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International J. Eng. Tech 8(4):841-846, December 2011
A publication of G-Science Implementation & Publication website: www.gscience.net or www.gurpukur.com


ADSORPTION OF PHENOL FROM AQUEOUS SYSTEM USING RICE STRAW

MOFIZUR RAHMAN
1
, MD. RAIHAN CHOWDHURY
2
, SURIA JAHAN
3
, MD. RAKIB UDDIN
4

and AHMAD ISMAIL MUSTAFA
5



ABSTRACT
An examination of adsorption of phenol and phenolic compound on Rice Straw is followed by a critical
assessment of low-cost adsorbents. Experiments have been conducted to examine the adsorption of phenol
and phenolic compounds from industrial effluent by using agricultural wastes on Rice Straw and were
carried out for the analysis of adsorption equilibrium capacities using a batch equilibrium technique. Batch
adsorption isotherm studies were carried out under varying experimental conditions of contact time,
operational temperature, adsorbent dose, initial phenol concentration, particle size and pH of phenol
solution. Adsorption equilibrium of Rice Straw was reached within 3 hour for phenol concentration
500g/L. Kinetics of adsorption obeyed a first-order rate equation. The suitability of the Freundlich and
Langmuir adsorption models to the equilibrium data were investigated for phenol-sorbent system. The
results showed that the equilibrium data for all the phenol-sorbent systems fitted the Freundlich model and
Langmuir modal within the concentration range studied. 83.2% removal of phenol were achieved at given
adsorption conditions from aqueous system which could be regenerated by desorption with the help of 1 M
NaOH and recovered 95.30% of adsorbed phenol. This study has proven that Rice Straw is a useful
agricultural waste product for the removal of phenol and phenolic compounds from aqueous system. This
study was mainly conducted at the laboratory of Applied Chemistry & Chemical Engineering, University of
Dhaka and partial work was done at laboratory of Analytical Research Division, Bangladesh Council of
Scientific and Research, during the period of December 2009 to July 2010.

Keywords: Aqueous system, Rice straw, Phenol, Freundlich and Langmuir adsorption model.

INTRODUCTION

Phenol is one of the most abundant organic pollutants in industrial wastewater. It is released to the
environment from industries such as petroleum refining, textile industries, coal tar, steel, tanning,
pesticides, pharmaceuticals, etc. Phenol has attracted public attention due to its presence in groundwater,
rivers and drinking waters. Even in small quantities, phenol causes toxicity and foul odor to the water.
Most countries specify maximum allowable concentration of phenol in effluent to be less than 1 ppm.
Continuous ingestion of phenol for a prolonged period of time causes mouth sore, diarrhoea, excretion of
dark urine and impaired vision at concentration levels 10/240 ppm. Lethal blood concentration for phenol
is around 1.3 g/L. phenols are toxic to several biochemical functions and to fish life. It acts as a substrate
inhibitor in the bio-transformation. World Health Organization (WHO) prescribed a concentration 1 ppb
as the guideline concentration in drinking water (WHO, 1984). Several treatment methods such as chemical
oxidation, biological treatment, wet oxidation, ozonolysis, precipitation, ion exchange, adsorption, electro
dialysis and adsorption have been proposed for removing phenol from industrial effluents. However, these
methods have limitations on selective separation and high cost of investment and operation of equipment.
By using agricultural waste, the adsorption of pollutants from aqueous solutions can be more economical
with regard to other similar physico-chemical processes. So, adsorption is an economically feasible
alternative method for removing trace phenol from wastewater. Adsorption is an effective purification and
separation technique used in effluent treatments. Use of agricultural wastes, has many advantages such as
low capital and operating costs, selective removal of phenol and phenolic compounds, adsorbent
regeneration and phenol and phenolic compounds recovery potentiality, rapid kinetics of adsorption and
desorption and no sludge generation (Frcd Gurnham, 1970). The binding mechanisms of phenol by
adsorption could be explained by the physical and chemical interactions between cell wall ligands and

