Chemical Engineering Communications

ISSN: 0098-6445 (Print) 1563-5201 (Online) Journal homepage: http://www.tandfonline.com/loi/gcec20

Synthesis of activated charcoal from saw-dust and

characterization for adsorptive separation of oil
from oil-in-water emulsion

V. K. Rajak, Sunil Kumar, N. V. Thombre & Ajay Mandal

To cite this article: V. K. Rajak, Sunil Kumar, N. V. Thombre & Ajay Mandal (2018) Synthesis
of activated charcoal from saw-dust and characterization for adsorptive separation of oil
from oil-in-water emulsion, Chemical Engineering Communications, 205:7, 897-913, DOI:
10.1080/00986445.2017.1423288

To link to this article: https://doi.org/10.1080/00986445.2017.1423288

Published online: 12 Mar 2018.

Submit your article to this journal

Article views: 40

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=gcec20
CHEMICAL ENGINEERING COMMUNICATIONS
2018, VOL. 205, NO. 7, 897–913
https://doi.org/10.1080/00986445.2017.1423288

none defined

Synthesis of activated charcoal from saw-dust and characterization

for adsorptive separation of oil from oil-in-water emulsion
V. K. Rajak, Sunil Kumar, N. V. Thombre, and Ajay Mandal
Department of Petroleum Engineering, Indian Institute of Technology (ISM), Dhanbad, India

ABSTRACT KEYWORDS
The paper represents the synthesis process of charcoal from saw dust by chemical activation with Activated charcoal;
different chemical agents like phosphoric acid, zinc chloride, and ferrous sulfate heptahydrate. The adsorption; kinetics;
synthesized charcoal samples were analyzed by scanning electron microscopy, energy dispersive oil-in-water emulsion;
X-ray spectroscopy, Fourier transform infrared spectroscopy, and BET surface analyser. The adsorption separation; synthesis
capacity of different charcoal samples was tested to separate oil from the oil-in-water emulsion.
Effects of different parameters like adsorbent dosage, contact time and temperature on adsorption of
oil from oil-in-water emulsion by synthesized charcoals have been investigated. Under optimized
condition, the oil separation efficiency is more than 98%, though it also depends on the initial
concentration of oil in the emulsion. Isotherm and kinetic study on adsorption of oil from oil-in-water
emulsion have also been studied. Three widely applied isotherm models viz., Langmuir, Freundlich,
and Temkin were used to analyze the experimental adsorption data. Different adsorption kinetic
models were considered to model the experimental data. Thermodynamics parameters were also
evaluated for the adsorption of oil onto the charcoal samples.

Introduction 2015), chemical-coagulation, electrocoagulation

(Mandal et al., 2003; Cerqueira et al., 2011), electro-
Petroleum industry invariably produces plenty of
flotation (Mickova, 2015), etc. One of the most com-
waste streams as produced water. The ratio of
monly used techniques for removing dissolved
volume of produced water to produced oil becomes
organics from the water is the transfer of matter
larger and larger in mature oil fields. Oil-in-water
from the liquid phase to the surface of solid phase
emulsions are generally found in produced water
by the process of adsorption. The adsorbing phase
in a significant amount. Because of the hazardous
is referred to as adsorbent and the adsorbed material
nature of oil present in oily wastewater, it is
is called adsorbate (Ho and Chan, 1986).
considered to be a threat to the environment and
A wide range of materials for water remediation
human beings. In general, the maximum concen-
has actually been used in recent years. A lot of
tration of oil and grease is 40 mg L−1 in discharge
studies have been conducted to separate the dye
water and this limit is becoming more enforced
chemicals from the effluent of different process
as to avoid environmental damage by oily
industries (Lasindrang et al., 2015; Nautiyal et al.,
wastewater (Moosai and Dawe, 2003).
2016; Popa and Visa, 2017). Depending upon the
To separate the oil from oil-in-water emulsion, a
composition of the effluent, activated carbon
variety of techniques are available which include a
(AC), bentonite, peat, sand, coal, organoclay, etc.
number of filters (Bansal et al., 2011), chemical dos-
may be used as the adsorbent (Emam, 2013; Huang
ing (Fu and Chung, 2011), reverse osmosis (Mondal
et al., 2007). Activated carbon is having wide appli-
and Wickramasinghe, 2008), gravity separation
cation particularly separation of organic materials
(Berman and Tamir, 2003), ultra-filtration (He and
and heavy metals from the effluent (Ayranci and
Jiang, 2008; Nayak et al., 2017), microfiltration
Duman, 2006; Xing et al., 2008; Wang et al.,
(Campos et al., 2002), biological processes
2017a; Agarwal and Singh, 2017), but a relatively
(Domenico et al., 2004), air flotation (Rajak et al.,

CONTACT Ajay Mandal [email protected]; [email protected] Department of Petroleum Engineering, Indian Institute of Technology (ISM),
Dhanbad 826004, India.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gcec.
© 2018 Taylor & Francis
898 V. K. RAJAK ET AL.

less literature is available on separation of oil from the liquid phases. Mesoporous ACs are used in
the emulsion by activated charcoal. Wang et al. purification of drinking water, treatment of
(2017a) and Lei et al. (2017) used hydrothermally wastewater, processing of food and chemical and
fabricated superhydrophobic cotton fibers for sweetener discolorization, whereas, microporous
efficient separation of oil-in-water emulsions. ACs are used in gasoline emission control,
Takeuchi et al. (2015) synthesized an exfoliated industrial gas treatment, gasoline emission control,
graphite for sorption of oil from oil–water emulsion. and cigarette filters.
Activated carbon has become technically promi- In the present work charcoal has been synthesized
nent and the most extensively used adsorbents from saw dust by chemical activation with different
because of its notably high adsorptive capacity. activators like phosphoric acid, zinc chloride, and
Activated charcoal is efficiently used to remove ferrous sulfateheptahydrate. Fourier transform
toxic and biorefractive material such as, herbicides, infrared spectroscopy (FTIR), scanning electron
oil and grease, insecticides, heavy metal ions, microscopy (SEM), energy dispersive spectroscopy
phenols, chlorinated hydrocarbons, chlorinated (EDAX) analyses and BET surface area measure-
hydrocarbons, etc., which are present in many ment of synthesized charcoals have been performed
wastewater (Ansari and Masoudi, 2004; Austin to check the efficacy of the charcoal samples as an
and Shreve, 1985; Bansode et al., 2003). Karaer adsorbent. Effects of different parameters like dose
and Kaya (2016) synthesized a chitosan/activated of adsorbent, concentration of emulsion, contact
charcoal composite for removal of methylene blue time and temperature during adsorption of oil from
and reactive blue4 from aqueous solution. A huge oil-in-water emulsion have been thoroughly
production of ACs is demanded by the present investigated. The experimental data are analyzed
technology with pertinent characteristics for each by different isotherm and kinetic models.
and every particular process. Usually, the AC
which is used in any applications must have the
Experimental section
competent adsorptive capacity and mechanical
strength. In conjunction with all these specifica- Materials used
tions, the production cost should also be low. By The activated charcoal precursor material used in
controlling the process of carbonization, dehy- this study is Indian white teak tree (locally known
dration and oxidation of organic substances, AC as gamhar) sawdust obtained from sawmill of
can be obtained. Any materials that contain a high Dhanbad area, Jharkhand. The crude oil sample
percentage of carbon can be converted into acti- collected from Mehsana oil field, India has been
vated charcoal by physical or chemical techniques. used in the experimental purpose. For FTIR study
However, the most commonly used ones in potassium bromide (KBr) with 99.99% purity was
commercial practice are coal, wood, lignite, peats, used as reference. It was supplied by Merck, India.
and agricultural by-products such as almond shell, H3PO4, ZnCl2, and FeSO4 · 7H2O were procured
rice husks, coconut shell, etc. It has been stated that from RFCL Limited, New Delhi, India.
the coconut shell and apricot pits are the good
sources of high grades of AC. Physical and chemi-
Synthesis of activated charcoal
cal activation are the two processes by which ACs
are prepared (Dąbrowski, 2001; Laine and Calafat, Before synthesizing, raw sawdust was crashed and
1989; Ogasawara et al., 1987; Wigmans, 1989). The sieved for uniform size and then characterized by
oxidation is preferred by a primary carbonization proximate analysis for determination of ash,
of raw material. AC is used to adsorb molecules moisture, volatile matter and fixed carbon contents
from both liquid and gasses, which extensively following the ASTM E871-82, E1755-01, and
depends upon the size of the adsorbate molecule, E872-82 methods. The size of particles was 250 to
pore size distribution and the geometry of the 350 µm. Ultimate analysis was performed to
adsorbent. Principally, the microporous carbon is determine the composition of basic elements viz.,
used in adsorption from the gas phase, whereas, carbon, hydrogen, nitrogen, and sulfur content
mesoporous carbon is used in the adsorption from using the (Vario EL III) carbon, hydrogen,
 CHEMICAL ENGINEERING COMMUNICATIONS 899

