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The Biosorption of Phenol from Petroleum Refinery Wastewater

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DOI: 10.1080/15567036.2013.855845

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The Biosorption of Phenol from

Petroleum Refinery Wastewater Using
Spent Waste Biomass
a a a a
Sh. A. Younis , N. Sh. El-Gendy , W. I. El-Azab , Y. M. Moustafa & A.
b
I. Hashem
a
Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
b
Chemistry Department, Faculty of Science, Ain Shams University,
Cairo, Egypt
Published online: 11 Nov 2014.

To cite this article: Sh. A. Younis, N. Sh. El-Gendy, W. I. El-Azab, Y. M. Moustafa & A. I. Hashem
(2014) The Biosorption of Phenol from Petroleum Refinery Wastewater Using Spent Waste Biomass,
Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 36:23, 2566-2578, DOI:
10.1080/15567036.2013.855845

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 Energy Sources, Part A, 36:2566–2578, 2014
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/15567036.2013.855845

The Biosorption of Phenol from Petroleum Refinery

Wastewater Using Spent Waste Biomass

Sh. A. Younis,1 N. Sh. El-Gendy,1 W. I. El-Azab,1 Y. M. Moustafa,1 and

A. I. Hashem2
1
Egyptian Petroleum Research Institute, Nasr City, Cairo, Egypt
Downloaded by [N. Sh. El-Gendy] at 07:20 20 November 2014

2
Chemistry Department, Faculty of Science, Ain Shams University, Cairo, Egypt

This work investigates the potentiality of application of spent waste biomass (yeast Saccharomyces
cerevisiae, rice straw, and sugarcane bagasse) from bioethanol production process as low-cost biosor-
bents for removal of phenol from petroleum refinery wastewater. Batch adsorption studies were
carried out under varying experimental conditions of contact time, initial phenol concentration, and
operational temperature. Rice straw showed better affinity towards phenol than sugarcane bagasse,
while S. cerevisiae did not express any biosorption capacity. The biosorption process on rice straw
or sugarcane bagasse was fast and the time to reach equilibrium was found to be 150 min. Kinetic
studies showed that biosorption follows the pseudo-second order rate expression. The results were
better described by the Langmuir isotherm model than the Freundlich and Temkin isotherm models.
The calculated heat of adsorption indicated that the biosorption process is taking place by chemical
adsorption and has an endothermic nature.

Keywords: biosorption, equilibrium isotherm, kinetic study, phenol, spent waste biomass, thermody-
namic analyses

1. INTRODUCTION

Phenolic compounds are present in the wastewaters of industries, such as pharmaceuticals, coking,
synthetic rubber, petrochemicals, paper, and pesticides, etc. (Fang and Chan, 1997; Amin et al.,
2012). The well known treatment methods for wastewater containing phenolic compounds are:
advanced oxidation, membrane filtration, biological degradation, electrochemical oxidation, photo-
catalytic degradation, and adsorption (Rzeszutek and Chow, 1998; Rodgers et al., 1999; Esplugas
et al., 2000; Dabrowski et al., 2005; Guo et al., 2006). The last process is the most widely used
for treating domestic and industrial effluents due to its relatively simple implementation and low
operation costs. However, in water treatment, the most widely used adsorbents are activated carbon
(Hanchao et al., 2011), silica (Forland and Blokhus, 2007), montmorillonite (Yapar and Yilmar,
2004), and organophilic clays (Navarro et al., 2009).
In recent years, there have been many investigations with the aim of finding more economic,
practical, and effective adsorbents for the treatment of phenolic aqueous wastes. In the search

Address correspondence to Dr. Nour El-Gendy, Egyptian Petroleum Research Institute, Nasr City, Cairo 11727, Egypt.
E-mail: nourepri@yahoo.com
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ueso.