1
Department of Applied Chemistry and Chemical Engineering, University of Dhaka, Email: mofizndc@yahoo.com,
2
Department
of Biochemistry & Molecular Biology, University of Dhaka, Email: mcraihan@gmail.com,
3
Department of Pharmacy,
Jahangirnagar University. Email: suriyapharma_2006@yahoo.com,
4
Department of Pharmaceutical Chemistry, University of
Dhaka, Email: rakibuddin.md@gmail.com and
5
Department of Applied Chemistry and Chemical Engineering, University of
Dhaka, Bangladesh. Email: mustafa@du.bangla.net.

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adsorbents by physical adsorption and diffusion of phenol from the bulk solution to active sites of
adsorbents predominantly occurs by passive transport mechanisms and various functional groups such as
carboxyl, hydroxyl, amino and phosphate existing on the cell wall of adsorbents which can bind the
phenol and phenolic compounds (Walter Lorch, 1986). Cost is an important parameter for comparing the
adsorbent materials. Rice straw has been used for wastewater treatment and the potential of their ultimate
usage may be determined by their adsorption capacity, regeneration characteristics and physical properties
of subsequent products. It was, therefore, thought worthwhile to make a venture in order to develop a very
simple but highly efficient and effective technique for the removal of Phenol from industrial effluents
using Rice Straw. Adsorption techniques are widely used to remove certain classes of pollutants from
wastewater. Phenolic compounds represent one of the problematic groups in wastewater management.
Although commercial activated carbon is a preferred adsorbent for phenol removal, its widespread use is
restricted due to the high cost. Economy of our country is yet dependent on agriculture, and rice is the
main crop our country. So considering the socioeconomic condition of our countryour main objective of
this study is to introduce low-cost agricultural waste like as rice straw which could be an effective agent
for industrial effluent treatment to remove phenol and phenolic compounds from the industrial waste.

MATERIALS AND METHODS

Preparation of adsorbent: Straw is an agricultural by-product, the dry stalks of cereal plants, after the grain
and chaff have been removed. Straw makes up about half of the yield of cereal crops such as rice. The rice
has long, slender leaves 50-100 cm long and 2-2.5 cm broad. The small wind-pollinated flowers are
produced in a branched arching to pendulous inflorescence 30-50 cm long. The edible seed is a grain
(caryopsis) 5-12 mm long and 2-3 mm thick. The Rice Straws were carefully collected without any
contamination from local area. After collecting, Rice Straws were treated to make them ready for use. The
Rice Straw were dried initially in an oven at about 70C and then ground to fine mesh and the particles of
40, 80, 120, 160, 200 mesh size were separated by sieving through standard test sieves.
Reagents and Materials: All the reagents and chemicals used were of Analytical Grade. Phenol, 4-
amino antipyrine was obtained from BDH Chemicals Ltd., Poole England. Potassium Ferricyanide was
obtained from Loba Chemie Pvt. Ltd. India. Stock solution of phenol (1000 ppm) was obtained by
dissolving 0.5 gm phenol in 500 ml double distilled water. Potassium Ferricyanide (8% W/V) Solution
was prepared by dissolving 8.0 gm of potassium ferricyanide in 100 ml double distilled water. And 4-
aminoantipyrine (2%-W/V) Solution was prepared by dissolving 2.0 gm 4- amino antipyrine in 100 ml
double distilled water (American Public Health Association, 1985). The phenol estimation was done by
using Shimadzu UV-VIS 1700 double beam spectrophotometer.