nitrogen, sulphur (CHNS) analyser. The analysis (FE-SEM) (Supra 55, Carl Zeiss, Germany). The
like proximate and ultimate of the precursor mate- various elements present in samples were analyzed
rials are given in Table 1. by energy dispersive X-ray spectroscopy (EDX).
Saw dust sample was washed many times to Specific surface area, pore radius and pore volume
remove any dust present and then dried at 110°C of synthesized charcoal were determined by BET-
for 24 h in drying oven. The dried saw dust sample analyzer (Nova 3200e, Quntachrome instruments,
was then used for the synthesis of ACs. H3PO4, USA). Thermal stability of the charcoal samples
ZnCl2, and FeSO4 · 7H2O were used separately as were tested by a thermogravimetric analysis
activating agents for the synthesis of AC. (TGA) analyzer (Netzsch-STA 449 Jupiter).
The chemical activation with different chemical
agents (H3PO4, ZnCl2, and FeSO4.7H2O) was per-
Emulsion preparation and adsorption
formed using an impregnation method (Karanfil
procedure
et al., 2006; Ghasemi et al., 2015). 100 g of saw dust
was well mixed with the desired amount of each For the preparation of the oil-in-water emulsion, the
activating agent separately. The saw dust samples distilled water and the crude oil were used as a con-
mixed with the solution of chemical agents were tinuous phase and as dispersed phase respectively.
placed for 1 h at room temperature and then com- There was no need to add a surfactant for making
pletely rinsed with the deionized water. Further, emulsion because of natural surfactants, such as
the washed wet solids were dried in a convection waxes, asphaltenes, resins, and naphthenic acids,
oven at 150°C for 2 h before being charred. were present in crude oil which stabilized the emul-
Thermal carbonization of activated samples were sion. Crude oil collected from Mewad oil field well
conducted in a carbolite LMF4 muffle furnace. no. 37, Mehsana, Gujarat was used for the prep-
The material is then charred in the absence of air aration of the emulsion. The amount of distilled
by keeping the samples in a sealed steel cubicle. water and crude oil was measured and placed in a
The temperature during charring has increased sonicator tank (FB15051, Fisherbrand, Germany)
until the predetermined temperature of 550°C at a temperature 25°C for about 5–10 h depending
was reached by a rate of 5°C min−1 and detained upon the oil concentration. The prepared yellowish
for 10 min. To remove the volatile matters, a gas emulsion was further placed in a separating funnel
release pipe was attached to the cubicle. The for 24 h, then free oil from emulsion was separated.
cubicle was then cooled in stages. After cooling, Adsorption experiments were performed by agitat-
the charcoal samples were washed with the distilled ing different amount of synthesized charcoal with
water and then dried at 90°C for 24 h to obtain the 50 mL of the oil-in-water emulsion of desired con-
desired product. centration in a Rotospin (Tarsons) test tube mixer.
After a predetermined time the sample was with-
drawn from the Rotospin. The amount of oil content
Characterization of synthesized activated in the emulsion was measured by an infracal total
charcoal oil and grease (TOG)/total petroleum hydrocarbon
The synthesized charcoal samples were characterized (TPH) analyzer (Wilks) (Kumar et al., 2015).
by FTIR analysis to identify the functional group
present in it by a FTIR analyzer (model). The Equilibrium studies
morphologies of the samples were observed using
field emission scanning electron microscopy The equilibrium studies were conducted by shak-
ing the sorption mixture (adsorbent and adsorbate)
in the Rotospin mixer at various programmed
Table 1. Chemical analysis of the raw sawdust.
intervals and conditions. Time to time the specific
Proximate analyses
(wt% dry basis) Ultimate analyses (wt% dry basis) samples were collected from the mixer and
Fixed analyzed for the adsorbate concentration. Kinetic
Volatile carbon Ash Carbon Hydrogen Oxygen Nitrogen Sulfur and isotherm adsorption experiments were
72.77 15.8 0.73 49.620 5.890 44.174 0.209 0.107 performed to evaluate the adsorption performance.
900 V. K. RAJAK ET AL.

