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Procedia Engineering 51 (2013) 300 – 307

Chemical, Civil and Mechanical Engineering Tracks of 3rd Nirma University International
Conference
(NUiCONE 2012)
Adsorption of Phenol from Wastewater in Fluidized Bed Using
Coconut Shell Activated Carbon
Sunil J.Kulkarnia* ,Ravi W.Tapre b,Suhas V. Patilc, Mukesh B. Sawarkard
a,b
Assistant Professor,Department of Chemical Engineering, Datta Meghe College of Engineering ,Airoli, Navi
Mumbai,India, Pincode:402107
c
Associate Professor, Gharda Institute of Technology,Lavel,Chiplun ,India,Pincode:415708
d
Lecturer,Government Polytechnic,Mumbra, Thane,Maharashtra Pincode:400612

Abstract

Phenol is the major pollutants in the wastewater from various industries such as coal conversion process, fertilizers, petroleum
refineries, coking plants, pharmaceutical, dye manufacturing etc. In the present study coconut shell activated carbon is used as an
adsorbent. The adsorption is carried out in a fluidized bed. Coconut shell has been used for the preparation of absorbent. The
effect of various parameters like concentration, fluid flow rate and adsorbent particle size has been studied. It is observed that as
the concentration increases the percent saturation of adsorbent increases. Also increase in fluid flow rate gives better adsorption
in case of coconut shell activated carbon. However, it is also observed that percent saturation of adsorption decreases with
increases in particle size of adsorbent. In the present study particle size of 0.420 mm is found more beneficial.

Keywords: Fluidized bed, activated carbon, adsorption, adsordate, isotherms

1. Introduction

The phenolic pollution is commonly observed in the chemical and pharmaceutical industries like petrochemical
industries, petroleum refineries, coal gasification operations, liquefaction process, resin manufacturing industries,
dye synthesis units, pulp and paper mills and pharmaceutical industries. It is a highly corrosive and nerve poisoning
agent. When these pollutants contaminate the groundwater, rivers and reservoirs, which are sources for human
consumption, harmful side effects, such as sour mouth, diarrhea, excretion of dark urine and impaired vision are
seen. The toxic levels usually range between the concentrations of 10-24 mg/l for human and the toxicity level for
fish is between 9-25 mg/l. Lethal blood concentration of phenol is around 150 mg/100 ml. Environmental Protection
Agency, EPA has set a limit of 0.1mg/lit of phenol in waste water, while that in drinking water is 0.002 mg/lit. A
total dose of 1.5 gms may be fatal. The specific tolerance limits (for effluent discharged with inland surface water)
for phenolic compounds is 5 mg/litre.As phenol is highly harmful compound, there is a necessity for its removal in
order to preserve the environmental quality. Recent studies have shown that biotic and abiotic processes can degrade
phenol. Phenol removal by resin has been tried by Gopalkrishnamoorthy and Shanmugam [1]. Abiotic and non–
biological processes include adsorption, photodecomposition, volatilization, coupling to soil humus and thermal
degradation. In biotic processes both aerobic and anaerobic processes have been employed for its removal. The
_____
* Tel.: 919833497367; fax: 91 22 2779 1665.
E-mail address: sunil_kulkarni2004@indiatimes.com

1877-7058 © 2013 The Authors. Published by Elsevier Ltd. Open access under CC BY-NC-ND license.
Selection and peer-review under responsibility of Institute of Technology, Nirma University, Ahmedabad.
doi:10.1016/j.proeng.2013.01.040
 Sunil J.Kulkarni et. al / Procedia Engineering 51 (2013) 300 – 307 301

study of biokinetic parameters for activated sludge treatment for phenolic water has been carried out by Pandey and
Kaul [2]. Kaushik Nath has studied the biological methods for phenol in wastewater [3]. Babu et. al. have used
various new adsorbents for phenol removal[4]. Electrochemical chlorination has also been tried by Nanjundam et
al.[5]. The work on new adsorbent from coconut husk has been carried out by Krishna and Yenkee[6]. The activated
carbon adsorption has also been used for coke effluents by Prasad and Singh[7]. The principle of adsorption, types
of adsorption and its the isotherms are described by Treybal[8]. A batch study for phenol adsorption using leaf litter
has been carried out by Mishra and Bhattacharya [9].
Besselievne and Schwartz have explained the treatment of industrial waste discharge [10]. The information
regarding source, analysis and characteristics of waste is descrided by Manivatsam[11]. The treatment of phenolic
wastewater in a multistage bubble column adsorber has been tried by Kumar et.al.[12]. The amount of material
adsorbed by activated carbon is surprisingly as large as compare to other carbon. Coony and Zhenpeng[13] have
studied activated carbon catalized reaction of phenolics during liquid phase adsorption. Kumar et al.[14] have
studied the characterization of activated carbon prepared from coconut shell wood for wastewater treatment. Similar
work has been carried out by other researcher’s usig different sources for activated carbon. Activated carbon as an
adsorbent is described by John [15]. The coconut shell activated carbon has been tried by many researchers for
removal of chromium and other heavy metals with resonable success. In current investigation coconut shell
activated carbon is used for phenol removal because of its good adsorption ability and low cost.

