters. It and this biological phenomenon is called biosorption. This
should be noted that the contamination of drinking water term is used to indicate a number of metabolism-independent
by phenolics at even a concentration of 1 mg l−1 could processes (physical and chemical adsorption, ion exchange,
bring about significant taste and odor problems making it complexation, chelation and microprecipitation) taking
unfit for use. Phenol becomes chlorophenols if chlorination place essentially in the cell wall. The main attraction of
is used to disinfect phenol-containing waters. Traditionally, biosorption are cost effectiveness and good removal perfor-
biological degradation, activated carbon adsorption, solvent mance; raw materials which are either abundant (sea weeds)
extraction and chemical oxidation are the most widely used or wastes from other industrial operations (fermentation
methods for removing phenols and its derivatives from wastes, activated sludge process wastes) can be used as
wastewaters [2–5]. Application of such traditional treatment biosorbents presenting performances often comparable with
techniques needs enormous cost and continuous input of those of ion exchange resins. The mechanism of binding by
inactivated biomass may depend on the chemical nature of
∗ Corresponding author. Tel.: +90-312-297-7434; pollutant (species, size, ionic charge), type of biomass, its
fax: +90-312-299-2124. preparation and its specific surface properties and environ-
E-mail address: zaksu@hacettepe.edu.tr (Z. Aksu). 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 ganisms are not affected by toxic wastes, they do not require
hydrophobic organic pollutants show a high tendency to a continuous supply of nutrients and they can be regener-
accumulate onto microbial cells or sludge, the microbial ated and reused for many cycles. However, the use of dead
biomass could be used as an adsorbent of biological origin biomass in powdered form has some problems, such as dif-
for the removal of very low concentration hazardous organics ficulty in the separation of biomass after biosorption, mass
from the wastewater. For all these reasons biosorption can be loss after regeneration and low strength and small particle
considered a promising technology for phenol removal from size, which make it difficult to use in column applications.
industrial waste streams and polluted natural waters [6–10]. To solve these problems, dead biomass can be immobilized
Both living and dead biomass can be used to remove haz- in a biopolymeric or polymeric matrix used as a support-
ardous organics, but maintaining a viable biomass during ing material. Immobilization may improve biomass perfor-
adsorption is difficult, because it requires a continuous sup- mance, biosorption capacity, increase mechanical strength
ply of nutrients and avoidance of organic toxicity to the mi- and facilitate separation of biomass from pollutant-bearing
croorganisms. The use of dead microbial cells in biosorption solution. Immobilization also allows higher biomass con-
is more advantageous for water treatment in that dead or- centration, resistance to chemical environments and column
Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613 601

operations and immobilized systems may be well suited for characteristics for use in typical chemical engineering oper-
non-destructive recovery. Indeed, the use of immobilized ations such as fixed beds. It has been used to demonstrate
biomass has a number of major disadvantages. In addition the potential for removal of phenol from waste streams in
to increasing the cost of biomass pre-treatment, immobiliza- a continuous packed bed column as a function of flow rate
tion adversely affects the mass transfer kinetics of phenol and inlet phenol concentration. The column phenol sorption
uptake. When biomass is immobilized the number of bind- equilibrium has been described by the use of Langmuir and
ing sites easily accessible to pollutant in solution is greatly Freundlich models. Several kinetic models are also applied
reduced since the majority of sites will lie within the bead. to experimental data to simulate the breakthrough curves in
So a good support material used for immobilization should order to predict the scale-up of a unit plant. To our knowl-
be rigid, chemically inert and cheap, should bind cells firmly, edge, this is the first attempt to immobilize a biomass in
should have high loading capacity and should have a loose Mowital® B30H resin in a fixed column and to test its use
structure for overcoming diffusion limitations [11,12]. as an biosorbent for the removal of phenol.
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 2. Mathematical description
is an effective process for cyclic sorption/desorption, as it
makes the best use of the concentration difference known to The performance of packed beds is described through
be a driving force for adsorption and allows more efficient the concept of the breakthrough curve. The time for break-
utilization of the sorbent capacity and results in a better qual- through appearance and the shape of the breakthrough curve
ity of the effluent. Continuous packed bed sorption has also are very important characteristics for determining the opera-
a number of process engineering advantages including high tion and the dynamic response of a biosorption column. The
yield operations and relatively easy scaling up from a labo- general position of the breakthrough curve along the volume
ratory scale procedure. The stages in the separation protocol axis depends on the capacity of the column with respect to
can also be automated and high degrees of purification can the feed concentration and flow rate. The breakthrough curve
often be achieved in a single step process. A large volume would be a step function for favorable separations, i.e. there
of wastewater can be continuously treated using a defined would be an instantaneous jump in the effluent concentra-
quantity of sorbent in the column. Reuse of microorganism tion from zero to the feed concentration at the moment the
is also possible. After pollutant loading the pollutant may column capacity is reached [8,11–19].