2566
 BIOSORPTION OF PHENOL 2567

for new and low-cost agricultural wastes as source material for wide use, bottom ash, brick-kiln
ash, fly ash, peat, soil, carbonized bark and pre-treated rice husk, rice straw, wood, saw dust, and
bagasse seem to be new inexpensive adsorbents that can be used for waste management (Srivastava
et al., 1997; Aksu and Yener, 2001; Rengaraj et al., 2002; Mandal et al., 2004; Barraclough et al.,
2005; Singh et al., 2008). However, the adsorption behavior of phenol on agricultural wastes,
without any pre-treatment, has not been extensively studied.
Therefore, the present work was performed to evaluate the use of spent waste biomass (Sac-
charomyces cerevisiae, rice straw and sugarcane bagasse) without any pre-treatment as low cost
adsorbents for treatment of petroleum refinery wastewater (PRW) containing phenols.

2. MATERIALS AND METHODS

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2.1. Biosorbents
In this study, spent biomass of yeast (Saccharomyces cerevisiae), rice straw (RS), and sugarcane
bagasse (SB) as spent waste by-products for the bioethanol production process undertaken in the
Petroleum Biotechnology Laboratory of the Egyptian Petroleum Research Institute, were used.
The collected biomaterials were washed with hot deionized water several times, dried in a
hot air oven at 105ıC until a constant weight, crushed with a grinder, sieved to constant sizes
(0.25–0.315 mm), and then used as it is without any further chemical or physical pretreatments.

2.2. Authentic Petroleum Refinery Wastewater Preparation

In order to simulate the real feed of PRW effluents, the authentic wastewater (WW) for the
present study was prepared based on previously measured physico-chemical characteristics of
PRW effluents collected from Cairo Oil Refining Company (CORC) plant (data not shown). The
authentic WW used in this study was composed of NaCl, 0.48 g; KCl, 0.019 g; MgSO4 , 0.074 g;
Na2 SO4 , 0.009 g; CaCl2 , 0.12 g; MgCl2 , 0.04 g; NaHCO3 , 0.18 g; and CaSO4 , 0.03 g dissolved
in 1,000 mL of deionized water.
A background solution comprised of authentic WW:Acetone (70:30 v/v) was used to grantee
complete dissolve of phenol, and 200 mg/L NaN3 was added to inhibit the degradation by
incidental bacteria as recommended by Chen et al. (2011). The initial pH of the background
solution was adjusted to pH 7 ˙ 0:2 using 0.1N HCl or NaOH aqueous solution without any
further adjustment during the sorption process.
A stock solution of phenol with a concentration 200 mg/L was prepared, which was further
diluted by background solution according to the experimental conditions.

2.3. Batch Biosorption Experiments

All of the batch biosorption experiments were conducted by contacting 25 mL of background
solution of a known phenol concentration (adsorbate) with 0.5 g of biosorbent in a 100-mL
Erlenmeyer flask closed with PARAFILM ‘M’ to prevent evaporative loss and placed in a rotary
shaking incubator of 150 rpm at different temperatures (Table 1). Biosorbent was separated from
the solution at predetermined time intervals by centrifugation at 4,000 rpm for 10 min. The
absorbance of the supernatant solution at 288 nm was measured to determine residual phenol
concentration and calculate the percentage of phenol removal.
Negative controls (without biosorbents) were carried out to ensure that sorption is by dried
biomass only and any sorption effect of phenols onto the wall of the flasks is negligible. Biosorp-
tion capacity and percentage of phenol removal were determined at different contact times with
 2568 SH. A. YOUNIS ET AL.

TABLE 1
Different Process Conditions Used for Biosorption of Phenol

Process Factors Other Conditions

Different biosorbents
Yeast, RS, and SB
Contact time (0–360 min)
Different temperatures
288, 303, and 318 K
Temperature: 303 K; Contact time: 24 h to grantee that equilibrium was attained.
Temperature: 303 K; Biosorbent type: RS and SB and different phenol
concentrations (10, 25, and 50 mg/L).
Contact time: 300 min; Different initial phenol concentrations: 2.5–150 mg/L.

different initial phenol concentrations to know the equilibrium contact time. Effect of temperature
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was also studied. Table 1 illustrates all of the process factors. All experiments were carried out
in duplicates.

