Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 460–468

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Journal of the Taiwan Institute of Chemical Engineers

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Influence of acidic and basic treatments of activated carbon derived from

waste rubber tires on adsorptive desulfurization of thiophenes
Tawfik A. Saleh a,∗, Gaddafi I. Danmaliki b
a
Chemistry Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
b
Environmental Science Department, King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia

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

Article history: This work reports on the influence of treatment conditions on the waste tire-derived activated carbon for ad-
Received 6 June 2015 sorptive desulfurization. The rubber tires were carbonized and activated. The obtained activated carbon (AC)
Revised 8 November 2015
was treated with HNO3 or NaOH at a temperature range of 30–90 °C. The morphology and surface proper-
Accepted 13 November 2015
ties of AC were characterized by surface pH, Boehm’s titration, N2 adsorption–desorption isotherms, Fourier-
Available online 7 December 2015
transform infrared spectroscopy, X-ray diffraction, and scanning electron microscope. The AC sample, treated
Keywords: with HNO3 at 90 °C, possess the highest surface oxygen containing functional groups (2.39 mmol/g), surface
Adsorptive desulfurization area (473.35 m2 /g) and pore volume (0.70 cm3 /g) and the more adsorption capacity to the refractory sulfur
Fixed bed compounds. The Boehm’s titration experiments indicated that the amount of surface oxygen containing func-
Waste tires tional groups on the surface of the acid-treated AC increases with treatment temperatures. Acid-treated AC
Carbon at 90 °C proves to be optimum for adsorptive desulfurization with the order of dibenzothiophene > benzoth-
iophene > thiophene.
© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
Combustion of fossil fuels is associated with the release of toxic
gases that pose serious environmental and health related impacts.
Sulfur and its refractory compounds found in fossil fuels are ex-
tremely reactive. They cause catalyst poisoning and corrode refining
equipment. In order to reduce air pollution and technological prob-
lems, EU and US have enacted laws to regulate sulfur emissions to
10 and 15 ppm respectively [1,2]. Various technologies are currently
in use to lower the organic sulfur compounds in fuels, these meth-
ods include: hydrodesulphurization (conventional method), oxida-
tive desulfurization, ionic liquids desulfurization, adsorptive desul-
furization and biodesulfurization [3–6]. Of all these technologies, ad-
sorptive desulfurization, one of the most promising technologies is
receiving much attention because of its facile and mild operating con-
ditions. Much attention is focused on the development of porous ad-
sorbents such as activated carbon, zeolites, alumina, and zirconia that
are cheap, easily regenerated and possesses high selectivity for sulfur
compounds [7–11].
The surface areas and porosities of AC are greatly influenced by the
parent material and the method employed in the production. Better
adsorption capacities and adsorption rates of AC are directly linked to
∗
Corresponding author. Tel.: +966 13 860 1734; fax: +966 13 860 1734.
E-mail address: tawfik@kfupm.edu.sa, tawfikas@hotmail.com (T.A. Saleh).
URL: http://faculty.kfupm.edu.sa/CHEM/tawfik/ (T.A. Saleh)
larger surface areas and pore size distributions [12]. Mesoporous and
microporous volumes of AC also play a crucial role in the adsorption
of larger molecules. In general, the selective adsorption of inorganic
molecules on the surface of AC directly depends on the amount of
oxygen containing complexes. The oxygen containing complexes are
mostly created using dry or wet oxidation methods [13–15]. Adsorp-
tive capability of AC modified with HNO3 at 120 °C was increased sig-
nificantly and modification using HNO3 even at high temperatures
showed a promising result in the removal of thiophenes from oil
[16,17].
The aim of this work was to produce AC from end of life tires as a
free-of-cost source, and to treat the AC using HNO3 and NaOH at var-
ious temperatures. The influence of acid/base treatment of AC for the
removal of thiophenes was examined. The adsorption performance of
the AC was evaluated.
2. Experimental
2.1. Development of the adsorbent
Waste rubber tires were cleaned by removing the iron wires from
the tire. Then, the waste rubber was cut into small pieces and thor-
oughly washed with deionized water, and then dried in an oven at
110 °C. The elemental analysis of the waste rubber indicated their ini-
tial elemental composition as 82.3 carbon, 9.2 oxygen, 0.7 nitrogen,
2.8 sulfur, 3.8 silicon and 1.2 silicon and silicon with different wt. %.

http://dx.doi.org/10.1016/j.jtice.2015.11.008
1876-1070/© 2015 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 T.A. Saleh, G.I. Danmaliki / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 460–468
The granules were heated up to 300 °C to separate the black tire
crude oil, distilled diesel oil and produced oil. Pyrolysis was carried
out in a muffle furnace at 500 °C for 5 h to isolate the ash and carbon
black from pyro-gas and other oils, followed by treatment with hy-
drogen peroxide solution to oxidize all adhering organic impurities.
The material was washed with deionized water and dried in vacuum
oven at 110 °C overnight. The char was then placed in the stainless
tube, inserted into the furnace, heated under nitrogen flow through
the sample bed at 200 ml/min at 20 °C/min to 900 °C and a holding
time of 5 h. Then the reactor was cooled down to room temperature
before the sample was removed, and kept in an oven overnight, then
grounded to small particles using pestle and mortar.