1.1. Fluidization and Fluidized Beds

Owning to the intense agitation in a well fluidizing bed, local temp and solid distribution are much more uniform
than in the fixed bed. This may be important in many chemical and catalytic processes. Since in a fluidized bed
particle size of a smaller order of magnitude than in the fixed bed, the resistance to diffusion through the particles is
smaller in the fluidized bed. This too, may benefit many chemical and catalytic reactions. Fluidization will permit
the ready additions of solids to or the withdrawals of solids from the bed. This is an important advantage over the
fixed bed, especially where rapid activity losses are involved.
This property of the fluidized bed system is responsible for the ease with which continuous operation is achieved.
Owing to the motion of the particles, part internal or external heat transfer surfaces, heat transfer coeffiC0ents in
fluidized beds are higher than in fixed beds operating under comparable flow conditions. Thus the fluidized bed
offers a great advantage where highly exothermic or endothermic reactions are involved. Although heat transfer
coefficients between solid particles and fluid appear to be of the same order of magnitude in both fluidized and fixed
beds when both are operating under comparable flow rates, the state of subdivision and heat transfer surfaces are so
much greater in the fluidized bed that the rate of solids fluid heat transfer is actually much higher in the fluidized
bed. Due to the high particle fluid heat transfer rates, fluidized solids tend themselves more readily to recovery of
heat from waste solids than to the generally larger solid particles of fixed bed. In many instances fluidization will
cause smaller pressure drop than fixed bed operation.

1.2. Minimum Fluidization Velocity

An equation for the minimum fluidization velocity can be obtained by setting the pressure drop across the bed
equal to the weight of the bed unit area of cross section, allowing for the forces of the displaced fluid .Drag force by
upward moving liquid is equal to weight of particles. Also Pressure drop across bed multiplied by Cross sectional
area of tube is equal to Volume of bed multiplied by Fraction of solids. This method is the simplest way of
calculating minimum fluidization velocity, Umf. The factors like particle size, particle shape, particle distribution,
liquid flow rate, particle density, particle porosity, liquid density, liquid viscosity, diameter of conduit, shape of
conduit, roughness of the surface, temperature and pressure affect the fluidization. Umf, the superficial velocity at
minimum fluidizing conditions is found by the equation 1.
s and l are solid and liquid densities respectively. μ is the liquid viscosity. Here Vom is the fluid velocity and dp
is the particle diameter. is void fraction, , the sphericity and μ is the liquid viscocity. The density of
adsorbent was found to be 0.42 gram/ml. At minimum fluidization velocity, Vom = Umf . The minimum fluidization
velocity was observed to be 2.5 cm/sec for the system.
302 Sunil J.Kulkarni et. al / Procedia Engineering 51 (2013) 300 – 307

2 2
1.75 d p V om l 150 1 mf d p V om l dp l l s g
3 3 2 (1)
s mf s mf

2. Methodology

2.1. Preparation of adsorbent

The coconut shells were first cleansed to avoid the presence of mud on it. Fixed batch of coconut shells were
allowed to stay in heating furnace where the temperature was maintained at about 250–275oC.The furnace used was
digitally controlled. So we get accurate temperature required for the preparation. The coconut shells were allowed to
stay in furnace till red hot. Thus fixed batch of shells were taken out according to our requirement. The red hot
coconut shell was allowed to cool for some time till it reached the room temperature. Thus the shells completely
burned were crushed using jaw crusher. As according to our requirement the jaw crusher was adjusted.The material
after crushing was send to sieve analysis.

2.2. Experimental Procerdure

Due to the non-availability of consistently uniform waste samples, synthetic phenol wastes of different
concentrations were made. The concentration range of Phenol in the waste sample varied from as low as 100 mg/lit
to as high as 300mg/lit for different runs. The parameters optimized were initial phenol concentration, flow rate and
particle size of the adsorbent.

2.3. Study of adsorption isotherms

Batch adsorption process is used for the study of equilibrium characteristics of the system. For the present
experimental work, synthetically prepared phenol – water solution is used. The experiments were carried out in a
batch reactor. During the experiments, mass of adsorbent and volumes of solution in each conical flask were kept
constant. Phenol solutions of different concentrations varying from 25 – 300 ppm i.e. (25, 50, 75, 100, 200, and 300)
were taken in different batches, thereafter 5 grams of coconut shell activated carbon was added to each reactor. The
contents were stirred till adsorbent reached its saturation point. Samples were collected at particular time interval
and analyzed by the volumetric titration to know the residual phenol concentration in the solution. The experiments
were conducted till the equilibrium is attained. Freundlich Isotherm is presented in figure 1.

2.4. Break through capacity of adsorbent

The break through capacity for coconut shell activated carbon was determined in fluidized bed type contactor for
each run by changing one parameter at a time keeping other parameters constant for each run, the carbon was filled
in the contactor and then phenol solution was run upward at a steady flow rate from bottom. The flow rate of
solution of contactor was kept constant. Then different volumes of effluent samples were taken and analyzed to see
whether the concentration of phenol reached the incoming phenol concentrations. When outlet phenol concentration
reached initial value, the experiment was stopped. Precautions were taken to see that the flow rate was kept constant
throughout the run and initially when filling the coconut shell activated carbon in the packed bed, to avoid
channeling or dead zone in the bed, the bed was filled with distilled water first and then the coconut shell activated
carbon was added so whatever air was there, it was removed in the form of bubbles and then the experiments were
started.