Estimation of phenol by modified method: The 4-aminoantipyrine method gave unsatisfactory result
(Rengaraj et al., 2002). So attempts were made to modify the 4-aminoantipyrine method. Preliminary
experiments showed that phenol does not give any appreciable color with 4-aminoantipyrine in presence
of potassium ferricyanide in acidic medium. But at pH 8.0 phenols gives a deep brownish red color whose
intensity gradually increases up to pH 10.0 and then sharply decreases. This color system was made the
basis for the development of the modified spectro photometric method for the determination of trace
amount of phenol at a pH 10.0 instead of pH 8.0. Absorbance measurements, carried out against reagent
blanks, revealed that the absorption maxima are at 500 nm and that the time required for full color
development is 25 minutes. Experimental result revealed that 0.4 mL of 2.0% (w/v) 4-aminoantipyrine
solution is sufficient for the development of maximum color intensity of the system containing 5 ppm
phenol solution. Results of the effect of potassium ferricyanide indicates that 0.5 mL of 8.0% of (w/v)
potassium ferricyanide solution is the optimum amount for the development of the maximum color
intensity of the system containing 5 ppm phenol solution. It was also observed that the color intensity
gradually decreases beyond this range. It was found that the modified method was more suitable.

Estimation of standard calibration curve: A standard curve is a graph relating a measured optical density
to concentration of the substance of interest in "known" samples. The standard calibration curve is
drawn by plotting absorbance (on the Y axis) vs. concentration (on the X axis). Result of standard

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calibration curve is shown in table (1). Standard curve is determined by the system containing 5 ppm
phenol solution with 0.5 ml potassium ferricyanide solution, 0.4 ml 4amino antipyrine, 5 ml buffer
solution (pH 10). The results are graphically represented in fig. (a).



Table 1. Phenol Vs Absorbance.

Phenol variation
max,
nm Absorbance
1 0.0998
2 0.1888
3 0.2801
4
500
0.3601
5 0.4745
6 0.6111
7 0.8301
8 0.9027
9 0.9454
10 0.9811





















Fig. (a). Standard curve.


Removal of phenol from aqueous solution: The batch experiments were conducted using 2.5 gm of
adsorbent in 250 mL capacity stopper bottles with 100 mL phenol solution. The whole study was
carried out at pH 8.0; at higher pH the texture of the adsorbent is changed. The bottles were then shaken
at uniform speed at room temperature using an electric shaker (Cooper, 1985). At predetermined time
intervals the contents were centrifuged and the remaining concentration of phenol in the supernatant
were analyzed spectro-photometrically against respective reagent blank. The bottles containing phenol
of different concentration and the specified pH were shaken for 3 hours to ensure complete saturation.
The amount of phenol adsorbed was determined from the difference between the amount of phenol
initially added and that left after adsorption. The concentration range of phenol adhering to Beer's law
under the conditions of investigation for the system was 0-10 ppm.

RESULTS AND DISCUSSION

Effect of different parameter
i. Effect of contact time variation: The adsorption of phenol on Rice Straw increases with increase of
contact time up to one hour; afterwards slightly decreases during next hour and then no significant
change are found and attain equilibrium. The removal was very rapid within initial 15 minutes to 1hr.
Initially the Rice Straws were dry so they intensively soaked water from solution which is irreversible

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process and the phenol and Phenolic compounds got adsorbed on the surface of the Rice Straw which is
a reversible process. Within 3 hr through desorption-adsorption the system reached equilibrium. The
kinetics of phenol adsorption on Rice Straw follows the first-order rate expression (Namasivayam and
Sangeetha, 2004). These results also indicate that the sorption process can be considered very fast
because of the largest amount of phenol adsorbed to the sorbent within the first 60 min of adsorption.
ii. Effect of temperature variation: Temperature is an important parameter for any separation process.
Removal of phenol by Rice Straw was studied at four different temperatures: 30, 35, 45 and 50
0
C. It
was found that adsorption of phenol on Rice Straw increases with increase of the temperature in the
range of 30 to 50
0
C. Although absorption of phenol is maximum at 50
0
C, but all subsequent
experiments were carried out at room temperature. Because it is very difficult to keep constant high
temperature (50
0
C) and shaking is also not possible properly. The intra particle diffusion rate of sorbate
ions into the pores will be intensified as temperature increases, as diffusion is an endothermic process
(Singh and Rawat, 1994). So the adsorption increases with temperature. Therefore, the adsorption
capacity would largely depend on the chemical interaction between the functional groups on the Rice
straw surfaces and the adsorbate and increase with temperature rising.