The produced black granules were sieved and the powdered car-
bon with a particle size of < 0.1 mm was used to allow good surface
contact with acid or base reagent solution. Chemical activation was
conducted on the prepared material using 4 M HNO3 and 4 M NaOH
at three different temperatures respectively (30, 60, and 90 °C) and a
duration of 3, 6 and 12 h. Then, the mixture was filtered and the ob-
tained activated carbon (AC) was washed with deionized water and
dried overnight.
It should be mentioned that increasing the refluxing time from
3 h to 12 h has an overall net negative effect on the removal of the
refractory sulfur compounds (see supporting information file, section
S3.1.). Therefore, 3 h refluxing time was selected.
2.2. Boehm’s method for surface functional groups
The amount of oxygen surface functional groups (both acidic and
basic) was determined according to modified Boehm’s method [18].
0.5 g of raw and treated carbon samples were added to beakers each
containing 25 ml of the following 0.05 M solutions: NaOH, Na2 CO3 ,
NaHCO3 and HCl. The beakers were sealed and shaken for 24 h and
then 10 ml of each filtrate was pipetted in an excess of 20 ml 0.05 M
HCl for the determination of acidic functional groups or NaOH for the
basic functional groups. The filtrate was titrated with 0.05 M NaOH
or HCl, respectively, using phenolphthalein indicator and the volume
required to reach the endpoint was noted. For Na2 CO3 reaction bases
an excess of 30 ml 0.05 M HCl was added rather than 20 ml due to
diprotic property of the base to ensure complete reaction with acid.
The number of acidic sites was calculated under the assumption that
NaOH neutralizes carboxylic, phenolic, and lactonic groups; Na2 CO3
neutralizes carboxylic and lactonic groups; and NaHCO3 neutralizes
only carboxylic groups. The number of surface basic sites was calcu-
lated from the amount of hydrochloric acid required. The following
formula was used to calculate the amount of surface acidic and basic
groups neutralized with NaOH and HCl respectively [19]:
Moles of Carbon functionality
([R a or b] Vr − ([X] Vx − [T ] Vt ))
=
m The amount of sulfur compounds adsorbed per unit mass of the
where [R a or b] and Vr denote the concentration and volume of the
reaction base or acid in mol/L and liters respectively. [X] and Vx de-
note the concentration and volume of the excess acid or base added
to the aliquot. [T ] and Vt denote the concentration and volume of the
titrant required to reach the endpoint. m stands for the mass of the
carbon used in grams.
The amount of surface acidic groups neutralized by Na2 CO3 and
NaHCO3 was calculated using the following formula [20,21]:
nHCl VB
ncsf = [B]VB − ([HCl]VHCl − [NaOH]VNaOH )
nB Va
where ncsf denotes the moles of carbon surface functionalities on
the surface of the carbon that reacted with base during the mix-
n
ing step. nHCl = molar ratio of acid to base [B] and VB are the con-
B
centration and volume of the reaction base mixed with the carbon.
[HCl] and VHCl are the concentration and volume of the acid added to
461
the aliquot taken from the original sample. [NaOH]VNaOH is the con-
centration and volume of the titrant in the back titration. Va is the
volume of the aliquot taken from VB .
Surface pH of the carbon samples was tested by HI 3512 bench-top
pH meter equipped with a graphic LCD display to gain insight about
the acidity and basicity of the samples. A suspension of 0.2 g of each
sample was added to 10 ml of water and the suspension was stirred
overnight to reach equilibrium. The samples were then filtrated and
the pH of the each solution was measured.
2.3. Characterization of the adsorbent
The FT-IR spectra of the samples were recorded using Nicolet 6700
spectrometer (Thermo electron, USA) with a resolution of 2.0 cm–1
well equipped with deuterated triglycine sulfate detector and an OM-
NIC program. The experiments were conducted on the powdered
samples ground in an agate mortar to produce KBr pellets and spec-
tra were obtained by adding 64 scans and corrected for the back-
ground noise. The spectra of the samples were recorded in transmis-
sion mode and the wavenumber range of 4000–400 cm–1 .
Scanning electron microscopy (SEM) analysis of the treated sam-
ples was conducted by using Hitachi model S- 3500 N instrument.
Energy dispersive X-ray spectroscopy (EDX) analysis was conducted
using Oxford Instrument (England) and X-Max detector to determine
the elemental composition of the treated samples.
X ray diffraction patterns of the adsorbents were taken using
(Rigaku Miniflex II desktop X-ray diffractometer) using Cu-Kά radi-
ation and an X-ray gun operated at 40 kV (voltage) and 200 mA cur-
rent. Data was collected from 2θ = 10°– 80° at a scan rate of 4°/min.
The porous structure of the AC samples was characterized by ad-
sorption/desorption of nitrogen at (−196 °C) on a Micromeritics ASAP
2020 surface area and porosimetry analyzer (Micromeritics, USA) to
determine the surface area (BET) and pore volume of the treated
sorbents.