2.4. Analysis
Phenol was obtained from Sigma Chemical Company (USA). Phenol concentration was measured
by a JASCO UV/Vis/NIR spectrophotometer (model V-570) at 288 nm. A standard curve for
different concentrations of phenol solution (2.5–50 mg/L), established as the concentration range
of phenol adhering to Beer’s law under the conditions of investigation for the system, was 0–50
mg/L and background solution was used as the blank.
The removal percentage and biosorption capacity qt mg/g were calculated as follows:
.C0 Ct /
Removal % D  100; (1)
Co
.Co Ct /V
qt D ; (2)
M
where Co and Ct are the initial and final concentrations of the solute in solution (mg/L), respec-
tively, V (L) is the volume of the solution, and M (g) is the mass of the biosorbent.

3. RESULTS AND DISCUSSION

3.1. Effect of Different Biosorbents

RS showed the highest biosorption capacity, while S. cerevisiae expressed no biosorption affinity
towards phenol. RS and SB removed 62 and 51.4% of 10 mg/L phenol with biosorption capacity
of 0.31 and 0.27 mg/g after 24 h, respectively.

3.2. Pre-equilibrium Kinetics of Different Phenol Concentration

Equilibrium time is one of the important considerations in the design of water and wastewater
treatment systems, as it influences the size of the reactor, thereby the plant economics. Thus,
biosorption of phenol was studied as a function of time at different initial phenol concentrations, to
determine the rate of phenol adsorption on the surface of biosorbent and determine the equilibrium
time for phenol uptake. It was noticed that the adsorption curves (Figure 1) were smooth and
continuous leading to saturation at various phenol concentrations on the outer interface of the
 BIOSORPTION OF PHENOL 2569
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FIGURE 1 Effect of contact time at different initial phenol concentration on its biosorption on RS and SB.

biomass. This might indicate the possibility of mono-layer coverage of phenol on the outer
interface of the biosorbent (Dogan et al., 2004; Farah et al., 2007 and Farah and El-Gendy,
2013). Phenol removal percentage decreased as the initial phenol concentration increased and
it was initially rapid and increased with time until equilibrium was attained, nearly after 150
min, with an adsorption of approximately 60, 59, and 53% for RS and 49, 47, and 40% for
SB, at initial phenol concentrations of 10, 25, and 50 mg/L, respectively. Almost no remarkable
increase in adsorption was observed after longer contact time. Therefore, equilibrium time was
set conservatively at 300 min for further experiments. Initially, a large number of vacant surface
sites is available for adsorption, thus, there would exist increased concentration gradient between
adsorbate in solution and adsorbate on the adsorbent. Hence, the adsorption rate is very fast
thus increasing rapidly the amount of phenol (adsorbate) accumulated on the RS or SB surface
approximately within the first hour of adsorption. As a result, the remaining vacant surface sites
are difficult to be occupied due to formation of repulsive forces between the phenol molecules
on the solid surface and the bulk phase. Phenol molecules have to penetrate deeper into pores
encountering much higher resistance. This might explain the decrease of adsorption rates. Similar
 2570 SH. A. YOUNIS ET AL.

observations were reported by Achak et al. (2009) using banana peels for removal of phenolic
compounds from olive mill wastewater and Amin et al. (2012) using rice straw for removal of
phenol from wastewater.
It is worth mentioning that the percentage of phenol removal decreased and the actual amounts
of phenol uptake by the biosorbent increased, with the initial increase of phenol concentration,
recording at 360 min, approximately 0.31, 0.73, and 1.33 mg/g RS and 0.25, 0.6, and 0.98 mg/g
SB at an initial phenol concentration of 10, 25, and 50 mg/L, respectively. This means that the
increase in adsorption is limited with biosorbent dose. According to Mane et al. (2007), this
phenomenon might be due to the increase in the driving force of the concentration gradient with
the initial adsorbate concentration. That would increase the mass transfer of phenol molecules from
the solution onto the biosorbent surface. Hence, a higher initial phenol concentration enhances
the adsorption process and, as the adsorption process proceeds, the driving force decreases with
time.
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3.3. Biosorption Kinetic Modeling

In order to investigate the biosorption process of phenol onto RS or SB, pseudo-first- and second-
order kinetic models were tested for the obtained data to elucidate the adsorption mechanism.
The best fit model was selected based on the linear regression correlation coefficient, R2 values,
statistical error function (Eq. (3)), and standard deviation analysis (Eq. (4)).
The sum of the squares of errors (SSE) (Wong et al., 2004):
N
X
SSE D .qt;cal qt;exp /2 : (3)
i D1