The equilibrium adsorption was completed by

adding a fixed amount of charcoal into 50 mL of
emulsion with different initial concentrations
(510, 650, 770, 890, and 1,000 mg L−1) of oil. The
kinetic adsorption studies were performed by add-
ing 0.25 g synthesized AC into 50 mL of emulsion
with the different initial concentration of oil. The
percentage reduction of oil from the emulsion in
an adsorption time of 3 h with different doses of
activated charcoal (2, 3, 4, 5, 6, 7, 8, and 9 g L−1)
for initial concentration 510, 650, 770, 890, and
1,000 mg L−1 have been determined respectively. Figure 1. FTIR spectra of synthesized charcoal (A: charcoal
The % removal of oil by the synthesized charcoal activated by FeSO4 · 7H2O, B: charcoal activated by ZnCl2, C:
charcoal activated by H3PO4). Note: FTIR, Fourier transform
samples was calculated using the following equation: infrared spectroscopy.
C0 Ce
% Removal ¼ � 100 ð1Þ
C0 adsorption of oil from emulsion were identified by
The adsorbed amount of oil after reaching the FTIR analysis (Liu et al., 2016). Figure 1 shows the
equilibrium was calculated by FTIR spectrum for the synthesized charcoal acti-
vated with different chemical agents. The different
ðC0
Ce ÞV peaks in the FTIR spectrum is assigned for the
qe ¼ ð2Þ
W respective functional groups present in AC. The
where C0 (mg L−1) is the initial concentration FTIR spectra shows that the functional groups of
and Ce (mg L−1) is the final concentration of oil. the synthesized charcoal samples obtained by acti-
V (L) is the volume of solution, and W (g) is the vation with different chemical agents (H3PO4,
mass of adsorbents used. The adsorption of oil qt ZnCl2, and FeSO4 · 7H2O) are almost same. The
in (mg g−1) at any time t, was then calculated by broad peak of O‒H stretching vibrations at around
ðC0
Ct ÞV 3,462 cm−1 reveals the presence of alcohols,
qt ¼ ð3Þ phenols, and carboxylic acids, etc. on the adsorbent
W
surface. The peaks at 2,919 cm−1 and 2,851 cm−1
where Ct is the concentration (mg L−1) of oil at correspond to the symmetric and asymmetric C‒H
any time. vibration of aliphatic acids respectively due to the
stretching. The peak at 1,698 cm−1 is attributed to
Kinetics studies the stretching vibration of carboxyl groups
(–COOH, –COOCH3). The peak observed at
Most of the adsorption of oil on synthesized 1,590 cm−1 is due to C=C stretching that can be
charcoal occurred within 3 h and then increases attributed to the aromatic C‒C bond. The peaks
only marginally. Therefore, the adsorption of around 1,430 cm−1 are due to the symmetric
oil on charcoal was measured for the first 3 h at bending of CH3 (Mehrasbi et al., 2009). The peaks
25°C with a dose of activated charcoal 5 g L−1 around 1,262 cm−1 show the presence of C‒N
for different initial concentrations of emulsion stretching in aromatic tertiary amines. The peaks
(510, 650, 770, 890, and 1,000 mg L−1). around 880 and 750 cm−1 indicate C‒H out-of-plane
bending in an aromatic ring.
Result and discussion
BET analysis
Characterization of synthesized charcoal
For identifying the BET surface area, pore volume
Fourier transformation infrared analysis (micro), pore volume (total), and average pore
of synthesized charcoal radius for fresh synthesized charcoals, the BET
The functional groups present in synthesized analysis was performed. The calculated parameters
activated charcoal, which plays a dominant role on are shown in Table 2. The BET surface area
 CHEMICAL ENGINEERING COMMUNICATIONS 901

Table 2. BET surface area and pore volume of different synthesized charcoal samples.
BET surface Micropore volume Average pore Total pore
Synthesized charcoal area (m2 g−1) (cm3 g−1) radius (Å) volume (cm3 g−1)
Activation by H3PO4 310.23 0.090 10.23 0.24
Activation by ZnCl2 292.12 0.085 11.67 0.22
Activation by FeSO4 · 7H2O 257.37 0.076 12.45 0.15

was found to vary from 257.37 to 310.23 m2 g−1. respectively. In Figure 3(a) charcoal activated with
The highest BET surface area was obtained for H3PO4, element P has appeared with 4.74 wt%
the charcoal activated by H3PO4. The BET surface because of activation. Similarly, in Figure 3(b)
area of the activated charcoals synthesized in the element Zn with 5.96 wt% and Cl with 10 wt%
present study are comparable with the charcoal has appeared. And in Figure 3(c) the element Fe
used in other studies (Popa and Visa, 2017; Shen has appeared with 5.6 wt%.
et al., 2018). The bulk density of the adsorbent is
around 0.55 g cm−3.
Adsorption studies
SEM of synthesized charcoal The surface area of the resulting activated charcoal
Figures 2(a)–(c) represent the SEM photographs of depends on the type of saw dust, type of chemical
synthesized charcoal samples activated with H3PO4, reagent, impregnation ratio of chemical reagents,
ZnCl2, and FeSO4 · 7H2O respectively. On the basis carbonization temperature, and duration of
of the texture as shown in the figures it is observed carbonization. High surface area developed on
that, the surface is heterogeneous and the pore synthesized charcoal is responsible for the
size is randomly distributed. Moreover, it is also adsorption of oil from oil-in-water emulsion. The
absorbed that the surface is irregular and highly efficiency of the adsorption process by charcoal
porous, which indicates relatively higher surface extensively depends on parameters like initial
area. This result can be supported by BET surface concentration of emulsion, contact time, adsorbent
area of 310.23, 292.12, and 257.37 m2 g−1 for dose, and operation temperature. The effects of the
synthesized charcoal activated with H3PO4, ZnCl2, above-mentioned parameters have been discussed
and FeSO4 · 7H2O, respectively. below with experimental results.

EDX analysis Oil separation efficiency of different synthesized

Energy dispersive X-ray spectroscopy analysis of charcoals
synthesized charcoals activated with H3PO4, ZnCl2, Adsorption capacity of synthesized charcoal
and FeSO4 · 7H2O are shown in Figures 3(a)–(c) activated with different chemical reagent was
respectively. It was apparent that chemistry analyzed. For the adsorption study, initial
composition of synthesized charcoal activated by concentration of oil in emulsion was kept at
H3PO4, ZnCl2, and FeSO4 · 7H2O consisted of C 1,000 mg L−1 and charcoal dose was varied from 2
element with 72.26 wt%, 67.08 wt%, and 70.56 wt%, to 9 g L−1. From the Figure 4, it was found that

Figure 2. SEM photographs of synthesized charcoal activated with H3PO4 (a), ZnCl2 (b), and FeSO4 · 7H2O (c). Note: SEM, scanning
electron microscopy.
902 V. K. RAJAK ET AL.

Figure 3. EDX analysis of charcoals activated by H3PO4 (a) ZnCl2 (b), and FeSO4 · 7H2O (c). Note: EDX, energy dispersive X-ray
spectroscopy.

adsorption curve follows the same trends but higher 93–96%, which is higher or comparable to the other
adsorption was observed for charcoal activated with reported works (Wang et al., 2017b; Takeuchi et al.,
H3PO4. Since BET surface area of charcoal activated 2015; Lei et al., 2017).
with H3PO4 is higher than other two, higher adsorp-
tion of oil from oil-in-water emulsion by charcoal Effect of dose of activated charcoal on oil removal
activated with H3PO4 was observed. Hence, charcoal efficiency
activated with H3PO4 was considered for further Effect of dose of charcoal activated by H3PO4 on
analysis of different parameters. The oil recovery adsorption under optimized condition (contact
efficiency increases only marginally after a moderate time of 3 h) for different initial concentrations
dose of charcoal (6 g L−1), at which the recovery is was studied. The results obtained are represented
 CHEMICAL ENGINEERING COMMUNICATIONS 903