be concentrated in a small volume of solid material or des- The breakthrough curves show the loading behavior of
orbed into a small volume of eluant for recovery, disposal phenol to be removed from solution in a fixed bed and is
or containment [8,11,12]. usually expressed in terms of adsorbed phenol concentration
Activated sludge is a well known biomass used for (Cad = inlet phenol concentration(Co )−Outlet phenol con-
the purification of some industrial effluents and domestic centration (C)) or normalized concentration defined as the
wastes. Part of the microorganisms over grown in such ratio of effluent phenol concentration to inlet phenol con-
wastewater systems can be separated and utilized for re- centration (C/Co ) as a function of time or volume of effluent
moval of phenol as an abundant and cheaper biosorbent. for a given bed height [11]. Effluent volume (Veff ) can be
Activated sludge from wastewater systems contains both calculated from Eq. (1).
bacteria and protozoa. The cell wall of bacteria essentially
consists of various organic compounds such as carboxyl, Veff = Qttotal (1)
acidic polysaccharides, lipids, amino acids and other com-
ponents. The protozoa are unicellular, motile, relatively where ttotal and Q are the total flow time (min) and volumet-
large eucaryotic cells that lack cell walls. They can absorb ric flow rate (ml min−1 ). The area under the breakthrough
components through their outer membranes that contain curve (A) obtained by integrating the adsorbed concentra-
proteins and lipids [6,7,9,11]. tion (Cad ; mg l−1 ) versus t (min) plot can be used to find the
Mowital® B30H resin (a polyvinyl butyral based polymer) total adsorbed phenol quantity (maximum column capacity).
is a well known polymer used extensively in painting and Total adsorbed phenol quantity (qtotal ; mg) in the column for
coating industries. While it is abundant, extremely cheap a given feed concentration and flow rate is calculated from
than other immobilizing agents, non toxic and chemically Eq. (2):
inert, more suitable for preparation of porous beads, the solid  t=ttotal
and rigid support, showing little change in volume under any QA Q
qtotal = = Cad dt (2)
conditions, with dimensional stability under pressure, pro- 1000 1000 t=0
duced in the desired size and thus highly competitive with
Total amount of phenol sent to column (mtotal ) is calcu-
ion exchange resins and activated carbon so it can be used
lated from Eq. (3).
for immobilization of microorganisms for biosorption [11].
Activated sludge has been immobilized in Mowital® B30H Co Qttotal
resin in order to produce a biosorbent material with proper mtotal = (3)
1000
602 Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613

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

where KF and n are the Freundlich constants characteristic 2.1. The Adams–Bohart model
on the system. KF and n are indicators of adsorption capacity
and adsorption intensity, respectively. Equation (8) can be The fundamental equations describing the relationship
linearized in logarithmic form and Freundlich constants can between C/Co and t in a flowing system were established
be determined. According to the Freundlich equation, the by Adams and Bohart (1920) for the adsorption of chlorine
amount adsorbed increases infinitely with increasing con- on charcoal. Although the original work by Adams–Bohart
centration. This equation is, therefore, satisfactory for low was done for the gas–charcoal adsorption system, its over-
concentrations. The Freundlich isotherm is also more widely 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- 3. Experimental


solved this system and obtained the following solution:
 1/n−1 3.1. Microorganism
Con−1
=C (22)
1 + [(Cn−1 −rt
o /Cbreak − 1)e break ]e
n−1 rt The waste activated sludge collected from wastewater
treatment system of Meteksan Company-Ankara Paper and
or
 1/n−1 Board Mill, Turkey was used in this study. The harvested
C 1 cells were washed thoroughly with sterile distilled water,
= (23)
Co 1 + Ae−rt centrifuged at 5000 rpm for 5 min, dried at 60 ◦ C for 24 h to
with constant weight and then powdered before immobilization.