A normalized deviation, qt % (Aksu and Yener, 2001):

N  
X qt;exp qt;cal
qt;exp
i D1
qt % D  100; (4)
N
where qt;exp and qt;cal are the experimental and calculated adsorption capacity mg/g, respectively,
and N is the number of data points. The higher the values of R2 and the lower the values of SSE
and qt %, the better the fit is.
The pseudo-first-order reaction equation of Lagergren (1898) is widely used for the adsorption
of liquid/solid system on the basis of solid capacity. Its linear form is generally expressed as
follows:
K1
log.qe qt / D log qe t: (5)
2:303
qe (mg/g) and qt (mg/g) are the adsorbed amount at equilibrium and time t (min), respectively.
K1 (min 1 ) is the rate constant in the pseudo-first-order adsorption process. The constants were
determined by plotting of log.qe qt / versus t as listed in Table 2. The R2 , SSE, and qt %,
values ranged between (0.96–0.99) and (0.86–0.92), (0.001–0.017) and (0.023–0.169), and (13.69–
14.69%) and (22.60–28.19%) for SB and RS, respectively.
The pseudo-second-order model proposed by Ho and McKay (1999) is based on the assumption
that the adsorption follows second order chemisorption. The linear form can be written as follows:
t 1 1
D C t; (6)
qt K2 qe2 qe
 BIOSORPTION OF PHENOL 2571

TABLE 2
Pseudo-first- and Second-order Kinetic Models for Biosorption of Different Phenol
Concentrations onto RS and SB

SB RS

Kinetic Models 10 mg/L 25 mg/L 50 mg/L 10 mg/L 25 mg/L 50 mg/L

Pseudo-first-order kinetic
R2 0.99 0.98 0.96 0.86 0.89 0.92
K1 (min 1 ) 0.020 0.019 0.017 0.039 0.033 0.028
qe;exp (mg/g) 0.25 0.60 1.01 0.31 0.75 1.33
qe;calc (mg/g) 0.23 0.57 0.95 0.24 0.62 1.16
SSE 0.001 0.006 0.017 0.023 0.095 0.169
qt (%) 13.69 14.69 13.73 28.19 26.30 22.60
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Pseudo-second-order kinetic
R2 0.99 1.00 0.96 0.98 0.98 0.99
K2 (g/mg min) 0.126 0.054 0.026 0.333 0.112 0.048
qe;exp (mg/g) 0.25 0.60 1.01 0.31 0.75 1.33
qe;calc (mg/g) 0.25 0.58 1.01 0.31 0.74 1.31
h0 (mg/g min) 0.008 0.018 0.027 0.033 0.062 0.081
SSE 0.00002 0.00003 0.0010 0.0005 0.0020 0.0033
qt (%) 1.22 0.27 3.52 3.99 3.96 3.07

where K2 is the pseudo-second-order rate constant (g/mg min). By plotting t=qt against t, qe and
K2 can be evaluated. The initial adsorption rate, ho (mg/g min), is defined as (Yao et al., 2010):

ho D K2 qe2 : (7)

The values of qe;cal, K2 , ho , and R2 are listed in Table 2. The dependence of t=qt versus t gives
an excellent straight line relation for all of the experimental concentrations, all of the R2 values
are close to unity with lower SSE and qt % than those of pseudo-first-order kinetic model. This
confirms the applicability of the pseudo-second order equation. In addition, there is nearly no
difference between the qe;exp and qe;cal , which reinforces the applicability of the pseudo-second-
order model equation. This suggests that the overall rate of the phenol biosorption process on
spent waste biomass of RS or SB appears to be controlled by the chemisorption process, which
may be partly due to the hydrogen-bonding between the hydroxyl group of phenol molecules and
the active functional groups in the RS and SB, and it may be the rate-limiting step. Ho (2003)
reported that chemical sorption can occur by the polar functional groups of lignin, which include
alcohols, aldehydes, ketones, acids, phenolic hyrdoxides, and ethers as chemical bonding agents.
It can also be seen in Table 2 that, with an increase in initial phenol concentration, initial
adsorption rate ho (mg/g min) and equilibrium sorption capacity increased. But the rate constant
of adsorption K2 (g/mg min) decreased.