Figure 4. Adsorption by all synthesized charcoal with varying

dose (initial concentration 1,000 mg L−1, contact time 3 h). Figure 6. Effect of contact time on amount of oil adsorbed per
unit mass of synthesized activated charcoal for different initial
oil concentration at 25°C.
in Figure 5. It is clear that with an increase in the
dose of AC the percent reduction of oil in treated per unit mass of synthesized activated charcoal as a
water increases due to increased number of function of time for different initial oil concentra-
adsorbent sites. These increased number of adsorb- tions between 510 and 1,000 mg L−1 at 25°C. When
ent sites allow to attach more adsorbate to their the concentration of oil in emulsion is higher, then
surfaces. Similar results have also been reported also, the driving force for adsorption of the oil on
by many authors for different types of absorbents the adsorbent surface is higher, which leads to
(Emam, 2013; Sulaymon and Kshash, 2010). higher adsorption uptake (Fard et al., 2016; Huang
et al., 2017). As the initial oil concentration
increases from 510 to 1,000 mg L−1, the adsorption
Effect of initial concentration on oil removal uptake of charcoal increases from 99 to 182 mg g−1
efficiency in 3 h. The figure also shows that a rapid adsorp-
The overall oil separation efficiency is always tion occurs within first 1 h as initial more active
dependent on the initial oil concentration in the sites of the charcoal are available for adsorption.
effluent. Figure 6 shows the amount of oil adsorbed The adsorption rate gradually decreases and
reaches equilibrium in about 3 h for different
samples. The time after which the adsorption is
negligible is referred to as equilibrium time and
the corresponding adsorption is termed as
maximum oil adsorption capacity of the adsorbent
under these particular conditions.
From Figure 7, it is observed that higher the
initial concentration of oil, lower is the percent
reduction of oil in the treated effluent and vice
versa. An increase in oil concentration from 510
to 1,000 mg L−1 decreases its removal from 97.06
to 91.0% due to the saturation of the adsorption
sites at the higher oil concentrations. The similar
type of phenomenon was noticed during the
experimental analysis of study adsorption of
phenol onto organobentonite and lignite AC
Figure 5. Effect of contact time on amount of oil adsorbed
per unit mass of synthesized charcoal for different initial oil (Ocampo-Perez et al., 2011; Guocheng et al.,
concentration at 25°C. 2011). This may be due to the fact that after the
904 V. K. RAJAK ET AL.

of oil removal decreases with respect to increasing

temperature. The smooth and continuous
adsorption curves was observed, which may be
due to coverage of monolayer of oil on the surface
of activated charcoal (Mane et al., 2007; Yang
et al., 2016). It reflects rapid uptake of oil at the
beginning and then it becomes constant. The
pattern of the curve also tells that adsorption of
oil onto charcoal is exothermic in nature. The solu-
bility of oil in water increases at higher temperature
which leads to less interaction between oil and
adsorption sites of charcoal, hence, adsorption
decreases at higher temperature. Iqbal and Ashiq
reported similar behavior for adsorption phenom-
enon of dyes from aqueous solution on adsorption
Figure 7. Effect of the initial concentration of oil on the sites of activated charcoal (Iqbal and Ashiq, 2007).
adsorption of oil under optimized condition (contact time 3 h
and 0.25 g adsorbent per 50 mL of solution).
Adsorption isotherms
formation of monolayer of oil on the adsorbate suf- During adsorption there exists a relation between
ficient surface area is not available for excess oil. At the solute concentration in the solution and the
low concentration of oil for a fixed amount of amount of solute adsorbed onto the adsorption
adsorbent more active sites of charcoal are sites at equilibrium at a fixed temperature, which
available for attachment of small quantity of oil. is defined as adsorption isotherm (Febrianto
However, at higher initial oil concentration, the et al., 2009). Adsorption phenomenon of oil onto
ratio between oily compound and available the activated charcoal can be explained by the
adsorption sites tend to increase, which leads to different adsorption isotherms, viz., Langmuir,
reduction of oil removal efficiency (Emam, 2013). Freundlich, and Temkin. The basic assumptions
for all the models are: the adsorbing sites is a
Effect of temperature on oil removal efficiency perfectly flat plane; all sites are equivalent; mono-
Figure 8 shows the efficiency of oil removal with layer coverage of adsorbate and no interactions
varying temperature. It was observed that efficiency between adsorbate molecules on adjacent sites;
each molecule adsorbs on a well-defined site and
the adsorbed molecules are localized. The amount
of oil adsorbed onto unit mass of adsorbent qe is
function of the concentration of oil at equilibrium
in the liquid phase Ce. The assumption involved in
the Langmuir isotherm model is the maximum
adsorption corresponding to a saturated monolayer
coverage of solute molecules on the solid surfaces
and there is no transmigration of the adsorbate
takes place on the plane of surface (Agyei et al.,
2000; Ho and McKay, 1999a; Hameed et al.,
2007). The adsorption energy is constant and there
is no immigration of adsorbate molecules on
the superficial plane. The equation of Langmuir
isotherm is given by:
Figure 8. Effect of contact time on the adsorption of oil on Ce 1 Ce
powder activated charcoal at different temperature (adsorbent ¼ þ ð4Þ
dose 5 g L−1 and initial oil concentration 1,000 mg L−1). q e q m KL q m
 CHEMICAL ENGINEERING COMMUNICATIONS 905

where qe (mg g−1) denotes the concentration of Table 3. Langmuir, Freundlich, and Temkin isotherm model
oil per unit mass of the charcoal, Ce (mg L−1) repre- parameters and correlation coefficients for adsorption of oil
onto synthesized charcoal.
sents concentration at equilibrium, qm (mg g−1) is
Solution temperature
the Langmuir constant which represents the Isotherm
models Parameters 25°C 40°C 50°C 60°C
maximum adsorption capacity of the charcoal
Langmuir qm (mg g−1) 505.05 471.69 462.96 442.48
phase loading, and KL (L mg−1) is the Langmuir KL (L mg−1) 0.0068 0.0066 0.0059 0.0053
constant which represents the energy constant of R2 0.988 0.988 0.986 0.976
v2 1.949 2.889 2.338 3.645
absorption capacity. The experimental adsorption
Freundlich Kf (mg g−1) 14.43 14.29 13.42 12.75
data (Ce/qe vs. Ce) are plotted in Figure 9. It may n 1.778 1.832 1.835 1.867
be seen that the resulted isotherm data well follow R2 0.991 0.991 0.994 0.995
v2 1.355 1.717 1.095 0.796
the Langmuir model. Slope and intercept of Temkin AT (L g−1) 0.063 0.059 0.054 0.049
Figure 9 was used to calculate the values of qm B (J mol−1) 112.94 106.50 104.15 99.06
(mg g−1) and KL (L mg−1) and are given in Table 3. R2 0.980 0.977 0.979 0.970
v2 6.028 7.183 5.645 6.430
The Freundlich isotherm model is one of the
most frequent empirical correlation used to explain
adsorption isotherm (Agyei et al., 2000; Baup The characteristics of the system are represented
et al., 2000). It describes the multilayer adsorption by the Freundlich constant Kf and n. The constants
phenomenon onto homogeneous surfaces. Kf and n indicate the adsorption capacity and the
According to this model, during adsorption adsorption intensity along with the extent of non-
process, different sites with numerous adsorption linearity between the concentration of the solution
energies are involved. The model describes the and adsorption respectively (Kumar et al., 2016).
kin relation between the concentrations of oil at The graph of log Ce vs. log qe are plotted in
equilibrium Ce and the amount of oil adsorbed Figure 10. Constant Kf and n were calculated from
per unit mass of adsorbent qe. the slope and intercept and values are given in
Table 3. Higher is the value of Kf and n, more
1 favorable will be the adsorption phenomenon. As
log qe ¼ log Kf þ log Ce ð5Þ
n seen from Table 3, n value is greater than 1.0,

Figure 9. Langmuir adsorption isotherm at different temperatures.