2.4. Adsorption experiment
2.4.1. Batch mode
In a typical run in the batch mode adsorption studies, various
amounts, in the range between 0.1 and 0.5 g of adsorbents were intro-
duced into 15 ml of the fuel solution containing thiophene (T), ben-
zothiophene (BT) and dibenzothiophene (DBT) in hexane (85%) and
toluene (15%) with initial concentration of 50 ppm each. The sulfur
removal efficiency of the AC was calculated using the formula below:
x = (C0 − Ce )/C0 ∗ 100% (1)
where x x = sulfur removal percentage (%) C0 = initial concentration
of sulfur in model is (ppmw), Ce = final sulfur concentration.
adsorbent at equilibrium (qe mg/g) and at any time t (qt mg/g) termed
as the adsorption capacity was calculated from the formulas:
V (C0 − Ce )
qe = (2)
m
V (C0 − Ct )
qt = (3)
m
where V (L) is the volume of the liquid phase, C0 (mg/L) is the initial
concentration of the sulfur compounds before they come in contact
with the adsorbent, Ce and Ct (mg/L) are the concentration at equilib-
rium and at any time t, and m (g) is the amount of the adsorbent.
2.4.2. Break-through experiments
Fixed-bed flow system was used to test the simultaneous adsorp-
tive desulfurization of the treated AC samples using a column system.
462 T.A. Saleh, G.I. Danmaliki / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 460–468
Table 1
Surface pH, total basic and acidic groups on the raw and treated AC.
Sample Surface pH Total basic groups (mmol/g)
Raw AC 4.92 1.62
AC-NaOH 30 °C 10.66 2.48
AC-NaOH 60 °C 10.18 1.98
AC-NaOH 90 °C 10.69 2.46
AC-HNO3 30 °C 4.21 1.37
AC-HNO3 60 °C 4.05 1.36
AC-HNO3 90 °C 3.09 1.33
The adsorbent was packed inside the column. The model fuel sam-
ple was then passed through the column by a peristaltic pump with
a controlled flow rate (150 rpm) at a temperature of 25 °C. Once the
adsorption process started, treated fuels were periodically sampled at
different time intervals for analysis. The experiments were repeated
three times and the relative standard deviation was calculated and
found to be < 1.5%.
2.5. Analysis
The concentrations of the refractory sulfur compounds were an-
alyzed by gas chromatography sulfur chemiluminescence detector
(GC-SCD) (Model 7890A) system (Agilent) equipped with auto sam-
pler (7693) and splitless injector. The column used was Agilent
19091S-001: 2638-45555 50 m × 0.2 mm dimensions and a film
thickness of 0.5 μm methyl siloxane stationary phase. The injection
volume was 1 μl with a flow rate of 0.839 ml/min. Inlet temperature
was a 60 °C and oven program of 60 °C for 1 min, then 10 °C/min to
230 °C for 2 min. Other parameters and conditions of the method are
listed in the Supporting information file, Table S1.
3. Results and discussion
3.1. Characterization
3.1.1. Boehm’s titration
The acidic functional groups are due to the presence of phenols,
lactols, lactones and carboxylic acids. The acidic groups are said to dif-
fer in their acidities that can be determined by reaction with 0.05 M
NaOH, Na2 CO3 and NaHCO3 respectively [17,22]. Phenols are neutral-
ized with NaOH, while lactones and carboxylic acids are neutralized
by Na2 CO3 , and NaHCO3 neutralizes only carboxyl groups. The raw
AC is acidic with relatively high amount of phenolic groups and total
acidic groups of 1.71 mmol/g. However, upon treatment with NaOH
at 30 °C the total acidic groups decreased to 1.23 mmol/g but the
phenolic groups were greater than that of the raw samples (Table 1).
The increase in phenolic groups can be attributed to the deforma-
tion of the lactone groups resulting in the formation of more phenolic
groups [23]. This can be clearly observed by comparing the amount
of the lactone groups on the base-treated ACs with that of the acid-
treated ACs. Moreover, for the AC treated with NaOH at 90 °C, the
carboxylic groups were reduced due to its significant deformation;
but only the phenolic and lactonic groups were determined which
contributed less acidity. The total basic functional groups on the sur-
face of the AC-NaOH 30 °C were higher in all the samples modified.
Although the influence of the temperature was not that significant,
it could be noticed that the treatment at 60 °C seems to be the best
temperature for NaOH modification giving the highest surface acidic
functional groups (1.72 mmol/g) and the lowest surface basic groups
(1.98 mmol/g). On the other side, the increase in the total acidity
of the acid-treated ACs can be ascribed to the introduction of the
new acidic functional groups on the surface of the ACs [17,22]. Total
acidic functional groups increased with treatment temperature from
Surface acidic groups (mmol/g)
Phenol Lactone Carboxyl Total
0.81 0.22 0.68 1.71
1.07 0.16 0.00 1.23
1.21 0.33 0.18 1.72
1.13 0.25 0.00 1.38
0.80 0.64 0.67 2.11
0.82 0.71 0.69 2.22
0.69 0.81 0.89 2.39
2.11 to 2.22 and finally 2.39 mmol/g for AC-HNO3 30, 60 and 90 °C
respectively, and the total basic groups slightly reduced from 1.37 to
1.36 and finally to 1.33 mmol/g for the same samples respectively.