 
Cn−1 3.2. Preparation of Mowital® B30H resin immobilized
A= o
− 1 ertbreak (24)
Cn−1
break activated sludge
and
The method used for the immobilization is based on
kCl
R(n − 1) = r and R= ␯ (25) solvent evaporation. For each batch immobilization, 1 g
Uo Mowital® B30H (Hoechst) was dissolved in 8 ml of chloro-
Eq. (23) is the generalized logistic function where n; form (Merck). When Mowital® B30H resin was completely
Cbreak and tbreak are the Freundlich constant, the outlet con- dissolved in this solution, 1 g of dried and powdered ac-
centration at breakthrough (or limit effluent concentration), tivated sludge biomass was added to this medium mixed
and the time at breakthrough, respectively. For a particular continuously by means of an agitator. 4 g of polyvinyl al-
adsorption process on a fixed bed and a chosen treatment cohol (Sigma) used as the stabilizator was solved in 500
objective, values of A and r can be determined by using ml of distilled water. After that, 0.3 g of sodium dodecyl
Eq. (23) by non-linear regression analysis, enabling the pre- sulfate (Sigma) used as the emulsifier was added to this
diction of the breakthrough curve according to the relation- mixture and mixed thoroughly. At the last step, the first
ship between C/Co and t in Eq. (23), [15–17]. prepared mixture was added to this mixture. The mixing
operation was continued for 6 h at 750 rpm to obtain the
2.5. The Yoon and Nelson model porous, uniform and spherical immobilized particles and to
evaporate chloroform. Finally, the particles were removed
Yoon and Nelson (1984) have developed a relatively sim- from the immobilization medium and washed with distilled
ple model addressing the adsorption and breakthrough of water. These particles had 1.0 mm of mean diameter and
adsorbate vapors or gases with respect to activated charcoal. contained 50% dried activated sludge by weight [11].
This model is based on the assumption that the rate of de-
crease in the probability of adsorption for each adsorbate 3.3. Preparation of phenol solutions
molecule is proportional to the probability of adsorbate ad-
sorption and the probability of adsorbate breakthrough on Phenol solutions were prepared by diluting 1 g l−1 of stock
the adsorbent. The Yoon and Nelson model not only is less phenol solution, which was obtained by dissolving exact
complicated than other models, but also requires no detailed quantity of phenol (Merck) in double distilled and de-ionized
data concerning the characteristics of adsorbate, the type of water. The range in concentrations of phenol prepared from
adsorbent, and the physical properties of adsorption bed. stock solution varied between 50 and 500 mg l−1 . Before
The Yoon and Nelson equation regarding to a single- the biosorption in the continuous column system, the pH of
component system is expressed as: each test solution was adjusted to the required value with
C diluted and concentrated H2 SO4 and NaOH solutions.
ln = kYN t − ␶k YN (26)
Co − C
3.4. Sorption studies in the batch and column systems
where kYN is the rate constant (min−1 ); ␶, the time re-
quired for 50% adsorbate breakthrough (min) and t is the The effect of initial pH on phenol biosorption by
breakthrough (sampling) time (min). The calculation of the- Mowital® B30H resin immobilized activated sludge was
oretical breakthrough curves for a single-component system examined in a batch system. For the batch system studies,
requires the determination of the parameters kYN and ␶ for immobilized particles containing 0.05 g of dried activated
the adsorbate of interest. These values may be determined sludge were contacted with the known concentration of
from available experimental data. The approach involves a 100 ml phenol-bearing solution in Erlenmayer flasks at
plot of ln C/(Co −C) versus sampling time (t) according to the desired pH. The flasks were agitated on a shaker for
Eq. (26). If the theoretical model accurately characterizes 120 h, which is more than ample time for sorption equi-
the experimental data, this plot will result in a straight line librium. Three milliliter samples of solution were taken in
with slope of kYN and intercept ␶kYN [19,20]. definite intervals and analyzed for the residual phenol. The
Z. Aksu, F. Gönen / Process Biochemistry 39 (2004) 599–613 605

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 Fig. 1. The effect of initial pH on the equilibrium phenol uptake in the
absence of entrapped biomass. batch system (temperature, 25 ◦ C; initial pH, 1.0; Co , 100 mg l−1 ; X, 0.5
The studies were performed at a constant temperature of g l−1 ; agitating rate, 150 rpm).