3.4. Effect of Temperature on the Biosorption Process

The phenol biosorption increased by increasing the temperature of the solution from 288–318 K
(Figure 2), therefore this system is endothermic. This also confirms a chemisorption mechanism,
where there is an increase in the number of molecules acquiring sufficient energy to undergo
chemical reaction with increasing temperature. The increase in phenol adsorption with temperature
may be due to dissolution of the adsorbing species, changes in the pores size of the adsorbents,
and enhanced rate of intra-particle diffusion. Ajmal et al. (2000) and Gupta et al. (2003) reported
 2572 SH. A. YOUNIS ET AL.
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FIGURE 2 Comparison of theoretical Langmuir isotherm plots (solid line) with experimental results (symbols)
for biosorption of phenol onto RS and SB.

that increasing the temperature is known to increase the diffusion rate of the adsorbate molecules
across the external boundary layer and in the internal pores of the adsorbent particles owing to
the decrease in the viscosity of the solution. In addition, the creation of some new active sites for
additional sorption on the surface of the sorbent is endothermic.

3.5. Sorption Equilibrium

The analysis and design of the sorption process requires relevant adsorption equilibrium data,
which provide fundamental physicochemical data for evaluating the applicability of the sorption
process to design a unit operation.
Langmuir, Freundlich, and Temkin models were used for the equilibrium modeling of the
studied biosorption system. Isotherm constants and the correlation coefficient, R2 , with SSE and
qe % are listed in Table 3.
Within all of the studied range of temperatures 288–318 K, as the initial phenol concentration
increased the biosorption capacity qe mg/g increased. The isotherm curves (Figure 2) became
 BIOSORPTION OF PHENOL 2573

TABLE 3
Isotherm Constants of Langmuir, Freundlich, and Temkin Isotherm Models for Biosorption of Phenol at
Different Temperatures onto RS and SB

Temperature

SB RS

288 K 303 K 318 K 288 K 303 K 318 K

Langmuir
aL (L/g) 0.084 0.045 0.041 0.057 0.050 0.140
KL (L/g) 0.045 0.067 0.091 0.051 0.098 0.280
qe max;exp (mg/g) 0.479 1.213 1.754 0.783 1.587 1.863
qe max;theo (mg/g) 0.494 1.262 1.837 0.787 1.665 1.885
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RL 0.07 0.13 0.14 0.10 0.12 0.05

R2 0.99 0.99 0.99 1.00 0.98 1.00
SSE 0.008 0.026 0.069 0.006 0.128 0.139
qeq (%) 6.55 4.37 5.36 5.60 8.10 6.97
Freundlich
n 2.31 1.70 1.55 2.00 1.61 2.13
Kf (L/g) 0.08 0.11 0.13 0.09 0.13 0.32
R2 0.900 0.94 0.950 0.934 0.922 0.907
SSE 0.069 0.449 1.118 0.134 1.355 1.799
qeq (%) 14.67 16.53 16.84 13.60 18.04 20.57
Temkin
Kt (L/mg) 0.79 0.49 0.49 0.60 0.54 1.66
B 0.12 0.32 0.46 0.19 0.40 0.42
b (J/mol) 20,511 7,996 5,782 12,709 5,965 6,674
R2 0.94 0.97 0.96 0.98 0.95 0.94
SSE 0.020 0.127 0.359 0.046 0.391 0.417
qeq (%) 12.24 33.66 51.28 20.25 45.53 29.76

smooth and approached the plateau value at higher phenol concentrations. The plateau region of
the isotherm represents well-packed phenol molecules covering the total surface of the biosorbent
(Sankar et al., 1999).
The Langmuir adsorption isotherm is based on the assumption of monolayer adsorption on a
structurally homogeneous adsorbent, where all the sorption sites are identical and energetically
equivalent. It can be expressed by the non-linear form of the Langmuir (1916) equation:

KL Ce
qe D : (8)
1 C aL Ce

Characteristic constants of the Langmuir equation, KL and aL , can be determined from the
linearized form of Eq. (8):

Ce 1 aL
D C Ce : (9)
qe KL KL

The theoretical maximum adsorption capacity .qe max;theo/ corresponding to Langmuir constants is
numerically equal to KL =aL (Allen et al., 2004).
 2574 SH. A. YOUNIS ET AL.