iii. P
H
Effect on adsorption: The adsorption of phenol from aqueous solution is dependent on the pH of
the solution, which affects the surface charge of the adsorbent, degree of ionization and speciation of
the adsorbate species. The adsorption of phenol by Rice Straw was studied at various pH values of 4, 7,
8, 9, 10. The adsorbed amount increases with increasing the pH up to pH 8 and start to decrease with
increasing the pH value. This can be attributed to the depending of phenol ionization on the pH value.
The ionic fraction of phenolate ion can be calculated from (Banat et al., 2000).

pH) (pKa
10 [1
1
ions

Obviously,
ions
increases as the pH value increased. Accordingly, phenol, which is a weak acid
(pKa=10), will be adsorbed to a lesser extent at higher pH values due to the repulsive force prevailing at
higher pH value (Banat et al., 2000). Also, in the higher pH range phenol forms salts, which readily
ionize leaving negative charge on the phenolic group. At the same time the presence of OH_ ions on the
adsorbent prevents the uptake of phenolate ions (Rengaraj et al., 2002); (Aksu and Yener, 2001). Similar
behavior has been reported by for the adsorption of phenol by activated carbon, and adsorption of
phenol onto bentonite by (William.Cooper, 1985). P
H
also affects the surface properties of the sorbent,
i.e., surface charge of the cells used as sorbent. At very low pH values, the surface of the sorbent would
also be surrounded by the hydronium ions, which enhance the phenol interaction with binding site of
the sorbent by greater attractive forces, hence its uptake on polar adsorbent is reduced.

iv. Effect of initial concentration of phenol variation: The equilibrium sorption capacities of the
sorbents increased with increasing phenol concentration while the adsorption yields of phenol showed
the opposite trend. It is evident that initially the number of adsorption sites available is higher and the
driving force for the mass transfer is greater. Therefore the adsorbate reaches the adsorption site with
ease. With the increase of initial concentration, number of active sites becomes less and the adsorbent
becomes crowded inside the particles, thus impeding the movement of the adsorbate. This can be
accounted for the decrease in adsorption rate with increase in concentration. Thus, the initial
concentration provides an important driving force to overcome all mass transfer resistances of phenol
between the aqueous and solid phases. This would results in higher phenol adsorption (Ahmaruzzaman
and Sharma, 2005). On a relative basis, however, the percentage adsorption of phenol decreases as the
initial phenol concentration increases.

v. Effect of adsorbent dose variation: The amount of adsorbent on the efficiency of adsorption was also
studied. Adsorbent dosage was varied from 0.5gm to 5gm for Rice Straw. The results show that for
removal of 500 mg/L of phenol in 100 ml of solution, a minimum dosage of 2.5 gm of Rice Straw is
required for 64.1% removal of phenol. This study determines the optimum quantity of Rice Straws. It
was found that adsorption is completed within 5 hr and the percentage of adsorption increases with the

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increasing amount of Rice Straw. The highest percentage of adsorption was obtained by using the 2.5
gm of Rice Straw. Therefore, optimum quantity was found to be 2.5 gm which is shown in the figure.
The results also clearly indicate that the removal efficiency increases up to the optimum dosage beyond
which the removal efficiency is negligible.

vi. Effect of particle size variation: The effect of particle size variation on the efficiency of adsorption
was also studied. Adsorbent dosage was varied from 40 meshes to 200 meshes for Rice Straw. The
results show that for removal of 500 mg/l of phenol in 100 ml of solution, a minimum dosage of 2.5 gm
of 200 meshes Rice Straw is required for maximum percentage of removal of phenol. The adsorption of
phenol increases with the increasing of mesh size. High mesh size has larger surface area which is the
main reason for increasing of adsorption of phenol on adsorption.