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. the hydroxyl group of phenol and the functional groups on
cell surface like carboxylic may play a certain role in phenol
3.5. Analysis of phenol adsorption at very low pH values. Moreover donor–acceptor
interactions between the aromatic ring of phenol activated
The concentration of phenol in the effluent was de- by the OH− , and the groups of the biosorbent surface may
termined spectrophotometrically. The absorbance of the be also important in this case. At very low pH values, the
coloured complex of phenol with p-nitroaniline was read at surface of sorbent would also be surrounded by the hydro-
470 nm after [21]. 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
4. Results and discussion surface charge on the cells became negative and biosorp-
tion decreased. Because phenol exhibit significant binding
4.1. Effect of initial pH at higher pHs, there must be some additional types of reten-
tion mechanisms, including alterations in cell surface prop-
The most important single parameter influencing the sorp- erties and interactions of phenols with the cells by complex
tion capacity is the pH of adsorption medium. The initial formation or electron share or membrane transport [6,8–10].
pH of adsorption medium is related to the adsorption mech-
anisms onto the adsorbent surface from water and reflects 4.2. Effect of flow rate
the nature of the physicochemical interaction of the species
in solution and the adsorptive sites of adsorbent. The vari- In the first stage of removal studies in the continuous-flow
ation of equilibrium phenol uptake with initial pH obtained fixed column with Mowital® B30H resin immobilized acti-
from batch system studies was given in Fig. 1. The removal vated sludge, the flow rate was changed from 0.8 to 3.2 ml
of phenol from aqueous solution was more efficient with de- min−1 while the inlet phenol concentration in the feed was
creasing pH and was the greatest at pH 1.0. The equilibrium held constant at 100 mg l−1 at pH 1.0. The plots of compar-
phenol uptake was 55.6 mg g−1 at this pH value. Packed ative normalized phenol concentration versus effluent vol-
bed column studies were also performed at the same pH. ume at different flow rates are given in Fig. 6. As indicated
pH primarily affects the surface properties of the acti- in Fig. 6, at the lowest flow rate of 0.8 ml min−1 , relatively
vated sludge biomass, i.e. surface charge of the cells used as higher uptake values were observed for phenol biosorption
biosorbent. The surface charge of biomass is predominantly to immobilized activated sludge at the beginning of column
negative over the pH range of 3.0–10.0. Phenol could be ex- operation. But, as solution continued to flow, the concentra-
pected to become negatively charged phenoxide ion above a tion of phenol in the effluent rapidly increased, the bed be-
pH of 9.0 as pKa for phenol molecules at 25 ◦ C is 9.99. Be- came saturated with phenol and the concentration of solute
low a pH of 3.0, the overall surface charge on cells becomes in the effluent suddenly rose to inlet phenol concentration.
positive due to isoelectric point of activated sludge so the Much sharper breakthrough curves were obtained by immo-
electrostatic attraction between phenol and activated sludge bilized activated sludge at higher flow rates. The breakpoint
biomass will be insignificant. The hydrogen binding between 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

ε% = × 100 (27)
Fig. 3. The linearized Freundlich adsorption isotherm for phenol biosorp-
N
tion to Mowital®B30H resin immobilized activated sludge. where the subscripts ‘exp’ and ‘calc’ show the experimental
and calculated values and N the number of measurements.
indicates that n is greater than unity, indicating that phenol
are favorably adsorbed by the sorbent. 4.6. Application of the Adams–Bohart and
The Langmuir constants of Q◦ and b were determined the Wolborska models
from Ceq /qeq versus Ceq plot as 9.6 and 0.03. The Q◦ defines
the total capacity of biosorbent for phenol. The Adams–Bohart (or Wolborska) sorption model was
The Langmuir model makes several assumptions, such applied to experimental data for the description of the initial
as monolayer coverage and constant adsorption energy part of the breakthrough curve. This approach was focused
while the Freundlich equation deals with heterogeneous on the estimation of characteristic parameters, such as max-
surface adsorption. The applicability of both Langmuir and imum adsorption capacity (No ) and kinetic constant (kAB )
Freundlich isotherms to the immobilized activated sludge from Adams–Bohart model and kinetic coefficient of the
system implies that both monolayer adsorption and het- external mass transfer (␤a ) from Wolbraska model. After
erogeneous surface conditions exist under the experimental applying Eq. (13) (or Eq. (16)) to the experimental data
conditions used. for varying flow rates and inlet phenol concentrations, a
In general as expected, the values of isotherm constants linear relationship between ln C/Co and t was obtained for
obtained in a batch system show the maximum values of the relative concentration region up to 0.5, i.e. up to 50%
these constants and are considerably higher than those ob- breakthrough, for all breakthrough curves (R2 > 0.900). Re-
tained in a fixed bed as flow rate of solution is zero in batch spective values of No , kAB and ␤a were calculated from the
system, that is, the contact time between sorbate solution and ln C/Co versus t plots at all flow rates and inlet phenol con-
adsorbent approximates infinite. These experimental data are centrations studied are presented in Table 2 together with
generally used in further studies concerning the dynamic the correlation coefficients. The values of kinetic constant
adsorption of solute in column studies for the prediction of was influenced by flow rate and increased with increasing
breakthrough curves. However, it is important to note that flow rate. This showed that the overall system kinetics is
adsorption isotherms and constants determined in a fixed bed dominated by external mass transfer in the initial part of
should be used for evaluating the breakthrough curves and biosorption in the column. ␤a is also an effective coefficient
kinetic constants to model such a system mathematically. 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 above this level for the phenol adsorption in immobilized cell
beds or at high flow rates of solution through the bed, the column.
