Chemical Engineering Journal 307 (2017) 914–927

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Effects of bimetallic Ce/Fe nanoparticles on the desulfurization of

thiophenes using activated carbon
Gaddafi I. Danmaliki a, Tawfik A. Saleh b,⇑
a
Environmental Science Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
b
Chemistry Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The effect of loading of cerium and

iron on AC was evaluated.

The adsorbents were evaluated for
the removal of thiophene,
benzothiophene, and
dibenzothiophene.

The efficiency of the adsorbents
followed the order AC < AC/Fe < AC/
Ce < AC/Ce/Fe.

a r t i c l e i n f o a b s t r a c t

Article history: Activated carbon (AC) was loaded with two different metals: cerium and iron. Three composites were
Received 29 June 2016 prepared namely AC/Ce, AC/Fe, and AC/Ce/Fe. The composites were investigated for the simultaneous
Received in revised form 28 August 2016 desulfurization of thiophene, benzothiophene (BT), and dibenzothiophene (DBT) in a model fuel. The sur-
Accepted 30 August 2016
face structures, morphologies, and pore structures were characterized. The unloaded AC had the highest
Available online 31 August 2016
surface area and pore volume of 460.27 m2/g and 0.71 cm3/g respectively. Moreover, the unloaded AC
showed the highest surface oxygen-containing groups but performed the least in desulfurization. The
Keywords:
adsorptive desulfurization efficiency followed the order: AC < AC/Fe < AC/Ce < AC/Ce/Fe. The AC/Ce/Fe
Nanocomposites
Desulfurization
performed the best in the adsorption of thiophene (31%), BT (30%), and DBT (75%) despite having the least
Regeneration surface area and pore volume of 430.44 m2/g and 0.64 cm3/g. All the adsorbents showed a greater affinity
Fixed-bed to the large size DBT. Batch and column experiments carried out using AC/Ce/Fe revealed a high absorp-
tive capacity and breakthrough for DBT i.e. 16 mg/g. The kinetic data showed a synergistic effect of sur-
face adsorption and intraparticle diffusion occurring concurrently, and the results complied with the
pseudo-second-order kinetic model. The equilibrium adsorption results are well fitted to the
Freundlich isotherm indicating a heterogeneous adsorption process. Thermal regeneration experiments
carried out on AC/Ce/Fe showed stable efficiency in the adsorptive desulfurization after regeneration
cycles. The regeneration properties displayed by the adsorbent could enhance its practical application
in an industrial setting.
Ó 2016 Elsevier B.V. All rights reserved.

1. Introduction

Desulfurization is significant in the refining process of crude oil

⇑ Corresponding author. because sulfur containing compounds cause environmental pollu-
E-mail addresses: tawfik@kfupm.edu.sa, tawfikas@hotmail.com (T.A. Saleh).
tion, poison catalysts, and corrode refining equipment. Thus, there