3.1.2. FTIR spectroscopy
FTIR spectra of the raw, HNO3 , and NaOH treated AC at various
temperatures (30, 60 and 90 °C) were taken to understand the func-
tional groups present in the AC and they are given in Fig. 1. The Raw
AC, NaOH and HNO3 treated AC have displayed varying degrees and
intensities of their bands though they all have similar patterns but
the bands increase with in treatment temperature. This implies that
temperature has an effect on the development of oxygen containing
functional groups and acidic and basic sites on the surface of the AC
[24,25]. It can be seen that the samples showed a broad peak cen-
tering around 3430 cm−1 that can be ascribed to O–H stretching vi-
brations of hydroxyl groups or to chemisorbed water. There is a no-
ticeable development peak at 2854 cm−1 and 2924 cm−1 as the tem-
perature increases and these peaks can be due to the presence of
aliphatic C–H stretch of CH, CH2 and CH3 . The peak at 1720 cm−1
is attributed to the carboxyl group. The peak at 1640 cm-1 is usu-
ally attributed to the carbonyl group. The peak around 1400 cm−1
appeared in HNO3 treated AC, may be attributed to the presence of
C=O stretching vibrations of the C=O, and C–O [19,26]. This confirms
the influence of temperature on the development of carbonyl groups
[27]. The NaOH treated AC at (30, 60 and 90 °C) have shown similar
patterns but the intensities are not well developed as compared to
the HNO3 treated AC. The results also confirm the influence of tem-
perature and HNO3 on the development of surface functional groups
such as nitrate, carboxyl, and carbonyl groups. In addition to the ab-
sorption peaks already discussed, the peaks around 2200–2400 cm−1
are almost certainly due to residual CO2 , either in the chamber or ad-
sorbed to the surface. The peaks at 500–700 cm–1 are noisy and dif-
ficult to attribute.
3.1.3. SEM/EDX result on the treated AC
The SEM/EDX result of the treated AC is depicted in Fig. 2. The
treatment with HNO3 at 30, 60, and 90 °C showed the presence of car-
bon and oxygen as the only elemental composition of the adsorbents
and they showed a significant improvement trend in the weight% of
oxygen from 11.01 to 11.86 and finally 14.39 meaning that oxygen con-
taining functional groups kept on increasing with temperature upon
acid treatment. This result is in accordance with the result obtained
from the FT-IR, Boehm’s titration experiment and XRD results. EDX
results on the base treated samples showed the presence of carbon,
oxygen and sodium in different proportions. Increase in treatment
temperature shows significant reduction in the wt. % of oxygen from
18.33 to 17.72 and finally 13.63 for AC-NaOH 30 °C, 60 °C and 90 °C
respectively.
3.1.4. XRD patterns of the treated AC
X-ray diffraction was conducted for the raw obtained AC, base-
treated AC and acid-treated AC samples (Figs. 3 and 4). The X-ray
 T.A. Saleh, G.I. Danmaliki / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 460–468
Fig. 1. FTIR spectra of raw AC and AC samples treated with sodium hydroxide or nitric acid at various temperatures.
diffraction profiles show two broad diffraction peaks of graphitic car-
bon with maxima at around 25° and 42° two theta. The two peaks
are indexed to (002) and (100) or (101) planes of crystalline hexag-
onal graphite lattice respectively (JCPDS card no. 41-1487) [28,29].
The relative intensities increased upon treatment signifying the im-
provement in the degree of graphitization structure and crystallinity
of the treated AC in addition to the removal of amorphous carbons
[7,30]. The peak, at approximately 25° two theta, was broadened on
increase of temperature, and this change in the width of the peak
can be attributed to the widening or expansion of the graphite lay-
ers in the individual crystalline (disintegration to relatively smaller
crystallites). It can be seen in Fig. 3 that the intensity of the peak, at
approximately 25° two theta, of AC treated with the base decreased
with increasing temperature from 60 to 90 °C indicating the induced
irregularity into the layered graphitic structure of the AC after the ac-
tivation process [31].
3.1.5. Brunauer–Emmett–Teller (BET) surface area and porosity studies
Nitrogen adsorption desorption isotherm is a useful tool in the
characterization of carbon materials. AC samples express Type I
isotherm according to Brunauer et al., 1940 [32,33], See Fig. S1 in
the Supporting information file. A hysteresis loop can be observed in
all the samples at the relative high pressure indicating the presence
of mesopores. As shown in Table 2, the surface area and pore vol-
umes were significantly enhanced upon NaOH and HNO3 treatments.
The N2 adsorption capacity followed the order: Raw < AC-NaOH
30 °C < AC-NaOH 90 °C < AC-NaOH 60 °C < AC-HNO3 -30 °C < AC-
HNO3 -60 °C < AC-HNO3 -90 °C. Temperature also enhanced the de-
velopment of the surface area in the acid treated AC. The change in
surface area caused by different treatments is summarized in Table 2.