vii. Adsorption isotherm: The batch adsorption experiments were carried out in 100 mL glass bottles
where 2.5 gm of Rice straw and 100 mL of phenol solutions were added. Initial phenol concentration
solutions ranged from 0.5-5 ppm (pH 8). The bottles were subsequently capped and shaken in a rotary
shaker for 1h at 25C. At the end of the equilibrium period the bottles were taken off the shaker and the
samples were left standing for a while to allow the adsorbent particles to settle. Then the solution is
filtered through glass-fiber filter paper to remove any remaining adsorbent particles. Linear calibration
curves were used to determine the phenol concentrations. The curves were based on standards in the
concentration range from 0.5-10 ppm. A phenol adsorption isotherm was obtained using the batch
equilibrium technique reported by (Ahmaruzzaman and Sharma, 2005). Several models have been
published in the literature to describe experimental data of which the most common are the Langmuir
isotherm (Tseng et al., 2003) and the Freundlich isotherm (Arinjay et al., 2003). The Langmuir isotherm is
used to describe single layer adsorption and can be written as
Amax k.c Amax m
1 1 1 1



The value A
max
represents the maximum adsorption that can take place in grams of adsorbate per gram
of adsorbent, when c is large relative to the constant k. When m approaches A
max
the coverage of the
surface is essentially complete. The Freundlich isotherm in its linearized form can be written as:
log q = log k + 1/n log C, Where, K is a Freundlich constant related to the adsorption capacity (mg/g)
and 1/n is the intensity of adsorption. The values of K and 1/n can be determined from the intercept and
slope, respectively of linear plot of log q versus log C. The linearized Langmuir and Freundlich
adsorption isotherms of rice straw for phenol are shown in fig. (2) and fig. (3).




Fig. 2. Frendlich isotherm graph.

Fig. 3. Langmuir isotherm graph.


Criteria of regeneration
Regeneration studies help elucidates the mechanism of adsorption. From the graph between the pH and
percentage of desorption, the maximum desorption efficiency was determined. 2.5 gm of spent
adsorbent after adsorption at pH 8 was shaken with 100mL of 1M NaOH, HCl, H
2
SO
4
, HNO
3
, KOH for
regeneration which was completed within 60 minute duration respectively. About 95.30%, 91.19%,
90.09%, 88.92%, 84.63% of the adsorbed quantity of phenol from the initially present 5 ppm was

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desorbed from the samples in a single step respectively. It was then washed with distilled water dried in
oven and was reused in subsequent operations. In this way after recovered samples can be reused in the
operation. It reduces the operation cost and thus may be very useful.
Application on real effluent treatment
Two industrial effluent samples were collected in a glass bottle with Teflon-lined caps directly from the
outlet of a textile (Bijoy Textile Industries Ltd.) and dyeing Industry (Color Thread Company) located at
Shampur, Kadamtali I/A, Dhaka and 42, Malitola, Dhaka respectively. The sample was immediately
brought to the laboratory to be placed in cool place. Before analysis, the effluents were decanted off and
filtered to remove some waste particle contained in the effluent and kept for further usage. Effluents were
then treated as method discussed above. Rice Straw is effectively removed 74.15%, 75.05% of phenol and
phenolic compounds by treating with Rice Straw. The adsorbed amount of phenol and phenolic compound
was recovered with 100 ml of 1 M NaOH and the percent recovery was found to be 96.76%, 97.13%.



CONCLUSION

Wastewater containing phenolic compounds presents a serious discharge problem due to their poor
biodegradability, high toxicity and ecological aspects. Phenolic compounds are frequent contaminants
of ground water because of their wide use in industrial sectors. Thus all surface water must be
considered as potentially dangerous and should be properly treated before ingestion. Activated carbons
are extensively used for wastewater treatment, its use is often limited due to its high cost and difficult
preparation methods whereas rice straw is widely abundant agricultural waste can be effectively used
for phenol removal from aquatic solution which can be regenerated and reused. Thus research work
regarding effluent is very important in context of our country, it may be concluded from the
experimental results that rice straw is an excellent adsorbent for phenol from aqueous system.

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