http://dx.doi.org/10.1016/j.cej.2016.08.143
1385-8947/Ó 2016 Elsevier B.V. All rights reserved.
 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927
are ongoing efforts to lower the limits of sulfur in all kinds of oils.
Environmental Protection Agency has mandated 15 ppm (wt) high-
way diesel since 2006 [1,2]. The conventional hydrodesulfurization
(HDS) technique cannot achieve 15 ppm ultra-low sulfur diesel
regulation set by so many countries to curtail the impacts of sulfur
to health, environment, and the economy. Additionally, HDS is not
effective in the removal of refractory sulfur compounds such as
thiophene, benzothiophene (BT), and dibenzothiophene (DBT) [3].
Hence the need for viable, cost-effective, and efficient techniques.
Alternative methods to supplement the drawbacks of HDS include
oxidative desulfurization, ionic liquid desulfurization, biodesulfur-
ization, and adsorptive desulfurization (ADS) [4–8].
Adsorbents such as zeolites, zirconia, silica, alumina, metal oxi-
des, nickel-based sorbents, membranes, and activated carbon (AC)
have been used in the ADS [9–13]. However, finding cost efficient
and regenerable adsorbents has been the subject of interesting
research [14,15]. AC proves to have a high adsorptive capacity, a
high surface area, relatively cheap, and can be easily regenerated
[16,17]. Additionally, AC can be synthesized from a variety of
sources such as charcoal, biochar, wood, peat, sewage sludge, ani-
mal bones, hair, and lignocellulosic biomass etc [18]. Modifying AC
with oxidizing agents, metals, and metal oxides is known to
improve its selectivity, reactivity, and capacity to sulfur com-
pounds. Carbon materials have been modified using elements such
as nickel, zinc, cobalt, silver, copper, and zirconium [19–22].
Xiong et al. prepared a cerium-loaded activated carbon by clas-
sical soaking impregnation method and evaluated the efficiency of
the adsorbent for the removal of DBT from model fuels. The study
confirmed that cerium loading on activated carbon enhanced the
selectivity and capacity towards DBT than virgin activated carbon
and the improved performance was mainly attributed to changes
in the surface chemistry [23]. Yan et al. demonstrated the
hydrothermal synthesis of CeO2 nanoparticles (200 nm) and its
successful loading onto AC for the removal of SO2. The result
showed a remarkable SO2 adsorption capacity and the reaction
mechanism of adsorbing and trapping SO2 by the modified AC
was elucidated. They showed that in the presence of SO2 and O2,
the generation of sulfate accompanied by the reduction of Ce4+ to
Ce3+ was the main contributing factor in the adsorption experi-
ments [24].
The simultaneous removal of SO2 and NOx by palm shell acti-
vated carbon (PSAC) impregnated with several metal oxides (Ni,
V, Fe, and Ce) have been reported by Sumathi et al. The result
showed that PSAC modified by CeO2 (PSAC-Ce) displayed the high-
est sorption capacity. They attributed the result mainly to the
physicochemical features of PSAC-Ce and its enhanced catalytic
activity [25].
Commercial activated carbon has been modified by iron oxyhy-
droxide nanoparticles for diesel fuel desulfurization of DBT and
4,6-dimethyl dibenzothiophene (DMDBT) having an initial concen-
tration of 20 ppm. The study used decane and hexadecane as the
solvents, and the effects of tert-butylbenzene and naphthalene
(aromatics) were evaluated. The result indicated that the concen-
tration of naphthalene affects the adsorption capacities of both
DBT and DMDBT. However, the concentration of tertbutylbenzene
affected only the uptake of DMDBT. The study also realized that at
low concentration of aromatics, the modified AC performed better
than unmodified AC. Additionally, oxidized species were identified
on the surface of the modified AC suggesting that iron was acting
as an oxidant and an acidic center, attracting basic DBT and
DMDBT [26].
Billions of waste rubber tires (WRTs) are generated worldwide
every year, and thus the non-biodegradable end-of-life tires have
to be disposed [27]. Disposal of WRTs presents a serious challenge
worldwide including land use problem, disruption of landfill lin-
ings leading to groundwater contamination, associated fire out-
915
breaks, and public health issues. However, despite their radical
nature, they still have other useful applications in the production
of fuel and valuable materials such as AC for industrial purposes
[28,29].
In this work, we focused on two global issues: waste manage-
ment and desulfurization. We loaded AC with cerium first (AC/
Ce), then iron (AC/Fe) separately, and a bimetallic composite of
these metals (AC/Ce/Fe). We monitored the effectiveness of these
nanocomposites in the simultaneous ADS of thiophene, BT, and
DBT. This work is highly significant and timely because it provides
solutions to environmental policies, health problems, management
initiatives, and defects in the refining industry.
2. Experimental
2.1. Preparation of AC from WRTs
AC was derived from waste rubber tires (WRTs) as per the
reported procedure [30,31]. In summary, WRTs were cleaned,
and dried in an oven at 110 °C, then heated at 300 °C to isolate
the produced oil, distilled diesel oil, and black tire crude oil. Car-
bonization was carried out in a muffle furnace at 500 °C for five
hours to remove the ash as well as the carbon black. The char
was then treated with an H2O2 solution to oxidize adhering organic
impurities. It was then washed and dried, then, activated at 900 °C
for five hours. The AC was washed with deionized water and dried
in an oven overnight. The dried AC was next treated with 4 M
HNO3 (1 g AC: 15 ml HNO3) at 90 °C for three hours to develop fur-
ther surface acidic functional groups that are known to enhance
adsorption [32]. The AC was then washed thoroughly and dried
in an oven at 110 °C for 24 h.
2.2. Synthesis of AC/Ce, AC/Fe, and AC/Ce/Fe
2.2.1. Loading 10% cerium on AC (AC/Ce)
Thermal co-precipitation method was used for the synthesis of
the nanocomposites. In a typical experiment, 7.0 g of AC was dis-
persed by sonication in 150 mL of deionized water and 100 mL
ethanol by the use of sonicator and stirred for five hours. 20 mL
of ethylene glycol was added serving as a linker to connect the
metal ions to the AC surface sites. Then, a 5 mL solution containing
2.17 g of cerium nitrate hexahydrate (Ce(NO3)36H2O) was added
drop-wise into the dispersed AC to make a 1 M solution. Then,
the pH at 8–9 was maintained by adding ammonia while stirring
for two hours. The temperature of the mixture was increased to
80 °C for six hours while stirring, and the precipitate was filtered,
washed and dried at 110 °C overnight. The dried adsorbent was
calcined at 350 °C for four hours to ensure adequate localization
of the metal to the surface of the adsorbent and to obtain the
chemical phase of the metals as discussed under XRD section.
2.2.2. Loading 10% iron on AC (AC/Fe)
7.0 g of AC was dispersed in 150 mL of deionized water and
100 mL ethanol by the use of sonicator and stirred for five hours.
Then, 20 mL of ethylene glycol was added followed by stirring for
two hours. 12.53 mL solution containing 5.06 g of Ferric Nitrate
(Fe(NO3)39H2O) solution was added drop-wise to the dispersed
AC to make a 1 M solution. The pH was maintained at 8–9 by add-
ing ammonia and NaOH, followed by heating to 80 °C for 6 h under
stirring. The precipitate was filtered, washed, dried at 110 °C over-
night and calcined at 350 °C for four hours.
2.2.3. Loading cerium and iron bimetallic composite on AC (AC/Ce/Fe)
7.0 g of AC was dispersed in 150 mL of deionized water, 100 mL
ethanol, and 20 mL ethylene glycol and stirred for five hours. Then,
916 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927
a 5 mL solution containing 0.88 g of cerium nitrate hexahydrate
solution was added drop-wise into the dispersed AC and main-
tained at a pH of 8–9. The mixture was refluxed at 90 °C for 5 h.
The precipitate was washed and dried at 110 °C overnight. The
dried material was dispersed in 150 mL deionized water, 100 mL
ethanol and 20 mL ethylene glycol. 13 mL solution containing
5.06 g of ferric nitrate nonahydrate was added to the mixture
and stirred for 2 h at pH of 8–9. The set up was refluxed at 90 °C
for five hours, and the precipitate was filtered, washed, dried at
110 °C overnight and then calcined at 350 °C for 4 h to ensure ade-
quate localization of the metals to the surface of the AC, Scheme 1.
2.3. Characterization of the nanocomposites
The porous structure and Brunauer-Emmett-Teller (BET) sur-
face area of the synthesized AC and the nanocomposites were char-
acterized by nitrogen adsorption/desorption on a Micromeritics
TriSta II PLUS. The X-ray diffraction (XRD) patterns of the prepared
materials were obtained with Cu Ka radiation (a = 1.5418 Å) on a
Rigaku(Miniflex-II) X-ray Powder Diffractometer. The X-ray gun
was operated at 40 kV and 200 mA with data collection at 4°/min
scan rate in the range 2h 15–80°. The mean grain size (D) of the
particles was determined from the XRD line broadening measure-
ment from the Scherrer equation.
Scanning electron microscope, JEOL-JSM-6610LV, equipped
with tungsten electron gun was used to examine the surface mor-
phology. The energy dispersive X-ray spectroscopy (EDX) analysis
was employed to obtain the elements forming the prepared mate-
rials. The Fourier transform infrared spectroscopy (FT-IR) was used
to identify the type of functional groups present on the prepared
adsorbents. The spectra were taken by Nicolet 6700 spectrometer
(Thermo Electron). The measurements were carried out by making
KBr pellets. The spectrum was obtained with 64 scans with back-
ground noise correction.
Scheme 1. Illustration of the preparation of cerium and iron bimetallic AC composite (AC/Ce/Fe).
2.4. Adsorption experiment
2.4.1. Batch adsorption
The adsorption experiment was carried out in both batch and
fixed bed models. A model diesel fuel was formed of thiophene,
BT, and DBT in a solvent of 85% hexane and 15% toluene. The total
sulfur concentration in the model fuel was 150 ppm composed by
50 ppm of each component in 1 L of hexane/toluene mixture. Batch
adsorption studies were carried out using AC, AC/Ce, AC/Fe and AC/
Ce/Fe nanocomposites in 250-mL Erlenmeyer flasks containing
25 mL of 150 ppm model fuel. The nanocomposites dosages were
varied from 0.1 to 0.5 g and the flasks were agitated in a ther-
mostat shaker at a speed of 150 rpm till equilibrium was achieved.
A syringe filter was used for aliquots collection for a particular per-
iod from each set of experiment, and the sulfur was monitored by
gas chromatography equipped with sulfur chemiluminescence
detector (GC-SCD). The efficiency of the nanocomposites was
determined as:
Co  Ce
x¼  100 ð1Þ
Co
where x is sulfur adsorption percentage (%) C0 is initial concentra-
tion of sulfur in model oils (ppm), Ce is the sulfur concentration
at equilibrium. The qe in mg/g was calculated by:
VðC 0  C e Þ
qe ¼ ð2Þ
m
where qe in mg/g is the capacity or sulfur compounds adsorbed per
unit mass of the adsorbent at equilibrium; V in a liter is the volume
of fuel, and m in gram is the sorbent amount.
2.4.2. Fixed bed adsorption
Fixed bed adsorption experiment was used to evaluate the
adsorption efficiency of the synthesized AC and the nanocompos-
 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927
ites. The breakthrough of the best adsorbent was noted using a col-
umn of length 11 cm  1 cm diameter, Scheme 2. It is worth men-
tioning that the longer the column, the better the result because it
provides wider area and surface for interaction. A model fuel sam-
ple was passed through a column packed with 0.5 g adsorbent
using a peristaltic pump. The lower the flow rate of the model fuel
the longer the breakthrough. Therefore, 50 rpm (0.0095 m3/s) was
employed at room temperature. Aliquots were collected, and the
sulfur concentration was monitored using GC-SCD. The set up
was halted upon reaching a breakthrough.
2.5. Analysis method
The sulfur level in the samples was monitored by GC-SCD
Model 7890A Agilent system equipped with an autosampler and
splitless injector and a column Agilent 19091S-001: 2638-45555
50 m  0.2 mm dimensions and a film thickness of 0.5 lm methyl
siloxane stationary phase. 1 lL of the sample was injected with a
flow rate of 0.839 mL/min. The oven program was 60 °C for 1 min
then 10 °C/min to 230 °C for two minutes (run time was 20 min).
The retention times for thiophene, BT and DBT were 2.67, 10.80,
and 18.18 min respectively.
2.6. Regeneration experiment
The primary environmental concern of ADS is the disposal of
spent adsorbents. Regenerable adsorbents, therefore, hold a great
promise for an environmentally friendly ADS. The regeneration of
the synthesized materials was evaluated after saturation of the
sorbents with refractory sulfur compounds. Thermal regeneration
method was used in a closed system to determine the recycling
potentials of the adsorbents; the boiling points of thiophene, BT,
and DBT are 84 °C, 221 °C and 333 °C respectively. The adsorbents
were treated at 350 °C for three hours to effectively dispose of the
sulfur compounds. This temperature was the optimum for vaporiz-
ing all adhered sulfur compounds to the adsorbent, and the regen-
erated adsorbents were tested further for the removal of the
refractory sulfur compounds in batch mode. GC-SCD was used to
analyze the aliquots taken at intervals.
Scheme 2. Illustration of the fixed bed reactor used for the breakthrough experiments.
917
2.7. Data evaluation
Kinetic models, isotherm analysis, and breakthrough curves
were employed to display the data obtained from the batch and
fixed bed adsorption experiments. The adsorbent that performed
best i.e. AC/Ce/Fe was selected for the evaluation. The results were
fitted to pseudo-first order, pseudo-second order, and intraparticle
diffusion models. Linear forms of Langmuir and Freundlich iso-
therms were employed to understand the surface adsorption
patterns.
3. Results and discussion
3.1. Characterization
The adsorption/desorption patterns to determine the porosity
of the synthesized AC and the metal loaded AC are depicted in
Fig. 1. The samples exhibit Type IV isotherm classification
[33,34]. A hysteresis loop was noted at 0.8–1 pressure, which indi-
cates the mesopores nature. Additionally, a low uptake of nitrogen
can be noted at 0 –0.2 pressure indicating the presence of low
micropores within the samples [35,36].
Table 1 summarizes the surface areas, pore volumes, and pore
sizes of all prepared adsorbents. Newly synthesized AC has the
highest surface area and pore volume of 460.27 m2/g and
0.71 cm3/g but possess the least pore size of 59.83 Å. However,
loading metal nanoparticles to AC’s surface reduced the overall
surface area and pore volume. The impregnation with cerium
resulted in a small decrease in surface area while incorporation
of iron caused a significant decrease in this property. A significant
portion of the AC’s surface and its oxygen-containing functional
groups were linked with metal nanoparticles. The bimetallic adsor-
bent AC/Ce/Fe gave the least surface area and pore volume of
430 m2/g and 0.64 cm3/g, which means the higher the metal load-
ing on the AC’s surface, the lower the surface area. The Nitrogen
adsorption followed the order: AC > AC/Ce > AC/Fe > AC/Ce/Fe.
The BET surface area result is in agreement with those from FTIR,
XRD, and SEM analyses, where they all point to the deposition of
nanoparticles on the AC’s surface.
918 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927