It can be clearly seen that AC-NaOH-60 °C sample has the highest
surface area (369 m2 /g), pore volume (0.69 cm3 /g) and pore size
(75.03 Å) in the base treated AC. However, AC-HNO3 -90 °C has the
highest surface area (473.35 m2 /g) and pore volume (0.70 cm3 /g) of
all the samples used which confirms the significance of acid treat-
ment of AC in the development of surface area and porosity. The re-
sults are in agreement with the results obtained from the XRD, FT-IR
and Boehm’s experiment.
3.2. Adsorption evaluation
3.2.1. Contact time
The influence of contact time on the efficiency of AC-HNO3 -90 °C
on the removal of refractory sulfur compounds is depicted in Fig. 5. It
463
can be seen that the removal is very rapid, nearly 95% of all the ad-
sorption process occur in the first 5 min of the process. This is because
of the available free sites for adsorption of the sulfur compounds at
the beginning of the adsorption process. Equilibrium was achieved
at around 30 min of adsorption process and afterwards the adsorp-
tion of the refractory sulfur compounds was noticed to decline due to
the desorption process of the analytes from the adsorbent. The size
of the adsorbent, concentration of the sulfur compounds, degree of
mixing, the affinity of the adsorbent to the sulfur compounds and the
diffusion coefficient of the adsorbent in bulk and solid phases play
a cardinal role in the percentage of sulfur compounds adsorbed on
the surface of the adsorbent [34]. The adsorption capacity followed
the order: DBT > BT > T. The vast majority of the area of the sam-
ples is mesoporous, which makes it easier for adsorption at the initial
time, however, when the contact time increases the refractory sulfur
compounds are faced with much larger resistance to pass through the
micropores.
3.2.2. Influence of adsorbent dosage on the performance of
AC-HNO3 -90 °C and AC-NaOH-60 °C
Adsorbent dosage is an important parameter in adsorptive studies
because it determines the maximum adsorptive capacity of a given
adsorbent using a starting concentration of the analyte of interest.
Best NaOH and HNO3 treated samples were selected for testing the ef-
fect of adsorbent dosage. The effect of AC-HNO3 -90 °C and AC-NaOH-
60 °C dosages on the uptake of refractory sulfur compounds (Thio-
phene 52 ppm, BT 50 ppm and DBT 51 ppm at room temperature)
were studied and the results are shown in Fig. 6a–b. The mass of the
adsorbent was varied from 0.1 g to 0.5 g and the amount of refractory
sulfur compounds adsorbed was found to be increasing with adsor-
bent dosage. The increase in adsorption capacity of sulfur compounds
with dosage is expected because more active surface areas and sites
for sulfur adsorption are introduced in the medium [35,36]. The re-
moval efficiency after 0.25 g was less, becoming almost constant after
0.5 g; due to this, we fixed the rest of the experiments at an adsorbent
dosage of 0.5 g. The trend of adsorption of the refractory sulfur com-
pounds followed the order of DBT > BT > T. DBT was removed higher
than all other refractory sulfur compounds which can be attributed to
the dispersive interactions formed between the AC and DBT and due
to the presence of double benzene rings in DBT [37,38].
3.2.3. Effect of treatment reagent
The raw and treated AC both with NaOH and HNO3 were com-
pared for their desulfurization efficiency. 0.5 g of each sample was
taken and added to 50 ppm mixture of thiophene, BT and DBT in
464 T.A. Saleh, G.I. Danmaliki / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 460–468

Fig. 2. SEM image and EDX spectrum with an elemental analysis table of the prepared carbon treated with nitric acid at 30 °C (a), 60 °C (b), 90 °C (c), sodium hydroxide at 30 °C
(d), 60 °C (e), 90 °C (f).
 T.A. Saleh, G.I. Danmaliki / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 460–468 465

Fig. 3. XRD pattern of Raw AC and NaOH treated AC at 30, 60 and 90 °C.

Fig. 4. XRD pattern of AC treated with HNO3 at 30, 60 and 90 °C.

Table 2
Surface area and pore volume analysis.

Adsorbents BET surface area (m2 /g) Pore volume (cm3 /g) Pore size (Å)

Raw AC 183.21 0.30 77.54

AC-NaOH 30 °C 220.48 0.44 79.83
AC-NaOH 60 °C 369.27 0.69 75.03
AC-NaOH 90 °C 268.11 0.47 70.47
AC-HNO3 30 °C 429.26 0.66 62.10
AC-HNO3 60 °C 454.80 0.67 59.60
AC-HNO3 90 °C 473.35 0.70 60.22

20 ml (85% hexane and 15% toluene). The set ups were stirred and
samples were taken after 30 mins and analyzed with GC-SCD. The
result is shown in Fig. 7 and the percentage removals of thiophene,
BT and DBT from the raw and treated samples at various temper-
atures were reported. It can be clearly seen that raw sample per-
formed the least. AC-NaOH-60 °C showed the best performance in
the base treated samples and this can be attributed to the presence
of oxygen containing functional groups, high surface area, pore vol-
ume, and pore size exhibited by the sample compared with other
base treated samples. AC-HNO3 -90 °C showed the best performance
regardless of treatment conditions because it showed the highest to-
tal acidic groups, the largest intensity in XRD analysis, and the highest
in % transmittance in FT-IR. It also possesses the highest surface area
and pore volume. It should be noted that the reagent type plays a
role while the temperature has a subtle effect. The adsorbents per-
formance and adsorptive capacities followed the order: AC-HNO3 -
90 °C > AC-HNO3 -60 °C > AC-HNO3 -30 °C > AC-NaOH-60 °C > AC-
NaOH-90 °C > AC-NaOH-30 °C > Raw AC. This order is consistent
with the increase in the surface area and pore volume of the ad-
sorbents and their total acidic groups [40,41]. This implies that both
surface area and surface chemistry play an important role in adsorp-
tion capacity. The adsorption capacities were calculated and listed in
Table S2.