906 V. K. RAJAK ET AL.

which indicates that the adsorption is a chemical oil-in-water emulsion by the synthesized AC, the
process (Desta, 2013). Freundlich isotherm shows best fit. The Chi-square
The Temkin isotherm (Choy et al., 1999) has (v2 ) test was also performed to support the best fit
been used in the following form: adsorption model. The equation for evaluating best
fit model can be expressed as
qe ¼ B ln AT þ B ln Ce ð6Þ
�
X qt;exp qt;cal 2
where, AT and B represent the equilibrium binding 2
v ¼ ð8Þ
constant (L g−1) and the heat of sorption (J mol−1) qt;cal
respectively for Temkin isotherm. b is the Temkin The lower is the value of v2 the better is the
isotherm constant linked to the energy parameter fitting of the experimental data with the corre-
B and R is the gas constant (J mol−1 k−1), as shown sponding model. The v2 value for the different
in equation: models are given in Table 3. In isotherm study it
RT has been found that v2 values are much less in
b¼ ð7Þ Freundlich isotherm model, which implies that
B
adsorption of oil onto charcoal follows the
where T is the absolute temperature (K). The Freundlich isotherm model. The similar trends have
values of the Temkin constants AT and B are been observed by Emam (2013) on study of adsorp-
presented in Table 3 based on the results obtained tion of emulsified petroleum hydrocarbon in
by the Temkin isotherm in Figure 11. aqueous solution onto modified AC and bentonite.
The obtained correlation coefficient shows that
the adsorption of oil also followed Temkin model.
The correlation coefficients for adsorption data Adsorption kinetics
fitted with Langmuir isotherm model and Temkin The controlling mechanism for adsorption process
isotherm model at 25°C are having 0.976 and 0.962, can be well described by kinetic study, which is the
respectively, while the same for adsorption data fundamental factor of mass transfer (Demirbas
fitted with Freundlich equation is 0.993. et al., 2009). To investigate the adsorption
Hence, to describe the adsorption of oil from the mechanism of oil by synthesized activated charcoal

Figure 10. Freundlich adsorption isotherm at different temperatures.

 CHEMICAL ENGINEERING COMMUNICATIONS 907

Figure 11. Temkin adsorption isotherm at different temperatures.

the pseudofirst-order, pseudosecond-order and Pseudosecond-order kinetic model. The kinetics of

intraparticle diffusion models have been used (Ho adsorption process may also be characterized
and McKay, 1999b). The adsorption kinetics were by the pseudosecond-order equation based on
considered to evaluate the amount of oil separated equilibrium adsorption and is expressed as (Ho
from the emulsion having different initial oil and McKay, 1998);
concentration. It was observed that the initial
adsorption rate much faster and the reaction t 1 t
¼ þ ð10Þ
approaches equilibrium within 180 min. 2
qt K2 qe qe

where qe (mg g−1) is the amount of oil adsorbed at

Pseudofirst-order kinetic model. Largergren in equilibrium and K2 (g.mg−1.min−1) is the equilib-
1898 proposed an adsorption model which rium rate constant of the pseudosecond-order
follow pseudofirst-order equation to determine chemical sorption. The pseudosecond-order is
the rate constant for any adsorption process as based on some assumptions, viz., the adsorption
given in Eq. (9) (Largergren, 1898). follows Langmuir isotherm, chemical adsorption
lnðqe qt Þ ¼ ln qe K1 t ð9Þ is rate controlling step, and the rate of occupation
of adsorption sites is proportional to the square of
where qe (mg g−1) is the amount of oil adsorbed at number of unoccupied sites. Equation (10) depicts
equilibrium, qt (mg g−1) is the amount of oil that the plot of t/qt vs t follow a linear relationship.
adsorbed at time t (min), K1 is the rate constant qe and K2 can be obtained from the slope and
for adsorption (min−1). Plots of lnðqe qt Þ vs t is intercept of the plot as shown Figure 13. The calcu-
shown in Figure 12 and was used to calculate the lated and the experimental values of qe and K2 are
values of K1. The experimental values qe are in given in Table 4. The regression (R2) values and
good agreement with calculated values from linear adequate fitting of the plots confirm that the
plots and reported in Table 4. This shows that the adsorption of oil onto the surface of the activated
adsorption kinetics of oil on the activated charcoal charcoal also follows the second-order kinetic
satisfies the pseudofirst-order model. model.
908 V. K. RAJAK ET AL.

Figure 12. Pseudofirst-order reaction for oil adsorbed onto powder activated charcoal at different concentrations.

Intra-particle diffusion. Weber and Morris there are two linear portions with different slopes
proposed a widely accepted model based on in each plot as shown in Figure 14. The initial parts
kinetic of the process, which is centered on time are ascribed by boundary layer diffusion effects,
dependent intra-particle diffusion of the compo- and the second parts implies the intra-particle dif-
nents (Weber and Morris, 1963). According to this fusion effects (Hall et al., 1966; Srihari and Das,
model the adsorption rate depends upon the dif- 2008). Kinetic studies were performed to evaluate
fusion rate of adsorbent and adsorbate among each the rate of the limiting adsorption process and
other. The model equation is shown as follows: the rate of adsorption of oil onto the synthesized
pffiffi AC. The rate constants; kd1 and kd2, of intraparticle
qt ¼ kd t þ C ð11Þ diffusion (mg g−1) are shown in Table 4. It is
where qt (mg g−1) is the instantaneous amount of observed from the table that kd1 is higher than
oil adsorbed per unit mass of activated charcoal kd2, due to the availability of higher number of acti-
and C (mg g−1) is a constant which is proportional vated sites in the beginning of adsorption.
to the boundary layer thickness.
pffiffi The Eq. (11) Based on the regression coefficients and
shows that the plot of qt vs t is straight line. predicted qe values for different models in
However, experimentally it has been found that Table 4, it is observed that the adsorption process
 CHEMICAL ENGINEERING COMMUNICATIONS 909

Figure 13. Pseudosecond-order reaction for oil adsorbed onto powder activated charcoal at different oil concentrations.

in presence of synthesized charcoal obeys both the

pseudofirst order as well as the pseudosecond-
order kinetic model. However, it has been found
that v2 values are much less in pseudosecond-order
than others (Table 4). Thus based on the high
corelation coefficient and low v2 value, it can be
concluded that adsorption of oil onto charcoal
follows the pseudosecond-order kinetic model.
Thermodynamic parameters
The rate constant of pseudosecond-order for oil
adsorption may be expressed by the Arrhenius
equation as a function of temperature:
Ea
ln k2 ¼ ln A ð12Þ
RT
Figure 14. Intra-particle diffusion reaction for oil adsorbed where Ea and A are the Arrhenius activation energy
onto powder activated charcoal at different oil concentrations. (kJ mol−1) and the Arrhenius factor respectively.
910 V. K. RAJAK ET AL.