of AC. However, the relative intensities of the broad signals are less
when compared to the loaded samples signifying replacement of
the carbon surface with nanoparticles. Additionally, the peaks cor-
responding to the diffraction patterns of Ce and Fe for the AC/Ce,
AC/Fe, and AC/Ce/Fe adsorbents were assigned accordingly. The
diffraction patterns of Ce are visible at the two theta values of
28.53 (1 1 1), 33 (2 0 0), 47 (2 2 0), 56 (311) signifying the presence
of CeO2 crystals in AC/Ce and AC/Ce/Fe. The pattern is in accor-
dance with JCPDS No: 34-0394. The peaks at two theta values of
43° and 63° were corresponding to 400 and 440 planes of iron
oxide to the AC/Fe and AC/Ce/Fe [38]. The average grain size (d)
of the Ce and Fe particles was estimated from the XRD related
peaks using the Scherrer equation [39]:

kk
d¼
bcosh

where k = 15.418 nm is the wavelength of the X-ray, b = FWHM (full

Fig. 1. Nitrogen adsorption/desorption pattern of AC, AC/Ce, AC/Fe and AC/Ce/Fe.
XRD is an important characterization tool used in elucidating
the crystalline phases of various materials. Each element has a dis-
tinct diffraction pattern when exposed to the X-ray beam. Fig. 2
shows the XRD patterns of the synthesized AC and the metal
loaded AC. All the samples showed broad diffraction peaks at 2
Theta values at around 26° (0 0 2) and 43° (1 0 1) indicating the
presence of amorphous carbon [37]. These peaks are due to the cre-
ation of pores upon decomposition of carbon along the direction of
graphitic structures, and they confirm the semi-crystalline nature
width at half maximum), h is diffraction angle and k is constant. The
average grain size of Ce and Fe particles calculated by using this
equation was found 35 and 58 nm.
The morphology of the synthesized adsorbents was character-
ized using SEM/EDX. Fig. 3 shows the SEM/EDX images displaying
the surface structures, elemental compositions, and the porous
nature of the adsorbents. Fig. 3a corresponds to pure AC synthe-
sized from WRTs, and it shows the presence of carbon and oxygen.
Additionally, it has the highest carbon weight percent (wt%) of
83.5, but the wt% decreases upon metal loading on the surface of
the adsorbent due to the deposition of nanoparticles. This result
correlates with the results of BET, XRD, and FTIR analyses. The car-
bon wt% followed the order AC (83.5) > AC/Fe (81) > AC/Ce (80.7) >
AC/Ce/Fe (79.2).
In addition to the carbon and oxygen, the samples loaded with
nanoparticles showed a homogeneous and relatively uniform load-
ing of metals and metal oxides on the surface of the AC. Fig. 3b

Table 1
Textural properties of AC, AC/Ce, AC/Fe and AC/Ce/Fe obtained from BET surface area analysis.