466 T.A. Saleh, G.I. Danmaliki / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 460–468
Fig. 5. Influence of contact time on removal of thiophene, BT and DBT by AC-HNO3 -
90 °C (adsorbent dosage 0.5 g, 20 ml volume of model fuel containing 52 ppm thio-
phene, 50 ppm BT and 51 ppm DBT).
Fig. 6. Influence of adsorbent dosage AC-HNO3 -90 °C (a) and AC-NaOH-60 °C (b) on
the adsorptive removal of thiophene, BT and DBT (initial concentrations 51, 50 and
52 ppm respectively, 20 ml volume of solution and 30 min contact time).
The decrease in the efficiency of the AC-NaOH-90 °C compared
with AC-NaOH-60 °C can be attributed to the increase in irregularity
of graphitic layer structures of AC treated with the base at 90 °C as
it has been discussed under the section of XRD results (see Fig. 3).
On the other side, the adsorption efficiency of the AC treated with
acid increases with treatment temperature. This trend is in consis-
tence with the XRD patterns of these samples, which indicated the
improvement in the crystallinity and graphitic structure of the AC
(see Fig. 4). From this point of view, it is conceivable that increas-
ing behaviors of the adsorption by acid-treated AC could reflect the
contribution of π –π interaction between the basal plane of carbon
and the aromatic ring of the adsorbate [39,40].
Fig. 7. Percentage removal of thiophene, BT, and DBT (initial concentration of 50 ppm
each) on acid and base treated AC samples after 30 min (dosage of each sample was
0.5 g in 20 ml initial solution volume) at 25 °C.
The percentage removal of the refractory sulfur compounds in all
the ACs followed the order: DBT > BT > T. The treated ACs showed at
least 80% percentage removal or greater of DBT and this is due to the
size of the molecule and acidic functional groups on the surfaces of
the larger pores which contributes to polar interactions [42,43]. Dis-
persive interactions between the delocalized π -electrons within the
benzene rings of DBT and the electron rich region of the nanoporous
carbon aromatic ring also play a major role in the adsorption. The re-
sults also confirm the influence of treatment conditions on the overall
performance in adsorptive studies.
3.3. Breakthrough curves
The performance of AC-NaOH-60 °C and AC-HNO3 -90 °C were fur-
ther studied in a fixed bed mode. Breakthrough curves were gener-
ated by plotting transient total sulfur concentration normalized by
the feed total sulfur concentration (C/C0 ) versus cumulative time. The
breakthroughs curves for thiophene, BT and DBT in the base and acid
treated samples are depicted in Fig. 8a–b. The starting concentrations
of thiophene, BT and DBT were 50 ppm, 51 ppm and 52 ppm respec-
tively. The acid treated sample showed higher breakthrough times
compared to the base treated sample. DBT was lowered to 0 ppm after
5 min of adsorption in all the samples tested; however, breakthrough
was not achieved even after 400 min of adsorption. This indicates the
suitability of acid treatment in the adsorption of this compound. A
breakthrough was achieved after 180 min for DBT using AC-NaOH-
60 °C. The breakthroughs of thiophene and BT in both AC-NaOH-60 °C
and AC-HNO3 -90 °C were achieved after 5 min and 10 min respec-
tively. For AC-NaOH-60 °C, thiophene returned to its initial concen-
tration after the first 120 min while BT returned to its initial concen-
tration after 50 min signifying no further adsorption that has taken
place after this time. This is in contrast with the AC-HNO3 -90 °C per-
formance, both thiophene and BT did not reach their initial concen-
tration even after 400 min of the column adsorption process. The ad-
sorption capacities in column mode for all the adsorbents followed
the order DBT > BT > T. This means that AC treated with HNO3 is
good in both batch and fixed bed mode.
3.4. Regeneration of the used adsorbent
The synthesized activated carbon (AC-HNO3 -90C) was evalu-
ated for its regeneration abilities. The regeneration was done by
heating the adsorbent in air for 3 h at 350 °C. The temperature
is said to vaporize all the sulfur compounds from the adsorbent.
As results showed in Fig. 9, the percentage removal of the sulfur
 T.A. Saleh, G.I. Danmaliki / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 460–468
Fig. 8. Breakthrough curve for AC-NaOH-60 °C (a) and AC-HNO3 -90 °C (b).