Table 4. Kinetic model parameters and correlation coefficients for adsorption of oil at different initial concentration onto
synthesized charcoal at 25°C.
Pseudofirst-order Pseudosecond-order Intra-particle diffusion
−1 −1
C0 qe exp K1 qe K2 (g mg min ) qe kd1 kd2
(mg L−1) (mg g−1) (min−1) (mg g−1) R2 v2 ð�10 4 Þ (mg g−1) R2 v2 (mg g−1) R2 v2 (mg g−1) R2 v2
510 99 −0.0218 99.3 0.994 0.541 1.66 126.1 0.998 0.131 9.94 0.999 0.0008 5.27 0.905 0.250
650 124 −0.0217 126.9 0.994 0.671 1.22 160.5 0.998 0.099 12.73 0.999 0.0016 6.74 0.906 0.289
770 145 −0.0215 149.9 0.994 1.217 0.97 190.5 0.998 0.117 15.04 0.999 0.0022 8.07 0.912 0.374
890 165.4 −0.0217 173.4 0.994 2.544 0.81 219.3 0.998 0.143 17.46 0.999 0.0021 9.23 0.908 0.446
1,000 182 −0.0219 196.1 0.995 6.118 0.67 246.9 0.996 0.494 19.79 0.999 0.0005 10.26 0.905 0.521

R is the gas constant (8.314 J mol−1 · K−1) and T (K) the distribution coefficient obtained at four
is temperature of the solution. Negative activation different solution temperatures of 25, 40, 50, and
energy indicates the absence of energy barriers to 60°C. DG0 is determined from the Eq. (13).
cause the adsorption to occur whereas, the positive The result presented in the Table 5 with negative
activation energy specifies the extra energy that value of DH 0 indicates that the adsorption of oil on
must be needed to overwhelmed for adsorption activated charcoal takes place by an exothermic
to occur (Güzel et al., 2008; Ofomaja, 2007). process. The negative values of Gibbs free energy
The obtained value of the activation energy ðDG0 Þ indicate that the adsorption process is
(−11.97 kJ mol−1) in Table 5 indicates that there spontaneous and feasible. On increasing tem-
is no energy barriers in the reaction process and perature the value of DG0 becomes less negative
the reaction is exothermic in nature. which directs that the reaction is less promising
The thermodynamic parameters such as free at elevated temperatures. The negative value of
energy (DG0 ), enthalpy ðDH 0 Þ, and entropy ðDS0 Þ DS0 (−13.66 J mol−1 K−1) indicates the reduced
give a description of adsorption behavior related randomness at the solid-solution interface.
to temperature. Parameters can be calculated from Al-Johani and Salam have observed the similar
DG0 ¼
RT ln Kd ð13Þ trends on the thermodynamic and kinetics study
DS 0
DH 0 of aniline adsorption in presence of multiwalled
ln Kd ¼ ð14Þ carbon nanotubes from aqueous solution
R RT
(Al-Johani and Salam, 2011).
where R (8.314 J mol−1 · K−1) is the universal gas
constant, T (K) is the absolute temperature of the
solution and Kd is the distribution coefficient Conclusion
which can be calculated as: Charcoal samples were synthesized from saw dust
CAe and activated with different chemicals viz.
Kd ¼ ð15Þ
Ce H3PO4, ZnCl2, and FeSO4 · 7H2O, for their uses
where Ce (mg L−1) is the equilibrium concentration on adsorption of oil from oil-in-water emulsion.
and CAe (mg L−1) is the amount adsorbed on solid From BET analysis highest BET surface area of
at equilibrium. Based on Eq. (14), the value of DS0 310.23 m2 g−1 is observed for the synthesized
and DH 0 were calculated respectively from the charcoal activated by H3PO4. SEM analysis of
slope and intercept of ln Kd vs 1/T, where Kd is charcoal samples reveals a heterogeneous surface
with a variety of randomly distributed pore size.
EDX analysis reveals that newer elements (P, Zn,
Table 5. Thermodynamics parameters for adsorption of oil
onto powder activated charcoal. Fe, and Cl) have been detected in charcoal
Activation samples activated with different chemical agents.
Temperature DG0 energy, Ea DH0 DS0 Synthesized charcoal has sufficient numbers of
(°C) (kJ mol−1) (kJ mol−1) (kJ mol−1) (J mol−1 K−1)
pores on a rough and snare type structure of
25 −5.735 −11.97 −9.89 −13.66
40 −5.720
surface where the oil droplets may be trapped
50 −5.562 and adsorbed easily. After adsorption, a layer of
60 −5.216 oil spreads over the surface of activated charcoal.
 CHEMICAL ENGINEERING COMMUNICATIONS 911