Parameter Amount
AC AC/Ce AC/Fe AC/Ce/Fe
Surface area
Single point surface area at p/p° = 0.202 473 m2/g 451 m2/g 434 m2/g 436 m2/g
BET Surface Area 469 m2/g 448 m2/g 432 m2/g 432 m2/g
Langmuir Surface Area 630 m2/g 606 m2/g 585 m2/g 584 m2/g
t-Plot Micropore Area 242 m2/g 216 m2/g 197 m2/g 218 m2/g
t-Plot External Surface Area 227 m2/g 232 m2/g 235 m2/g 214 m2/g
BJH Adsorption cumulative surface area of pores
Between 17 Å and 3000 Å width 217 m2/g 220 m2/g 225 m2/g 207 m2/g
BJH Desorption cumulative surface area of pores
Between 17 Å and 3000 Å width 231 m2/g 234 m2/g 241 m2/g 223 m2/g
Pore Volume
Single point adsorption total pore volume of pores
Less than 651 Å width at p/p° = 0.969 0.706 cm3/g 0.670 cm3/g 0.675 cm3/g 0.644 cm3/g
t-Plot micropore volume 0.111 cm3/g 0.099 cm3/g 0.090 cm3/g 0.100 cm3/g
BJH Adsorption cumulative volume of pores
Between 17 Å and 3000 Å width 0.656 cm3/g 0.642 cm3/g 0.606 cm3/g 0.613 cm3/g
BJH Desorption cumulative volume of pores
Between 17 Å and 3000 Å width 0.662 cm3/g 0.647 cm3/g 0.614 cm3/g 0.620 cm3/g
Pore Size
Adsorption average pore width (4V/A by BET) 60 Å 60 Å 62 Å 60 Å
BJH Adsorption average pore width (4V/A) 121 Å 117 Å 108 Å 118 Å
BJH Desorption average pore width (4V/A) 115 Å 111 Å 102 Å 111 Å
Horvath-Kawazoe
Maximum pore volume at p/p° = 0.993 0.765 cm3/g 0.740 cm3/g 0.695 cm3/g 0.710 cm3/g
Median pore width 240 Å 238 Å 196 Å 229 Å
 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927
Fig. 2. XRD diffraction patterns of AC, AC/Fe, AC/Ce and AC/Ce/Fe.
shows calcium as one of the elements found on the surface of AC/
Ce because Ce and Ca overlap in the EDX spectrum. The image
reveals some white deposits on the surface of the adsorbent indi-
cating the formation of cerium nanoparticles. Fig. 3c corresponds
to AC/Fe, and it has some obvious large crystals of Fe deposited
on the surface of the adsorbent. These crystals contribute presum-
ably to the chemisorption of thiophenes through sulfur to metal
interaction. Fig. 3d is the SEM/EDX image of AC/Ce/Fe nanocom-
posite; it combines the white crystals of cerium oxide and the large
crystals of iron oxide at the surface of the adsorbent. The uniform
distribution of the bimetals on the AC, as shown in Fig. 3e might be
the reason the bimetallic complex gave us the best removal of the
refractory sulfur compounds.
The FTIR spectra of all the adsorbents are depicted in Fig. 4 to
understand the type of functional groups present on the adsorbent,
and to monitor if there are similarities in the relative intensities of
each functional group. Each adsorbent showed varying degrees of
the relative intensities of the functional groups, but they all dis-
played a similar pattern.
All adsorbents exhibited peaks around 3500–3400 cm1 which
can be assigned to O–H stretching vibrations of hydroxyl or car-
boxylic groups or due to chemisorbed water. They also displayed
peaks around 2900–2800 cm1 due to an aliphatic C–H stretch of
CH, CH2, and CH3. The broad peaks centered at 1720 and
1660 cm1 are assigned to C@O stretching vibration in ketones
and carboxylic acids [40]. Additionally, the peaks at 1400 cm1
and 2200–2400 cm1 are assigned to C@O stretching vibrations
and double bonded carbon-oxygen groups [41]. The last peak that
appeared at 1054 cm1 is attributed to C–O stretching vibration.
These peaks are characteristics of amorphous carbon, hence, the
919
reason purely synthesized AC gave the highest intensities. How-
ever, the intensities of the peaks decreased upon metal loading
supporting the results obtained from BET, XRD, and SEM. The result
confirms the attachment of oxygen-containing functional groups
with nanoparticles.
The peak at 550.84 cm1 signifies the presence of Ce–O within
AC/Ce sample, but it does not appear in AC/Ce/Fe because the con-
centration of Ce in that adsorbent was minuscule. The band that
appeared around 1080 cm1 is assigned to the Ce–O–C interaction
[42,43]. The small peaks that appeared at 798 and 895 cm1 are
attributed to the Fe–O bending vibrations, while the peak at
624 cm1 is due to the Fe–O stretching vibrations within the AC/
Fe and AC/Ce/Fe [44,45].
3.2. Adsorption evaluation
The desulfurization efficiency of the adsorbents was studied in
batch adsorption experiment [46]. 30 min was chosen because the
adsorption process was a rapid process, attaining equilibrium at
about 10 min. Fig. 5 depicts the percentage adsorption of the sulfur
compounds. The overall performance followed the sequence: AC/
Ce/Fe > AC/Ce > AC/Fe > AC. The bimetallic composite performed
the best despite having the lowest surface area and pore volume.
The trend confirms the hypothesis that modifying carbon’s surface
with metals and metal oxides enhance its selectivity and adsorp-
tive capacity to the refractory sulfur compounds. AC/Ce had better
performance than AC/Fe. The result signifies that Ce has a better
efficiency for the sulfur compounds which indicates that Ce can
interact more with the sulfur-compounds. However, AC/Ce/Fe has
better efficiency than AC/Ce and AC/Fe. Fe might have a subtle
920 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927

(a)

(b)

(c)

(d)

(e)

Fig. 3. SEM image and EDX spectrum of the surface structure of AC (a), AC/Ce (b), AC/Fe (c) and AC/Ce/Fe (d).
 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927
(a)
(b)
Fig. 4. FTIR spectrum of AC; and AC/Ce, AC/Fe, and AC/Ce/Fe.
Fig. 5. Percentage adsorption of thiophene, BT, and DBT by AC, AC/Fe, AC/Ce and
AC/Ce/Fe.
effect on the solution by providing some acidic sites necessary for
the adsorption of Lewis bases. A medium containing thiophene sul-
fur compounds accommodates Lewis bases in nature and prefer to
associate with acidic sites. Combined effects of Ce and Fe on AC
(AC/Ce/Fe) had an overall net positive synergistic effect on the
adsorption of thiophene compounds.
The adsorption of sulfur compounds in all the adsorbents fol-
lowed the order: DBT > BT > Thiophene.
921
The adsorbents performed excellently in the removal of DBT
probably because of its structure containing more p-systems that
provide more possible interactions, such as p-interaction with
the active sites on the surfaces. Thus, dispersive interactions
between the delocalized p-electrons within the benzene rings of
DBT and the electron-rich region on the nano-porous carbon aro-
matic ring play a significant role in the adsorption.
In addition to the above mechanism, a feature common for the
three S-compounds is the possible coordination with the metal
species through S–M interactions. Several coordination configura-
tions can be formed between the sulfur compounds and the metal
including the (i) n-type donor by donating the lone pairs of elec-
trons that lie in the plane of the ring to the nanoparticles and the
interaction between S and the oxygen atom on the metal oxide
nanoparticles. Because of its better performance, AC/Ce/Fe was
selected for further investigation from this point forward.
It is noteworthy that SEM/EDX image of AC/Ce/Fe taken after
adsorption, Fig. 6, shows the surface structure and the presence
of sulfur. The image indicates the presence of sulfur, which con-
firms the efficiency of the adsorption process, and whether the
refractory sulfur compounds will remain attached to the surface
of the adsorbent or they will be diffused through the pores of the
nanocomposite. The result confirms that the sulfur to metal inter-
action occurs at the AC/Ce/Fe adsorbent’s surface. Fig. 6b showed
the distribution of the elements on the adsorbent. It showed clearly
the presence of the sulfur on the surface confirming the adsorption
of thiophenes by the prepared material.
The IR spectrum of the AC/Ce/Fe after thiophenes adsorption is
shown in Fig. 6c. The stretching vibrations of the thiophene rings
were detected in the frequency range between 820 and 850 cm1
[47]. The symmetric C@C stretching vibration bands of the thio-
phene rings were shown in the range between 1455 and
1470 cm1. On the other hand, the antisymmetric C@C stretching
vibration bands of the rings appeared around 1510 cm1 [47].
The band at 1418 cm1 could be assigned to thiophene coordinated
via its sulfur atom to coordinately unsaturated metal sites created
by dihydroxylation of the metal oxides, and the band at 1400 cm1
is due to thiophene hydrogen bonded to hydroxyl groups on the
surface of the adsorbent. The appearance of the IR band at
1434 cm1, the symmetric mode of adsorbed thiophene, can be
used to determine the adsorption mode of thiophene on AC/Ce/
Fe. The appearance of this band in the IR spectrum, Fig. 6c could
explain why the AC/Ce/Fe showed better-enhanced adsorption of
thiophenes than the AC, AC/Ce, or AC/Fe. It should be noted that
because the vibrational frequencies of ring stretching modes of
heterocyclic aromatic molecules are sensitive to their bonding
environment on a catalyst surface, the coordination of thiophenes
to surface sites via the sulfur atom might cause a shift of the vibra-
tional band to higher wavenumbers while to lower wavenumbers
for p-bonded thiophenes [48].
3.3. Effect of dosage
The effect of AC/Ce/Fe dosage on the percentage adsorption of
refractory sulfur compounds is given in Fig. 7. Determining the
optimum dosage of an adsorbent is an important parameter in
adsorption studies, and so the dosage (0.1–0.5 g) was investigated
with a fixed starting concentration of thiophene, BT and DBT of 52,
50 and 51 ppm in 25 mL of the fuel sample. An overall improve-
ment in the adsorption was noticed with an increase in dose of
the adsorbent because more sorbent surface area is provided that
increases the adsorption sites in the medium. The order of sulfur
compounds adsorption by AC/Ce/Fe was DBT > BT > Thiophene,
and the percent adsorption of DBT was >70% regardless of the dose.
In contrast, the percent removal of thiophene combined with BT
922 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927