Fig. 9. Regeneration efficiency of AC-HNO3 -90 °C on the adsorption of sulfur
compounds.
compounds showed some decrease in the adsorptive capacity of the
adsorbent. However, it still showed great promise in the removal
DBT even after three cycles of regeneration. The order of desulfur-
ization after three regeneration cycles followed the sequence: DBT
(59%) > T (6%) > BT (5%).
4. Conclusion
Waste tires can be effectively used as a raw material for the
preparation of high-surface area AC after treatment. Upon treatment
with NaOH or HNO3 , the surface area and functional groups, such
as carboxyl, lactone and phenol groups were enhanced. The effect
of the treatment temperature on the adsorption performance was
limited. The highest total acidic functional groups of 2.39 mmol/g was
467
obtained for AC-HNO3 at 90 °C. The adsorption of dibenzothiophene,
benzothiophene and thiophene by the AC-HNO3 90 °C were higher
than that of the raw AC by about 2.2, 3.4 and 3.8 times respectively.
This can be explained according to Lewis acid–base theory, most thio-
phene sulfur compounds are Lewis base, which are easy to be ad-
sorbed at acid sites. The study has the advantages of solving dou-
bly environmental problems by converting such negative-value waste
tires to value-added activated carbon for adsorptive desulfurization
toward clean fuel.
Acknowledgments
The authors gratefully acknowledge the support provided by King
Fahd University of Petroleum & Minerals (KFUPM). This project was
funded by the National Plan for Science, Technology and Innova-
tion (MAARIFAH)—King AbdulAziz City for Science and Technology—
through the Science & Technology Unit at King Fahd University of
Petroleum & Minerals (KFUPM)—the Kingdom of Saudi Arabia, award
number (13-PET393-04).
Supplementary materials
Supplementary material associated with this article can be found,
in the online version, at doi:10.1016/j.jtice.2015.11.008.
References
[1] Khan NA, Hasan Z, Jhung SH. Adsorptive removal of hazardous materials using
metal–organic frameworks (MOFs): a review. J Hazard Mater 2013;244–245:444–
56.
[2] Srivastava VC. An evaluation of desulfurization technologies for sulfur removal
from liquid fuels. RSC Adv 2012;2:759–83.
[3] Pawelec B, Navarro RM, Castano P, Alvarez-Galvan MC, Fierro JLG. Energy Fuels
2009;23:1364–72.
[4] Hasan Z, Jeon J, Jhung SH. Oxidative desulfurization of benzothiophene and thio-
phene with WOx/ZrO2 catalysts: effect of calcination temperature of catalysts.
J Hazard Mater 2012;205–6:216–21.
[5] Rodríguez-Cabo B, Rodríguez H, Rodil E, Arce A, Soto A. Extractive and oxidative-
extractive desulfurization of fuels with ionic liquids. Fuel 2014;117:882–9.
[6] Martinez I, Santos VE, Alcon A, Garcia-Ochoa F. Enhancement of the biodesulfu-
rization capacity of Pseudomonas putida CECT5279 by co-substrate addition. Pro-
cess Biochem 2015;50:119–24.
[7] Ma X, Yang H, Yu L, Chen Y, Li Y. Preparation, surface and pore structure of high
surface area activated carbon fibers from bamboo by steam activation. Materials
2014;7:4431–41.
[8] Zhang HX, Huang HL, Li CX, Meng H, Lu YZ, Zhong CL. Adsorption behavior of
metal–organic frameworks for thiophenic sulfur from diesel oil. Ind Eng Chem
Res 2012;51:12449–55.
[9] Srivastava VC. An evaluation of desulfurization technologies for sulfur removal
from liquid fuels. RSC Adv 2012;2:759–83.
[10] Martinez I, Santos VE, Alcon A, Garcia-Ochoa F. Enhancement of the biodesulfu-
rization capacity of Pseudomonas putida CECT5279 by co-substrate addition. Pro-
cess Biochem 2015;50:119–24.
[11] Xiao J, Li Z, Liu B, Xia Q, Yu M. Adsorption of benzothiophene and dibenzothio-
phene on ion-impregnated activated carbons and ion-exchanged Y zeolites. En-
ergy Fuels 2008;22:3858–63.
[12] Chiang HL, Huang CP, Chiang PC, You JH. Effect of metal additives on the physico-
chemical characteristics of activated carbon exemplified by benzene and acetic
acid adsorption. Carbon 1999;37:1919–28.
[13] Jiang Z, Liu Y, Sun X, Tian F, Sun F, Liang C, et al. Activated carbons chem-
ically modified by concentrated h2 so4 for the adsorption of the pollutants
from wastewater and the dibenzothiophene from fuel oils. Langmuir
2003;19:731–6.
[14] Jung BK, Jhung SH. Adsorptive removal of benzothiophene from model fuel, using
modified activated carbons, in presence of diethylether. Fuel 2015;145:249–55.
[15] Boehm HP. Surface oxides on carbon and their analysis: a critical assessment.
Carbon 2002;40:145–9.
[16] Moreno-Castilla C, Lo´pez-Ramo´n MV, Carrasco-Marin F. Changes in
surface chemistry of activated carbons by wet oxidation. Carbon 2000;38:1995–
2001.