The essential features of Langmuir can be expressed in terms of dimensionless constant

separation factor RL , which was defined by Weber and Chakravorti (1974) as:
1
RL D : (10)
1 C aL Co
Values of RL indicate the shapes of isotherms to be either unfavorable .RL > 1/, linear .RL D 1/,
favorable .0 < RL < 1/, or irreversible .RL D 0/, where Co (150 mg/L) is the maximum initial
phenol concentration used in isotherm studies. Langmuir constants aL and KL can be determined
from the linear plots of Ce =qe versus Ce at different temperatures. The qe max;exp, qe max;theo mg/g
and RL values are listed in Table 3.
It can be observed that RL at different temperatures ranged between 0 and 1 for RS and SB,
which confirms favorable isotherm.
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The Freundlich isotherm model (1906) is an empirical expression that can be used for non-ideal
sorption that involves heterogeneous sorption. The non-linear form of the Freundlich equation is:

qe D Kf Ce1=n: (11)

The characteristic constants of the Freundlich model, Kf (L/g) and n, were determined from the
logarithmic linearized form of Eq. (11):
1
log qe D log Ce C log Kf : (12)
n
When plotting log qe versus log Ce , straight lines were obtained with R2  0:90. The obtained
exponent n (Table 3) indicates the favorability of the adsorbent/adsorbate system where values
of n were >1 for all studied temperature ranges. According to Treybal (1980) n > 1 represents
favorable adsorption.
Temkin and Pyzhev (1940) considered the effect of some indirect sorbate/adsorbate interactions
on the adsorption isotherm. This isotherm assumes that the heat of adsorption of all the molecules
in a layer decreases linearly with surface coverage of adsorbent due to sorbate-adsorbate interac-
tions (Liu and Liu, 2008). This adsorption is characterized by a uniform distribution of binding
energies. The Temkin isotherm can be represented by the following equation:
RT
qe D ln.Kt Ce /: (13)
b
This can be expressed in its linear form:

qe D B ln Kt C B ln Ce ; (14)

where B D RT=b, T is the absolute temperature in K, R is the universal gas constant (8.314
J/Kmol), and Kt is the equilibrium binding constant. By plotting qe versus ln Ce , straight lines
were obtained with R2  0:94 (Table 3). Constant B, which is related to the heat of adsorption,
increases with the increase in temperature, proving endothermic adsorption. The values of B are
greater than 8 J/mol, indicating strong interaction between phenol molecules and biomass and
considered as chemisorption of an adsorbate onto the adsorbent (Anwar et al., 2010; Boparai
et al., 2011; Farah and El-Gendy, 2013).
By comparing results listed in Table 3, it is clear that equilibrium data fit Langmuir, Freundlich,
and Temkin models, where R2  0:90. But Langmuir model expressed the highest R2 , close
to unity with the lowest SSE and qe %. That means the Langmuir sorption isotherm model
gives the best agreement with obtained experimental data and more accurately describes the
 BIOSORPTION OF PHENOL 2575

sorption of phenol on RS and SB, as shown in Figure 2. This gives a possibility of mono-
and hetero-layer phenol molecules formation on the adsorbent surface. Similar observations were
reported by Annadurai et al. (2002) for adsorption of dye on cellulose-based wastes; Vázquez
et al. (2007) for adsorption of phenols from coke wastewater; Achak et al. (2009) for adsorption
of phenolic compounds onto banana peels; and Mohd Din et al. (2009) for adsorption of phenol
onto physicochemical-activated coconut shell. They attributed this phenomenon to the surface
chemistry of the adsorbent.
The spent waste RS and SB used in this study are composed of  15–18% hemicellulose,
17–21% cellulose, 7–8% lignin, and the rest are ashes containing silicates and other minor and
trace elements (Madian et al., 2012; Abo State et al., 2013). The presence of active functional
groups with different intensity and non-uniform distribution may cause differences in the energy
level of the active sites available on the RS and SB surfaces, which consequently would affect their
biosorption capacity. According to Achak et al. (2009), active sites with a higher energy level tend
Downloaded by [N. Sh. El-Gendy] at 07:20 20 November 2014