FTIR study of charcoal shows that all the charcoal Austin, G. T., and Shreve, S. (1985). Chemical Process
samples are having similar types of desired func- Industries, 5th ed., McGraw Hill Company, New York.
tional groups. The studies show that synthesized Ayranci, E., and Duman, O. (2006). Adsorption of aromatic
organic acids onto high area activated carbon cloth
charcoal activated by H3PO4 is having higher
in relation to wastewater purification, J. Hazard. Mater.,
adsorption capacity for removal of oil from the 136(3), 542–552.
oil-in-water emulsion. The adsorbed amount of Bansal, S., Von Arnim, V., Stegmaier T., and Plank, H. (2011).
oil increases with increasing the dosage of the Effect of fibrous filter properties on the oil-n-water
adsorbent, but after dosage of 4 g L−1, the increase emulsion separation and filtration performance, J. Hazard.
in percent oil removal is only marginal. The Mater., 190(1–3), 45–50.
Bansode, R. R., Losso, J. N., Marshall, W. E., Rao, R. M., and
adsorbed amount of oil is dependent on the initial
Portier, R. J. (2003). Adsorption of volatile organic
oil concentration. It decreases as the initial oil con- compounds by pecan shell-and almond shell-based granu-
centration increases. Oil removal (%) decreases lar activated carbons, Bioresour. Technol., 90(2), 175–184.
with increase in temperature which implies that Baup, S., Jaffre, C., Wolbert, D., and Laplanche, A. (2000).
adsorption of oil on synthesized charcoal is Adsorption of pesticides onto granular activated carbon:
exothermic in nature. The adsorption of oils from Determination of surface diffusivities using simple batch
experiments, Adsorption, 6(3), 219–228.
the oil–water emulsion by activated charcoal is best
Berman, Y., and Tamir, A. (2003). Kinetics of droplets’
described by Freundlich isotherm. The adsorption sedimentation in a continuous gravity settler, Chem. Eng.
process follows both the pseudofirst-order as well Sci., 58(10), 2089–2102.
as the pseudosecond-order kinetics with a better Campos, J. C., Borges, R. M. H., Oliveira Filho, A. M. D.,
fit for the later. Along with surface adsorption, Nobrega, R., and Sant’Anna, G. L. (2002). Oilfield
intra-particle diffusion also contributes to control wastewater treatment by combined microfiltration and
biological processes, Water. Res., 36(1), 95–104.
of the rate of adsorption. The negative value of
Cerqueira, A. A., Marques, M. D. C., and Russo, C. (2011).
Arrhenius activation energy (−11.97 kJ mol−1) and Avaliação do processo eletrolítico em corrente alternada
enthalpy change ðDH 0 Þ suggest that the reaction no tratamento de água de produção, Quim. Nova, 34(1),
is exothermic and also reveals the absence of 59–63.
energy barriers in the reaction process. Negative Choy, K. K., McKay, G., and Porter, J. F. (1999). Sorption of
values of Gibb’s free energy change ðDG0 Þ shows acid dyes from effluents using activated carbon, Resour.
Conserv. Recycl., 27(1), 57–71.
that the adsorption is spontaneous and feasible.
Dąbrowski, A. (2001). Adsorption—From theory to practice,
Adv. Colloid Interface Sci., 93(1), 135–224.
Demirbas, E., Dizge, N., Sulak, M. T., and Kobya, M. (2009).
Acknowledgment Adsorption kinetics and equilibrium of copper from
aqueous solutions using hazelnut shell activated carbon,
Author would like to thank the central research facility Chem. Eng. J., 148(2), 480–487.
(CRF) Indian Institute of Technology (ISM) Dhanbad for Desta, M. B. (2013). Batch sorption experiments: Langmuir
conducting the experiments. and Freundlich isotherm studies for the adsorption
of textile metal ions onto teff straw (Eragrostis tef)
References agricultural waste, J. Thermodyn., 2013, 1–6.
Domenico, M., Giudice, A. L., Michaud, L., Saitta, M., and
Agarwal, M., and Singh, K. (2017). Heavy metal removal from Bruni, V. (2004). Diesel oil and PCB degrading
wastewater using various adsorbents: A review, J. Water psychrotrophic bacteria isolated from Antarctic seawaters
Reuse Desal., 7(4), 387–419. (Terra Nova Bay, Ross Sea), Polar Res., 23(2), 141–146.
Agyei, N. M., Strydom, C. A., and Potgieter, J. H. (2000). An Emam, E. A. (2013). Modified activated carbon and bentonite
investigation of phosphate ion adsorption from aqueous used to adsorb petroleum hydrocarbons emulsified in
solution by fly ash and slag, Cement Concrete Res., 30(5), aqueous solution, Am. J. Environ. Prot., 2(6), 161–169.
823–826. Fard, A. K., Rhadfi, T., Mckay, G., Al-marri, M., Abdala, A.,
Al-Johani, H., and Salam, M. A. (2011). Kinetics and Hilal, N., and Hussien, M. A. (2016). Enhancing oil
thermodynamic study of aniline adsorption by multi- removal from water using ferric oxide nanoparticles doped
walled carbon nanotubes from aqueous solution, J. Colloid carbon nanotubes adsorbents. Chem. Eng. J., 293, 90–101.
Interface Sci., 360(2), 760–767. Febrianto, J., Kosasih, A. N., Sunarso, J., Ju, Y. H., Indraswati,
Ansari, R., and Masoudi, M. (2004). Removal of chromium N., and Ismadji, S. (2009). Equilibrium and kinetic studies
hexavalent from aqueous solution using activated carbon, in adsorption of heavy metals using biosorbent: A summary
IJC, 14(3), 139–142. of recent studies, J. Hazard. Mater., 162(2), 616–645.
912 V. K. RAJAK ET AL.