(a)

(b)

(c)

Fig. 6. SEM and EDX spectrum (a), Mapping (b) and IR spectrum (c) of the surface structure AC/Ce/Fe after adsorption.
 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927
Fig. 7. Effect of AC/Ce/Fe dosage on the percentage adsorption of thiophene, BT and
DBT after 30 min at room temperature.
Fig. 8. Effect of contact time on the adsorption of refractory sulfur compounds by
AC/Ce/Fe in batch mode.
was between 30 and 40% in all the doses evaluated. The acid-base
interaction between the refractory sulfur compound and the
oxygen-containing groups also plays a fundamental role.
3.4. Effect of contact time
The effect of contact time of AC/Ce/Fe on the adsorption of the
S-compounds at room temperature is shown in Fig. 8. The adsorp-
tion process was very rapid, around 98% of the adsorption occurs
after five minutes. The equilibrium was achieved after 10 min
through the batch adsorption indicating fast adsorption process.
The sulfur compounds were large enough to be stacked to the sur-
face of the adsorbent preventing their easy passage.
The rate and quantity of sulfur adsorbed by the adsorbent are
limited to the size of adsorbent molecules, the concentration of
the analytes and affinity towards the analytes, the diffusion coeffi-
cient of the adsorbent in the bulk and solid phase, and the degree
of mixing in the batch experiment. The number of available
adsorption sites decreased as the number of sulfur ions adsorbed
increased by increasing the contact time. A majority of the area
of the adsorbent is mesoporous, making it easy for adsorption of
target analytes at the initial stage. After sometimes, the sulfur com-
pounds have to traverse further and deeper into the micro-pores
encountering much larger resistance that results in the slowing
down of the adsorption rate during the later period. The adsorption
capacity followed the order: DBT (16.5 mg of Sulfur/gram of the
923
Fig. 9. Breakthrough curve for thiophene, BT, and DBT using AC/Ce/Fe.
adsorbent) > T (7.0 mg of S/g of the adsorbent) > BT (6.7 mg of S/g
of the adsorbent).
3.5. Breakthrough curve
The effectiveness AC/Ce/Fe was further investigated in column
mode (continuous flow mode). The breakthrough curve was gener-
ated by plotting transient total sulfur concentration normalized by
the feed total sulfur concentration (Ct/C0) vs. cumulative time. The
plot is given in Fig. 9, and DBT showed the best performance
because the breakthrough was achieved after 60 min. However,
the concentration of DBT did not return to the initial level even
after 240 min meaning that adsorption of DBT still continued
entirely in the column studies. The breakthrough for BT was
reached after 30 min, and it almost returned close to Co after
60 min of adsorption. The breakthrough for thiophene was around
5 min; it performed the least in the analytes evaluated because of
its size and its affinity to the surface. It tends to diffuse readily
within the adsorbent, and since it is within a column, the larger
size analytes might displace the smaller size analytes on the sur-
face since the large size molecules have more p-systems on their
structure, and thus more interaction of their molecules with the
surface. The breakthrough followed the order: DBT > BT > T.
3.6. Adsorption kinetics
Adsorption kinetics elucidates sorption mechanism and the
interaction between the adsorbent (AC/Ce/Fe) and the analytes
(DBT, BT, and Thiophene). The linear forms of pseudo-first order,
pseudo-second order, and intraparticle diffusion models were used
to understand the mechanism of adsorption, as described by Lager-
gren, Weber and Morris, and Ho and McKay [49–51]. The correla-
tion between experimental data and the model expected values
was evaluated using correlation coefficient (R2) values. The range
is between 0 and 1, and high R2 value translates a strong correla-
tion between the model and the experimental results.
Lagergren’s pseudo-first order model can be used to get an idea
of the adsorption capacity of the adsorbent (AC/Ce/Fe) towards the
analyte molecules, and it gives an account of the initial stages of
the adsorption process. The linear form of the model is given as:
lnðqe  qt Þ ¼ lnqe  k1 t
where qe (mg/g) and qt (mg/g) are the amount of analytes absorbed
per unit weight of the adsorbent at equilibrium and at contact time
t (min), while k1 (min1) is the rate constant of the Lagergren
924 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927

(a) data obtained were applied at various contact time between the
analytes to the adsorbent to the linear form of the pseudo-
y = -0.0353x + 0.9099 second order model given as follows:
R² = 0.922
t t 1
¼ þ
qt qe k2 q2e

where qe , qt , and qt were already given from the pseudo-first order

description while k2 (g/mg min) stands for the rate constant for the
pseudo-second-order adsorption. The plot of qt vs t of different ana-
t
y = -0.0389x + 0.8139 lytes i.e. Thiophene, BT and DBT at fixed concentrations is given in
R² = 0.9864 Fig. 10b. The slope and intercept of the linear plot of t/qt against t
were used to determine the amount adsorbed at equilibrium (qe)
y = -0.0556x - 0.91 and second-order rate constant (k2) and the results along with the
R² = 0.9748 correlation coefficients, are shown in Table 2. The values of the cor-
relation coefficients R2 and the calculated qe values of thiophene, BT,
and DBT when compared to the experimental qe agree with the sec-
ond order kinetic model. The result means that adsorption of S-
compounds on AC/Ce/Fe is controlled by the chemisorption mecha-
nism where covalent bonds or electrons participate between the
(b) surface of the adsorbent and the analytes.
The results were subjected to the Weber’s intraparticle diffu-
sion mechanism to have an idea of rate controlling steps affecting
the adsorption kinetics [52] using the eq:

y = 0.1406x + 0.2064
R² = 0.9984
y = 0.1319x + 0.2842
R² = 0.9961
y = 0.0605x + 0.0093
R² = 0.9998
Fig. 10. Adsorption kinetic investigation of AC/Ce/Fe on the adsorption of
thiophene, BT, and DBT (a) Pseudo-first order (b) Pseudo-second order.
first-order kinetic model. The plot between lnðqe  qt Þ versus t is
shown in Fig. 10a.
The k1 and qe were calculated from the slope and intercept of
the plot lnðqe  qt Þ versus t and the values are given in Table 2. Lack
of agreement between the experimental qe and the calculated qe
for all the refractory sulfur compounds suggests that the adsorp-
tion process does not comply with the pseudo-first-order model.
Also, the values obtained from the correlation coefficients (R2) of
DBT, BT, and thiophene from the Fig. 10a are lower when compared
to the pseudo-seconder order kinetic model confirming the lack of
linearity with the first order model. The result indicated clearly
that the adsorption of refractory sulfur compounds on the surface
of AC/Ce/Fe deviated from the pseudo-first-order kinetic model.
Pseudo-second order model describes the adsorption process
and capacity by assuming the rate limiting step as chemisorption
involving valence forces by sharing or electron exchange. So, the
qt ¼ ki:d t1=2 þ C
where qt is the amount of refractory sulfur compounds adsorbed at
time t. t1/2 is the square root of the time, ki.d is the slope which rep-
resents the intraparticle diffusion rate constant (mg/g.min), which
can be calculated from the slope of the linear plot of qt versus t1/2.
C is the intercept in mg/g correlated with boundary layer thickness.
The ki.d result displayed a gradual uptake of the refractory sul-
fur compounds Table 2. The values for the rate constants of thio-
phene, BT, and DBT were 0.1948, 0.2777, and 0.019 mg/g.min
respectively. The boundary layer thickness (C) results indicate that
DBT had a much larger resistance to diffuse into the particles, and
the R2 value of 0.3935 confirmed the lack of linearity between DBT
to the intraparticle diffusion model. At the same time reinforcing
the p–p dispersive interaction and chemisorption that took place
between DBT and AC/Ce/Fe. However, the R2 values of thiophene
and BT show a good correlation probably because of their size;
they tend to have a much lower resistance to diffuse into the par-
ticles. Having said that, if the regression of qt versus t1/2 is linear
and passes through the origin, then intraparticle diffusion is the
only rate-limiting step in the adsorption. It is also noteworthy that
when ‘C’ is not equal to zero then intraparticle diffusion will not be
the only rate limiting step of the adsorption process. The linear
plots of each analyte did not pass through the origin, and all the
‘C’ values were not equal to zero. The plot indicates that the intra-
particle diffusion was not the only rate limiting step, but a complex
mixture of adsorption mechanisms was in play.
3.7. Adsorption isotherms
The purpose of adsorption isotherms is to relate the adsorbate
concentration in the bulk and the adsorbed amount at the interface
[53]. An adsorption isotherm is characterized by certain constant

Table 2
Parameters of kinetics models for the adsorption on AC/Ce/Fe.