to form hetero-layer phenol molecules coverage with robust support from strong chemical bonding,
while active sites with lower energy level will induce monolayer coverage due to electrostatic
forces.
In this study, the experimental (qe max;exp 0.479–1.754 and 0.783–1.863 mg/g) and theoretical
(qe max;exp 0.494–1.837 and 0.787–1.885 mg/g) maximum sorption capacity for phenol onto SB and
RS (Table 3) were higher than those reported by other researchers. Maleki et al. (2010) reported,
0.067 mg/g for phenol biosorption on barley straw. Amin et al. (2012) reported, 0.15 mg/g for
phenol biosorption on rice straw.

3.6. Thermodynamic Analyses of Biosorption Isotherm Data

The values of thermodynamic parameters are relevant for the practical application of biosorption
process. Isotherm data related to biosorption of phenol onto untreated spent waste RS and SB
at different temperatures (288–318 K) were analyzed to obtain the values of thermodynamic
parameters; Gibbs free energy change G (kJ/mol), enthalpy change H (kJ/mol), and entropy
change S (kJ/mol K), which were estimated using Clausius-Clapeyron equation:

G D RT ln KL ; (15)
G S 
ln KL D D ; (16)
RT R RT
G D H TS: (17)
Hence, a plot of ln KL versus 1/T yields a line with a slope D H=R from which H can
be calculated (Figure 3).
From data listed in Table 4, it can be concluded that the positive value of G indicates the
nonspontaneous nature of phenol biosorption on RS and SB. The G decreased with increase in
temperature, thus biosorption of phenol onto RS and SB was enhanced at a higher temperature.
The positive value of S reflects the good affinity of phenol towards RS and SB and suggests
the increase of randomness at the solid-solution interface during the sorption of phenol onto the
biomass. The positive value of H indicates chemical adsorption, confirms the endothermic nature
of the biosorption process, which is an indication of the existence of a strong interaction between
biomass and phenol molecules (Shahryari et al., 2010; Farah and El-Gendy, 2013), and suggests
some structural changes in adsorbate and adsorbent. This also suggests that the chemical bonds
between the biosorbent and phenol molecules are strong enough and phenol molecules cannot be
easily desorbed by physical means, such as simple shaking or heating. Similar observation was
reported by Ajmal et al. (2003) for adsorption of Cd(II) from wastewater onto rice husk.
 2576 SH. A. YOUNIS ET AL.
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FIGURE 3 Clausius-Clapeyron plots for adsorption of phenol onto RS and SB.

TABLE 4
Thermodynamics Parameters for Biosorption of Phenol onto RS and SB

SB RS
Biosorption
Temperature, G, H, S, G, H, S,
K kJ/mol kJ/mol J/mol K kJ/mol kJ/mol J/mol K

288 7.44 18.02 40 7.13 43.06 120

303 6.82 5.86
318 6.34 3.37

4. CONCLUSIONS

The spent waste biomass of yeast Saccharomyces cerevisiae does not show any affinity towards
phenol and further pre-treatment before its application is recommended, e.g., to be acid treated.
The spent waste biomass of rice straw (RS) and sugarcane bagasse (SB) as waste by-products for
the bioethanol production process proved to be a promising material for removal of phenols from
petroleum refinery wastewater. The rapid observed kinetics of biosorption of phenol on RS and SB
 BIOSORPTION OF PHENOL 2577

has significant practical importance, as it will facilitate smaller reactor volumes ensuring efficiency
and economy. The biosorption mechanism follows a pseudo-second-order reaction model. The
initial phenol concentration provides a driving force to overcome mass transfer resistance. The
increase in temperatures results in a higher phenol loadings per unit weight of the sorbent. Results
obtained from this study are well described by Langmuir isotherm model and to a lower degree
by Freundlich and Temkin. Thermodynamic analyses indicates that the biosorption of phenol onto
RS and SB takes place by chemical adsorption and has an endothermic nature.

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