Fu, Y., and Chung, D. D. L. (2011). Coagulation of oil in water Kumar, S., Panigrahi, P., Saw, R. K., and Mandal, A. (2016).
using sawdust, bentonite and calcium hydroxide to form Interfacial interaction of cationic surfactants and its effect
floating sheets, Appl. Clay Sci., 54(4), 634–641. on wettability alteration of oil-wet carbonate rock, Energy
Ghasemi, M., Ghoreyshi, A. A. Younesi, H., and Khoshhal, S. Fuels, 30(4), 2846–2857.
(2015). Synthesis of a high characteristics activated Laine, J., and Calafat, A. (1989). Preparation and characteriza-
carbon from walnut shell for the removal of Cr (VI) and tion of activated carbons from coconut shell impregnated
Fe (II) from aqueous solution: Single and binary solutes with phosphoric acid, Carbon, 27(2), 191–195.
adsorption, IJChE, 12(4), 29. Largergren, S. (1898). Zur theorie der sogenannten adsorption
Guocheng, L. Ü., Jiao, H., Liu, L., Hongwen, M. A., Qinfang, geloster stoffe. Kungliga Svenska Vetenskapsakademiens,
F. A. N. G., Limei, W. U., … Zhang, Y. (2011). The Handlingar, 24(4), 1–39.
adsorption of phenol by lignite activated carbon, Chin. J. Lasindrang, M., Suwarno, H., Tandjung, S. D., and Kamiso,
Chem. Eng., 19(3), 380–385. H. N. (2015). Adsorption pollution leather tanning
Güzel, F., Yakut, H., and Topal, G. (2008). Determination of industry wastewater by chitosan coated coconut shell active
kinetic and equilibrium parameters of the batch adsorption charcoal, Agric. Agric. Sci. Procedia, 3, 241–247.
of Mn (II), Co (II), Ni (II) and Cu (II) from aqueous Lei, S., Shi, Z., Ou, J., Wang, F., Xue, M., Li, W., Qiao, G.,
solution by black carrot (Daucus carota L.) residues, Guan, X., and Zhang, J. (2017). Durable superhydrophobic
J. Hazard. Mater., 153(3), 1275–1287. cotton fabric for oil/water separation, Colloids Surf. A
Hall, K. R., Eagleton, L. C., Acrivos, A., and Vermeulen, T. Physicochem. Eng. Aspects, 533, 249–254.
(1966). Pore-and solid-diffusion kinetics in fixed-bed Liu, Z., Huang, Y., and Zhao, G. (2016). Preparation
adsorption under constant-pattern conditions, Ind. Eng. and characterization of activated carbon fibers from
Chem. Fundam., 5(2), 212–223. liquefied wood by ZnCl2 activation, BioResources, 11(2),
Hameed, B. H., Din, A. M., and Ahmad, A. L. (2007). 3178–3190.
Adsorption of methylene blue onto bamboo-based Mandal, A., Ojha, K., and Ghosh, D. N. (2003). Removal of
activated carbon: Kinetics and equilibrium studies, colour from distillery wastewater by different processes,
J. Hazard. Mater., 141(3), 819–825. Indian Chem. Eng., 45(4), 264–267.
He, Y., and Jiang, Z. W. (2008). Technology review: treating Mane, V. S., Mall, I. D., and Srivastava, V. C. (2007). Use of
oilfield wastewater, Filtr. Separat., 45(5), 14–16. bagasse fly ash as an adsorbent for the removal of brilliant
Ho, C. C., and Chan, C. Y. (1986). The application of lead green dye from aqueous solution, Dyes. Pigm., 73(3),
dioxide-coated titanium anode in the electroflotation of 269–278.
palm oil mill effluent, Water Res., 20(12), 1523–1527. Mehrasbi, M. R., Farahmandkia, Z., Taghibeigloo B., and
Ho, Y. S., and McKay, G. (1998). Sorption of dye from Taromi, A. (2009). Adsorption of lead and cadmium from
aqueous solution by peat, Chem. Eng. J., 70(2), 115–124. aqueous solution by using almond shells, Water Air Soil
Ho, Y. S., and McKay, G. (1999a). Competitive sorption of Pollut., 199(1–4), 343.
copper and nickel ions from aqueous solution using peat, Mickova, I. L. (2015). Advanced electrochemical technologies
Adsorption, 5(4), 409–417. in wastewater treatment. Part II: Electro-flocculation and
Ho, Y. S., and McKay, G. (1999b). Pseudo-second order model electro-flotation, ASRJETS, 14(2), 273–294.
for sorption processes, Process Biochem., 34(5), 451–465. Mondal, S., and Wickramasinghe, S. R. (2008). Produced
Huang, J., Liu, H., Chen, S., and Ding, C. (2017). Graphene water treatment by nanofiltration and reverse osmosis
aerogel prepared through double hydrothermal reduction membranes, J. Membr. Sci., 322(1), 162–170.
as high-performance oil adsorbent. Mater. Sci. Eng. B, Moosai, R., and Dawe, R. A. (2003). Gas attachment of oil
226, 141–150. droplets for gas flotation for oily wastewater cleanup, Sep.
Huang, J., Wang, X., Jin, Q., Liu, Y., and Wang, Y. (2007). Purif. Technol., 33(3), 303–314.
Removal of phenol from aqueous solution by adsorption Nautiyal, P., Subramanian, K. A., and Dastidar, M. G. (2016).
onto OTMAC-modified attapulgite, J. Environ. Manage., Adsorptive removal of dye using biochar derived from
84(2), 229–236. residual algae after in-situ transesterification: Alternate
Iqbal, M. J., and Ashiq, M. N. (2007). Adsorption of dyes from use of waste of biodiesel industry, J. Environ. Manage.,
aqueous solutions on activated charcoal, J. Hazard. Mater., 182, 187–197.
139(1), 57–66. Nayak, M. C., Isloor, A. M., Moslehyani, A., and Ismail, A. F.
Karaer, H., and Kaya, İ. (2016). Synthesis, characterization (2017). Preparation and characterization of PPSU
of magnetic chitosan/active charcoal composite and using membranes with BiOCl nanowafers loaded on activated
at the adsorption of methylene blue and reactive blue4. charcoal for oil in water separation, J. Taiwan Inst. Chem.
Microporous Mesoporous Mater., 232, 26–38. Eng., 77, 293–301.
Karanfil, T., Yadav, A., Zhang, C. C., Ghosh, S., and Ahmed, Ocampo-Perez, R., Leyva-Ramos, R., Mendoza-Barron, J., and
S. (2006). Physico-chemical processes, Water Environ. Res., Guerrero-Coronado, R. M. (2011). Adsorption rate of
78(10), 1193–1260. phenol from aqueous solution onto organobentonite:
Kumar, S., Guria, C., and Mandal, A. (2015). Characterization and Surface diffusion and kinetic models, J. Colloid Interface
stability analysis of crude oil-water emulsions, JPET, 5, 1–10. Sci., 364(1), 195–204.
 CHEMICAL ENGINEERING COMMUNICATIONS 913

Ofomaja, A. E. (2007). Sorption dynamics and isotherm Takeuchi, K., Fujishige, M., Kitazawa, H., Akuzawa, N.,
studies of methylene blue uptake on to palm kernel fibre, Medina, J. O., Morelos-Gomez, A., Cruz-Silva, R.,
Chem. Eng. J., 126(1), 35–43. Araki, T., Hayashi, T., Terrones, M., and Endo, M.
Ogasawara, S., Kuroda, M., and Wakao, N. (1987). Preparation (2015). Oil sorption by exfoliated graphite from dilute
of activated carbon by thermal decomposition of used oil–water emulsion for practical applications in produced
automotive tires, Ind. Eng. Chem. Res., 26(12), 2552–2556. water treatments, J. Water Process Eng., 8, 91–98.
Popa, N., and Visa, M. (2017). The synthesis, activation and Wang, J., Han, F., Liang, B., and Geng, G. (2017a). Hydrother-
characterization of charcoal powder for the removal mal fabrication of robustly superhydrophobic cotton
of methylene blue and cadmium from wastewater, Adv. fibers for efficient separation of oil/water mixtures and
Powder Technol., 28(8), 1866–1876. oil-in-water emulsions, J. Ind. Eng. Chem., 54, 174–183.
Rajak, V. K., Relish, K. K., Kumar, S., and Mandal, A. (2015). Wang, Y., Zhu, L., Zhu, F., You, L., Shen, X., and Li, S.
Mechanism and kinetics of separation of oil from (2017b). Removal of organic solvents/oils using carbon
oil-in-water emulsion by air flotation, Petrol. Sci. Technol., aerogels derived from waste durian shell, J. Taiwan Inst.
33(23–24), 1861–1868. Chem. Eng., 78, 351–358.
Shen, J., Huang, G., An, C., Xin, X., Huang, C., and Weber, W. J., and Morris, J. C. (1963). Kinetics of adsorption
Rosendahl, S. (2018). Removal of Tetrabromobisphenol A on carbon from solution, J. Sanitary Eng. Div., 89(2), 31–60.
by adsorption on pinecone-derived activated charcoals: Wigmans, T. (1989). Industrial aspects of production and use
Synchrotron FTIR, kinetics and surface functionality of activated carbons, Carbon, 27(1), 13–22.
analyses, Bioresour. Technol., 247, 812–820. Xing, W., Ngo, H. H., Kim, S. H., Guo, W. S., and Hagare, P.
Srihari, V., and Das, A. (2008). The kinetic and thermodyn- (2008). Adsorption and bioadsorption of granular activated
amic studies of phenol-sorption onto three agro-based carbon (GAC) for dissolved organic carbon (DOC) removal
carbons, Desalination, 225(1–3), 220–234. in wastewater, Bioresour. Technol., 99(18), 8674–8678.
Sulaymon, A. H., and Kshash, J. M. (2010). Removal of oil Yang, H., Bian, S., Hu, J., Li, F., and Yao, T. (2016). Effect
from wastewater by organoclay prepared from Iraqi of water chemistry on the adsorption of lubricating oil on
bentonite, J. Eng., 16(4), 5778. oxidized graphite, J. Mol. Liq., 219, 1157–1160.