2.5. Estimaton of % saturation

We determined the area under curve for a graph of (C/C0) v/s (V-Vb)/(Vx-Vb). C and C0 are the outlet
 Sunil J.Kulkarni et. al / Procedia Engineering 51 (2013) 300 – 307 303

Figure 1: Freundlich isotherm

concentration at any time and concentration at the inlet respectively. V, Vb and Vx are the volume of the liquid
passed through the column at given time, breakthrough and exhaustion respectively. Area under the curve is the
fractional capacity (f) .The value of (V-Vb)/(Vx-Vb) was calculated by plotting 1/(C-C0) verses C. The area under
curve at any concentration C gives corresponding value of (V-Vb)/(Vx-Vb). Depth of the bed
using equation 2 and percentage saturation by equation 3.

L[V x Vb ]
(2)
Vb f [V x Vb ]

Where L is a bed height = 0.07m

L (f 1)
% saturation 100 (3)
L

3. Experimental results and discussion

The experiments conducted at various phenol concentration by keeping particle size and flowrate constant, are
presented and discussed in this section.

3.1. Effect of initial phenol concentration

The variation of C/C0 with time at different initial phenol concentration is shown in the figure 2. It was found
that C/C0 value is minimum for first couple of readings and then it goes on increasing at reaches maximum value of
1. It reaches the maximum value in minimum time for the initial phenol concentration of 300 mg/l.This happens due
to fact that as the time progresses the capacity of the bed reduces and at higher time adsorption capacity of bed
becomes negligible. It is observed from same figure that for the initial phenol concentration of 300 mg/l, it takes
minimum time i.e. 33 minutes to reach the maximum value of C/C0 . It is also observed that the rate of change in
concentration is very high for initial period of 15 to 20 minutes and it goes on decreasing and is almost negligible
towards the end.

3.2. Effect of flow rate

304 Sunil J.Kulkarni et. al / Procedia Engineering 51 (2013) 300 – 307

Figure 3 shows the variation of C/C0 with time at different flow rates by keeping particle size and the initial phenol
concentration constant. It is observed from the figure that as time increases C/C0 increases with increasing flow rate.
At flow rate of 4.2 lpm, C/C0 reaches maximum value of 1 within minimum time interval of 50 minutes.

3.3. Effect of particle size

The variation of C/C0 with time at different particle size is shown in the figure 4. The experiments were
conducted at various particle size by keeping flow rates and the initial phenol concentration constant. From the
figure, it has been observed that as time increases C/C0 increases with time at a given particle size. It is also
observed from that as particle size decreases the required contact time reduces. The particle size of 0.420 mm was
found to be more suitable than other particle size, since it requires minimum time i.e. 46 minutes to attain maximum
C/C0 value of 1. The minimum paricle size offers more surface area for adsorption.

3.4. Effect on percentage saturation

The effect of initial phenol concentration on percentage saturation is presented in Figure 5. It is observed from
this figure that percentage saturation increases with initial phenol concentration at constant particle size and flow
rate. Percentage saturation is realized maximum at initial phenol concentration of 300 mg/l. The variation of
percentage saturation with flow rate is presented in Figure 6. It is also observed that from figure 6 that at the fixed
particle size and initial phenol concentration, the maximum percentage saturation of 46 percent is observed at the
flow rate of 4.2 lpm and percentage saturation increases with increase in flow rate. Figure 7 shows the effect of
particle size on percentage saturation. It is observed from the figure that the percentage saturation attains the
maximum value of 57 at corresponding particle size of 0.420 mm. It is also observed that percentage saturation
decreases with increase in particle size.

Conclusion

The experimental studies on removal of phenol from waste water in a fluidized bed column using coconut shell
activated carbon as a adsorbent have been reported. Experimental results agree well with well known Freundlich
adsorption isotherm within 5 percent discrepancy. It is found from the present study that percentage saturation
increases with increase in initial concentration of phenol and flow rate. Particle size also found to affect the
adsorption operation. The inlet concentration of phenol and flow rate has significant effect on the adsorption
operation. It is observed from present experimental study that percent saturation decreases with increase in particle
size. The flow rate of 4.2 lpm yields maximum percent saturation of 46 percent.

Figure 2: Variation of C/C0 with time at different initial concentrations

 Sunil J.Kulkarni et. al / Procedia Engineering 51 (2013) 300 – 307 305

Figure 3: Variation of C/C0 with time at different flow rates

Figure 4: Variation of C/C0 with time for different particle sizes

Figure 5: Effect of initial concentration on percentage saturation

306 Sunil J.Kulkarni et. al / Procedia Engineering 51 (2013) 300 – 307

Figure 6 : Effect of flow rate on percentage saturation

Figure 7: Effect of particle size on percentage saturation

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