axial diffusion is negligible and ␤a = ␤o , the external mass Although the Adams–Bohart (or Wolbraska) model pro-
transfer coefficient. Increasing flow rate from 0.8 to 3.2 ml vides a simple and comprehensive approach to running and
min−1 increased the ␤a value since increased turbulence re- evaluating sorption-column tests, its validity is limited to the
duces the film boundary layer surrounding the immobilized range of conditions used.
particle. As expected, maximum adsorption capacity (No )
increased with increasing inlet phenol concentration. Pre- 4.7. Application of the Thomas model
dicted and experimental breakthrough curves with respect to
flow rate and inlet phenol concentration are shown in Figs. 4 The column data were fitted to the Thomas model to
and 5. It is clear from figures and average percentage errors determine the Thomas rate constant (kTh ) and maximum
(<22.4%) in Table 2 that there is a good agreement between solid-phase concentration (qo ). Application of Thomas
the experimental and predicted values, suggesting that the model to the data at C/Co ratios higher than 0.08 and lower
Adams–Bohart (or Wolbraska) model is valid for the relative than 0.97 with respect to flow rate and inlet phenol concen-
concentration region up to 0.5 where as large discrepancies trations enabled the determination of the kinetic coefficients
were found between the experimental and predicted curves 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 4.8. Application of the Clark model
from slope and intercept. Inspection of each of the regressed
lines indicated that they were all acceptable fits with linear In a part of study, it was found that the Freundlich model
regression coefficients ranging from 0.935 to 0.989 except was approximately valid for the adsorption of phenol on
the regressed lines obtained for 250 mg l−1 inlet phenol the immobilized activated sludge in the fixed bed column
concentration and 1.6 ml min−1 flow rate. The values of so the Freundlich constant n obtained were used to cal-
kTh and qo are presented in Table 3. As flow rate increased, culate the parameters in the Clark model. The adsorption
the values of kTh increased and the values of qo decreased. breakthrough could be well described by Clark model at
The bed capacity qo increased and the coefficient kTh de- the ratios of C/Co higher than 0.08 with respect to flow
creased with increasing inlet phenol concentration. The rate and inlet phenol concentration. Below these levels the
data in Table 3 also showed a negligible difference between model could not applied to experimental data. The values
the experimental and predicted values of the bed capacity of A and r in the Clark equation were determined using
(qo ) obtained at all inlet phenol concentrations studied al- Eq. (23) by non-linear regression analysis and are shown
though the deviations of experimental data from predicted in Table 4. The non-linearized regression analysis provided
values were evident at 1.6 and 3.2 ml min−1 flow rates. It the deviation values changing between 3.7 and 13.6% for
is clear from Figs. 6 and 7 that although the model gave a the model fit. From Table 4 as both flow rate and inlet
poor fit of the experimental data at higher flow rates, there phenol concentration increased, the values of r increased.
was a good agreement between the experimental and pre- Plotting C/Co against t according to this equation also gives
dicted normalized concentration values at all phenol inlet the breakthrough curves predicted by the Clark model.
concentrations. Figs. 8 and 9 showed the experimental and model-calculated
The Thomas model is suitable for adsorption processes breakthrough curves obtained at different flow rates and
where the external and internal diffusions will not be the at different inlet phenol concentrations. It appears that the
limiting step. 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 dried activated sludge has a considerable potential for the


removal of phenol over a wide range of phenol concen-
The biosorption of phenol from aqueous solution on tration. The results also indicated that the sorption process
Mowital® B30H resin immobilized dried activated sludge could only deal with lower flow rates and lower concentra-
was investigated in a continuous packed bed column. The tions of phenol solutions if a high percentage removal was
breakthrough curves for column sorption of phenol from required for extended periods. By adjusting the operating
dilute solutions to immobilized activated sludge have been characteristics of the packed column, for example the flow
measured at various flow rates and inlet phenol concentra- rate, inlet phenol concentration, particle size, biomass quan-
tions at 25 ◦ C. The results obtained showed that the sorption tity very rapid and efficient phenol uptake can be achieved
of phenol is dependent on both the flow rate and the inlet for the system.
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 References
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