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continuous packed bed: prediction of breakthrough curves

Zümriye Aksu∗ , Ferda Gönen

Chemical Engineering Department, Hacettepe University, 06532 Beytepe, Ankara, Turkey

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

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 4o 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

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

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

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

of kinetic constants

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

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%

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%

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 ).

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%

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 ).

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

used for the mathematical description of the biosorption

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and nickel(II) onto dried aerobic activated sludge. Sep Pur Technol

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