Compound Experimental qe (mg/g) Pseudo first order Pseudo second order Intraparticle diffusion
2 2
K1 Calculated qe R K2 (g/mg min) Calculated qe R Ki.d C R2
Thiophene 7.78 0.035 2.48 0.922 0.061 7.58 0.996 0.195 5.60 0.905
BT 7.23 0.039 2.26 0.986 0.095 7.11 0.998 0.278 4.79 0.928
DBT 16.63 0.056 0.40 0.975 0.394 16.52 0.999 0.019 16.40 0.394
 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927
Fig. 11. SEM/EDX image of AC/Ce/Fe after regeneration.
values, which express the surface properties and affinity of the
adsorbent and can be used to compare the adsorptive capacities
of the adsorbent for different pollutants. Adsorption capacity is
an important parameter in adsorption because it determines how
much of an adsorbent is required for quantitative enrichment of
adsorbates from given solutions. There are several mathematical
models that can be used to describe experimental data of adsorp-
tion, so the study was limited to the most widely used models
i.e. Langmuir and Freundlich isotherms to evaluate the adsorption
of thiophene, BT, and DBT on AC/Ce/Fe [51].
The Langmuir adsorption model is based on the assumption
that maximum adsorption corresponds to a saturated monolayer
of solute molecules on the adsorbent’s surface, with no lateral
interaction between the sorbed molecules [54]. The Langmuir
equation used is:
Ce 1 Ce
¼ þ
qe K L qm qm
where qe in mg/g: the amount adsorbed at Ce (mg/L); qm in mg/g:
the Langmuir constant that represents monolayer capacity: KL:
the Langmuir constant. The slope and intercept of a linear plot of
Ce/qe against Ce yield the values of 1/qm and 1/KLqm.
The adsorption capacity qm for the refractory sulfur compounds
on AC/Ce/Fe from Table 3 followed the order thiophene < BT < DBT.
The dimensionless constant separation factor RL is an integral part
of Langmuir isotherm as:
1 adsorption of sulfur compounds showed constant level within
RL ¼
1 þ K LC0
where C0 in mg/L is the initial concentration of the analytes and KL
in L/mg is Langmuir constant. RL > 1 indicates an unfavorable
process, RL = 1 indicates linearity, 0 < RL < 1 indicates a favorable
process and RL = 0 signifies an irreversible adsorption. The result
obtained from Table 3 shows that the adsorption of the
S-compounds on AC/Ce/Fe is a favorable process. The R2 values
obtained for the refractory sulfur compounds in the Langmuir
isotherm column (Table 3) show a good linearity, but the linearity
of the Freundlich isotherm is stronger.
Table 3
Parameters of Langmuir and Freundlich isotherms using AC/Ce/Fe.
S-compound Langmuir isotherm constant
2
qm (mg/g) KL (L/mg) R RL
Thiophene 0.33 0.019 0.969
BT 2.48 0.065 0.958
DBT 3.70 0.033 0.985
925
The Freundlich isotherm describes heterogeneous process or
multilayer adsorption as [55]:
1
ln qe ¼ lnK F þ lnC e
n
where qe (mg/g) is a number of analytes on the absorbent’s surface,
KF (mg/g) and n are Freundlich constants relating to the adsorption
capacity of the sorbent and adsorption intensity. The ‘‘n” values give
an indication of the favorability of the adsorption process, and val-
ues of n > 1 represent favorable adsorption condition [56]. The slope
and intercept of the graph of ln qe versus ln Ce are used to determine
Freundlich isotherm constants KF and n.
Results from Table 3 show that the values of n > 1 with a favor-
able adsorption. The Freundlich adsorption capacity of AC/Ce/Fe
towards the refractory sulfur compounds followed the sequence:
DBT > BT > Thiophene. The correlation coefficient (R2) values indi-
cate that Freundlich isotherm model fit the experimental data.
3.8. Regeneration
The major concerns about the use of adsorbents in ADS are
regeneration and disposal of the spent adsorbents. The regenera-
tion methods currently in use to restore carbon adsorptive capacity
are thermal, solvent, and ultrasound approaches [57–59]. Thermal
regeneration method was employed in this work. The percentage
the experimental errors after three cycles in the adsorptive capac-
ity of the AC/Ce/Fe adsorbent.
SEM image of AC/Ce/Fe was taken after thermal regeneration to
confirm the efficiency of the regeneration process. The result from
the SEM//EDX analysis is given in Fig. 11, and the image confirms
the absence of elemental sulfur after the batch adsorption process.
However, the percent weight of the metals in the adsorbent
increased showing the effect of calcination on the adsorbent. The
weight percent of the elements found on the surface of the adsor-
bent is as follows: carbon (54.89), oxygen (25.35), iron (13.87) and
cerium (5.89).
Freundlich isotherm constant
Kf n R2
0.483 6.4E08 4.5 0.999
0.747 2.3E05 2.9 0.999
0.366 0.0656 1.6 0.999
926 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927
4. Conclusion
The feasibility of converting WRTs to AC as a management strat-
egy was examined so that industries can reap into that alternative;
we proceeded to offer a solution to one of the pressing global
issues leading to environmental pollution i.e. the discharge of sul-
fur to the environment. The effect of nanoparticles support on the
surface of the adsorbent towards ADS was evaluated. Conclusively,
the bimetallic composite AC/Ce/Fe enhanced the adsorption capac-
ity and selectivity towards the refractory sulfur compounds despite
having the least surface area, pore volume, and less surface
oxygen-containing functional groups. The improved performance
can be attributed mainly to changes in the chemical composition
of the adsorbent, the acidic nature of cerium, and the crystal nature
of iron. The kinetic and isotherm analyses also supported the argu-
ment because they displayed chemisorption and heterogeneous
adsorption occurring on the surface. Thermal regeneration of the
adsorbent yielded an excellent performance, and the result showed
the possibility of using this adsorbent in a large-scale application.
Acknowledgements
The authors would like to acknowledge the support provided by
King Abdulaziz City for Science and Technology (KACST) through
the Science & Technology Unit at King Fahd University of Petro-
leum & Minerals (KFUPM) for funding this work through project
No. 13-PET393-04 as part of the National Science, Technology,
and Innovation Plan.
References
[1] X.L. Song, L.B. Sun, G.S. He, X.Q. Liu, Isolated Cu (I) sites supported on b-
cyclodextrin: an efficient p-complexation adsorbent for thiophene capture,
Chem. Commun. 47 (2011) 650–652.
[2] United States Environmental Protection Agency (USEPA), Introduction of
Cleaner-Burning Diesel Fuel Enables Advanced Pollution Control for Cars,
Trucks and Busses, EPA420-F-06-064, <www.epa.gov/otaq/highway-diesel/
regs/420f06064.pdf>, 2006.
[3] S.K. Bej, Revamping of diesel hydrodesulfurizers: options available and future
research needs, Fuel Process. Technol. 85 (2004) 1503–1517.
[4] M.F. Ali, A. Al-Malki, B. El-Ali, G. Martinie, M.N. Siddiqui, Deep
desulphurization of gasoline and diesel fuels using non-hydrogen consuming
techniques, Fuel 85 (2006) 1354–1363.
[5] G. Yu, S. Lu, H. Chen, Z. Zhu, Oxidative desulfurization of diesel fuels with
hydrogen peroxide in the presence of activated carbon and formic acid, Energy
Fuels 19 (2005) 447–452.
[6] M. Soleimani, A. Bassi, A. Margaritis, Biodesulfurization of refractory organic
sulfur compounds in fossil fuels, Biotechnol. Adv. 25 (2007) 570–596.
[7] I.A.H. Al Zubaidy, F.B. Tarsh, N.N. Darwish, B.S.S. Abdul Majeed, A. Al Sharafi, L.
A. Chacra, Adsorption process of sulfur removal from diesel oil using sorbent
materials, JOCET 1 (2013) 66–68.
[8] C. Marín-Rosas, L.F. Ramírez-Verduzco, F.R. Murrieta-Guevara, G. Hernández-
Tapia, L.M. Rodríguez-Otal, Desulfurization of low sulfur diesel by adsorption
using activated carbon: adsorption isotherms, Ind. Eng. Chem. Res. 49 (2010)
4372–4376.
[9] B. Li, W. Liu, H. Wu, S. Yu, R. Cao, Z. Jiang, Desulfurization of model gasoline by
bioinspired oleophilic nanocomposite membranes, J. Membr. Sci. 415–416
(2012) 278–287.
[10] X. Ma, M. Sprague, C. Song, Deep desulfurization of gasoline by selective
adsorption over nickel-based adsorbent for fuel cell applications, Ind. Eng.
Chem. Res. 44 (2005) 5768–5775.
[11] T. Fukunaga, H. Katsuno, H. Matsumoto, O. Takahashi, Y. Akai, Development of
kerosene fuel processing system for PEFC, Catal. Today 84 (2003) 197–200.
[12] T.A. Saleh, A strategy for integrating basic concepts of nanotechnology to
enhance undergraduate nano-education: Statistical evaluation of an
application study, J. Nano Educ. 4 (1–2) (2013) 1–7.
[13] S.P. Hernandez, D. Fino, N. Russo, High performance sorbents for diesel oil
desulfurization, Chem. Eng. Sci. 65 (2010) 603–609.
[14] I. Ali, M. Asim, T.A. Khan, Low cost adsorbents for the removal of organic
pollutants from wastewater, J. Environ. Manage. 113 (2012) 170–183.
[15] V.K. Gupta, Suhas, Application of low-cost adsorbents for dye removal – a
review, J. Environ. Manage. 90 (2009) 2313–2342.
[16] J.H. Kim, X. Ma, A. Zhou, C. Song, Ultra-deep desulfurization and
denitrogenation of diesel fuel by selective adsorption over three different
adsorbents: a study on adsorptive selectivity and mechanism, Catal. Today 111
(2006) 74–83.
[17] R.M. Fallah, S. Azizian, Removal of thiophenic compounds from liquid fuel by
different modified activated carbon cloths, Fuel Process. Technol. 93 (2012)
45–52.
[18] A. Bhatnagar, M. Sillanpää, Utilization of agro-industrial and municipal waste
materials as potential adsorbents for water treatment—a review, Chem. Eng. J.
157 (2010) 277–296.
[19] M. Yu, Z. Li, Q. Xia, H. Xi, S. Wang, Desorption activation energy of
dibenzothiophene on the activated carbons modified by different metal salt
solutions, Chem. Eng. J. 132 (2007) 233–239.
[20] T.A. Saleh, M.M. Al-Shalalfeh, A.A. Al-Saadi, Graphene Dendrimer-stabilized
silver nanoparticles for detection of methimazole using Surface-enhanced
Raman scattering with computational assignment, Sci. Rep. 6 (2016) 32185,
http://dx.doi.org/10.1038/srep32185.
[21] T.A. Saleh, Isotherm, kinetic, and thermodynamic studies on Hg (II) adsorption
from aqueous solution by silica-multiwall carbon nanotubes, Environ. Sci.
Pollut. Res. 22 (2015) 16721–16731.
[22] T.A. Saleh, Nanocomposite of carbon nanotubes/silica nanoparticles and their
use for adsorption of Pb (II): from surface properties to sorption mechanism,
Desalin. Water Treat. 57 (2016) 10730–10744.
[23] L. Xiong, X. Min Yan, P. Mei, Synthesis and characterization of a ZrO2/AC
composite as a novel adsorbent for dibenzothiophene, Adsorpt. Sci. Technol.
28 (2010) 341–350.
[24] Z. Yan, J. Wang, R. Zou, L. Liu, Z. Zhang, X. Wang, Hydrothermal synthesis of
CeO2 nanoparticles on activated carbon with enhanced desulfurization
activity, Energy Fuels 26 (2012) 5879–5886.
[25] S. Sumathi, S. Bhatia, K.T. Lee, A.R. Mohamed, Performance of palm shell
activated carbon impregnated with CeO2 and V2O5 catalyst in simultaneous
removal of SO2 and NO, J. Appl. Sci. 10 (2010) 1052–1059.
[26] J.A. Arcibar-Orozco, J.R. Rangel-Mendez, T.J. Bandosz, Desulfurization of model
diesel fuel on activated carbon modified with iron oxyhydroxide
nanoparticles: effect of tert-butylbenzene and naphthalene concentrations,
Energy Fuels 27 (2013) 5380–5387.
[27] World Business Council for Sustainable Development (WBCSD 2008):
Managing End of Life Tires-Full Report, Atar Roto Presse SA, Switzerland,
<http://www.rubberassociation.ca/files/ELT%20Full%20Report,%202008.pdf>.
[28] T.A. Saleh, G.I. Danmaliki, Adsorptive desulfurization of dibenzothiophene
from fuels by rubber tyres-derived carbons: kinetics and isotherms evaluation,
Process Saf. Environ. Prot. 102 (2016) 9–19.
[29] G.I. Danmaliki, T.A. Saleh, Influence of conversion parameters of waste tires to
activated carbon on adsorption of dibenzothiophene from model fuels, J. Clean.
Prod. 117 (2016) 50–55.
[30] T.A. Saleh, G.I. Danmaliki, Influence of acidic and basic treatments of activated
carbon derived from waste rubber tires on adsorptive desulfurization of
thiophenes, J. Taiwan Inst. Chem. Eng. 60 (2016) 460–468.
[31] T.A. Saleh, The influence of treatment temperature on the acidity of MWCNT
oxidized by HNO3 or a mixture of HNO3/H2SO4, Appl. Surf. Sci. 257 (2011)
7746–7751.
[32] T.A. Saleh, Mercury sorption by silica/carbon nanotubes and silica/activated
carbon: a comparison study, J. Water Supply Res. T. 64 (8) (2015) 892–903.
[33] S.J. Gregg, K.S.W. Sing, Adsorption, Surface Area and Porosity, second ed.,
Academic Press, London, 1982.
[34] T.A. Saleh, K.R. Alhooshani, M.S.A. Abdelbassit, Evaluation of AC/ZnO
composite for sorption of dichloromethane, trichloromethane and carbon
tetrachloride: kinetics and isotherms, J. Taiwan Inst. Chem. Eng. 55 (2015)
159–169.
[35] A. Min, A.T. Harris, Influence of carbon dioxide partial pressure and fluidization
velocity on activated carbons prepared from scrap car tyre in a fluidized bed,
Chem. Eng. Sci. 61 (2006) 8050–8059.
[36] X. Ma, H. Yang, L. Yu, Y. Chen, Y. Li, Preparation, surface and pore structure of
high surface area activated carbon fibers from bamboo by steam activation,
Materials 7 (2014) 4431–4441.
[37] S. Mahadevan, S.P. Behera, G. Gnanaprakash, T. Jayakumar, J. Philip, B.P.C. Rao,
Size distribution of magnetic iron oxide nanoparticles using Warren-Averbach
XRD analysis, J. Phys. Chem. Solids 73 (2012) 867–872.
[38] N. Morlanes, Reaction mechanism of naphtha steam reforming on nickel-
based catalysts, and FTIR spectroscopy with CO adsorption to elucidate real
active sites, Int. J. Hydrogen Energy 38 (2013) 3588–3596.
[39] T.A. Saleh, M.A. Gondal, Q.A. Drmosh, Z.H. Yamani, A. AL-yamani, Enhancement
in photocatalytic activity for acetaldehyde removal by embedding ZnO
nano particles on multiwall carbon nanotubes, Chem. Eng. J. 166 (2011)
407–412.
[40] X. Wu, X. Hong, Z. Luo, K.S. Hui, H. Chen, J. Wu, K.N. Hui, L. Li, J. Nan, Q. Zhang,
The effects of surface modification on the supercapacitive behaviors of novel
mesoporous carbon derived from rod-like hydroxyapatite template,
Electrochim. Acta 89 (2013) 400–406.
[41] A.A. Ansari, P.R. Solanki, B.D. Malhotra, Hydrogen peroxide sensor based on
horseradish peroxidase immobilized nanostructured cerium oxide film, J.
Biotechnol. 142 (2009) 179–184.
[42] B. Ksapabutr, E. Gulari, S. Wongkasemjit, Sol–gel derived porous ceria powders
using cerium glycolate complex as precursor, Mater. Chem. Phys. 99 (2006)
318–324.
[43] M. Gotic, S. Music, Mössbauer, FT-IR and FE SEM investigation of iron
oxides precipitated from FeSO4 solutions, J. Mol. Struct. 834–836 (2007)
445–453.
[44] L. Tian, C. Li, Q. Li, G. Zeng, Z. Gao, S. Li, X. Fan, Removal of elemental mercury
by activated carbon impregnated with CeO2, Fuel 88 (2009) 1687–1691.
 G.I. Danmaliki, T.A. Saleh / Chemical Engineering Journal 307 (2017) 914–927
[45] T.A. Saleh, A. Sarı, M. Tuzen, Effective adsorption of antimony (III) from
aqueous solutions by polyamide-graphene composite as a novel adsorbent,
Chem. Eng. J. 307 (2017) 230–238.
[46] I. Shah, R. Adnan, W.S.W. Ngah, N. Mohamed, Iron impregnated activated
carbon as an efficient adsorbent for the removal of methylene blue:
regeneration and kinetics studies, PLoS One 10 (2015) e0122603.
[47] A. Tamanai, S. Beck, A. Pucci, Mid-infrared characterization of thiophene-based
thin polymer films, Displays 34 (2013) 399–405.
[48] Z. Wu, C. Li, Z. Wei, P. Ying, Q. Xin, FT-IR spectroscopic studies of thiophene
adsorption and reactions on Mo2N/c-Al2O3 catalysts, J. Phys. Chem. B 106
(2002) 979–987.
[49] S. Lagergren, About the theory of so-called adsorption of soluble substances (in
German), Kungliga Svenska Vetenskapsakademiens Handlingar 24 (4) (1898)
1–39.
[50] W.J. Weber Jr., J.C. Morris, Kinetics of adsorption carbon from solutions, J. Sanit.
Eng. Div. Am. Soc. Civ. Eng. 89 (1963) 31–60.
[51] Y.S. Ho, G. McKay, Sorption of dye from aqueous solution by peat, Chem. Eng. J.
70 (1998) 115–124.
[52] T.W. Weber, R.K. Chakravorti, Pore and solid diffusion models for fixed-bed
adsorbers, AIChE 20 (1974) 228–238.
927
[53] J. Eastoe, J.S. Dalton, Dynamic surface tension and adsorption mechanisms of
surfactants at the air-water interface, Adv. J. Colloid Interface Sci. 85 (2000)
103–144.
[54] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and
platinum, J. Am. Chem. Soc. 40 (9) (1918) 1361–1403.
[55] H. Freundlich, Uber die adsorption in losungen, Zeitschrift fur Physikalische
Chemie-Leipzig 57 (1906) 385–470.
[56] V.J.P. Poots, G. McKay, J.J. Healy, Removal of basic dye from effluents using
wood as an adsorbent, J. Water Pollut. Control Fed. 50 (1978) 926–935.
[57] X. Han, H. Lin, Y. Zheng, Regeneration methods to restore carbon adsorptive
capacity of dibenzothiophene and neutral nitrogen heteroaromatic
compounds, Chem. Eng. J. 243 (2014) 315–325.
[58] T.A. Saleh, G.I. Danmaliki, T.D. Shuaib, Nanocomposites and Hybrid Materials
for Adsorptive Desulfurization, Applying Nanotechnology to the
Desulfurization Process in Petroleum Engineering, IGI Global, USA, 2016, pp.
129–153.
[59] G.S. Miguel, S.D. Lambert, N.J.D. Graham, Thermal regeneration of granular
activated carbons using inert atmospheric conditions, Environ. Technol. 23
(2002) 1337–1346.