[17] Yu V, Qiu JS, Sun YF, Li XH, Chen G, Zhao ZB. Adsorption removal of thiophene and
dibenzothiophene from oils with activated carbon as adsorbent: effect of surface
chemistry. J. Porous Mater. 2008;15:151–7.
[18] Boehm HP. Chemical identification of surface groups. Adv Catal. 1966;16:179.
[19] Chen PJ, Shunnian W. Acid/base-treated activated carbons: characterization of
functional groups and metal adsorptive properties. Langmuir 2004;20:2233–42.
[20] Oickle AM, Goertzen SL, Hopper KR, Abdalla YO, Andreas HA. Standardization of
the Boehm titration: Part II. Method of agitation, effect of filtering and dilute
titrant. Carbon 2010;48:3313–22.
468 T.A. Saleh, G.I. Danmaliki / Journal of the Taiwan Institute of Chemical Engineers 60 (2016) 460–468
[21] Goertzen SL, Theriault KD, Oickle AM, Tarasuk AC, Andreas HA. Standardization
of the Boehm titration. Part I. CO2 expulsion and endpoint determination. Carbon
2010;48:1252–61.
[22] Boehm HP. Surface properties of carbons. Studies Surface Sci Catal 1989;48:145–
57.
[23] Park S, Seo M-K. Interface Science and Composites. Academic Press; 2011. p. 197–
8.
[24] Saleh TA. The influence of treatment temperature on the acidity of MWCNT oxi-
dized by HNO3 or a mixture of HNO3 /H2 SO4 . Appl Surface Sci 2011;257(17):7746–
51.
[25] Guo JX, Liu XL, Luo DM, Yin HQ, Li JJ, Chu YH. Influence of calcination tem-
peratures on the desulfurization performance of fe supported activated carbons
treated by HNO3 . Ind Eng Chem Res 2015;54:1261–70.
[26] Wu XH, Hong XT, Luo ZP, Hui KS, Chen HY, Wu JW. The effects of surface mod-
ification on the super-capacitive behaviors of novel mesoporous carbon derived
from rod-like hydroxyapatite template. Electrochim Acta 2013;89:400–6.
[27] Tazibet S, Boucheffa Y, Lodewyckx P. Heat treatment effect on the textural, hy-
drophobic and adsorptive properties of activated carbons obtained from olive
waste. Microporous Mesoporous Mater 2013;170:293–8.
[28] Babu VS, Seehr MS. Modeling of disorder and X-ray diffraction in coal-based
graphitic carbons. Carbon 1996;34(10):1259–65.
[29] Ji Y, Li T, Zhu L, Wang X, Lin Q. Preparation of activated carbons by microwave
heating KOH activation. Appl Surface Sci 2007;254:506–12.
[30] Viswanathan B, Neel PI, Varadarajan TK. Methods of activation and specific ap-
plications of carbon materials. Nat Centre Catal Res., Indian Inst Technol Madras
Chennai 2009;600:036.
[31] Kim BJ, Lee YS, Park SJ. A study on pore-opening behaviors of graphite nanofibers
by a chemical activation process. J Colloid Interface Sci 2007;306:454.
[32] Brunauer S, Deming LS, Demomg WE, Teller DE. On a theory of the van der Waals
adsorption of gases. J Am Chem Soc. 1940;62:1723–32.
[33] Deng H, Yang L, Tao G, Dai J. Preparation and characterization of activated
carbon from cotton stalk by microwave assisted chemical activation: application
in methylene blue adsorption from aqueous solution. J Hazard Mater 2009;166(2–
3):1514–21.
[34] Srivastav A, Srivastava VC. Adsorptive desulfurization by activated alumina. J Haz-
ard Mater 2009;170:1133–40.
[35] Xu X, Zhang S, Li P, Shen Y. Adsorptive desulfurization of liquid Jet-A fuel at ambi-
ent conditions with an improved adsorbent for on-board fuel treatment for SOFC
applications. Fuel Process Technol 2014;124:140–6.
[36] Hernández-Maldonado AJ, Yang RT. Desulfurization of transportation fuels by ad-
sorption. Catal Rev 2004;46(2):111–50.
[37] Bu J, Loh G, Gwie CG, Dewiyanti S, Tasrif M, Borgna A. Desulfurization of diesel fu-
els by selective adsorption on activated carbons: competitive adsorption of poly-
cyclic aromatic sulfur heterocycles and polycyclic aromatic hydrocarbons. Chem
Eng J 2011;166:207–17.
[38] Takahashi A, Yang FH, Yang RT. New sorbents for desulfurization by
π -complexation: thiophene/benzene adsorption. Ind Eng Chem Res.
2002;41(10):2487–96.
[39] Wang Y, Yang RT. Desulfurization of liquid fuels by adsorption on carbon-
based sorbents and ultrasound-assisted sorbent regeneration. Langmuir
2007;23(7):3825–31.
[40] Saleh TA. Nanocomposite of carbon nanotubes/silica nanoparticles and their use
for adsorption of Pb (II): from surface properties to sorption mechanism. Desalin
Water Treatment 2015:1–15. doi:10.1080/19443994.2015.1036784.
[41] Saleh TA. Isotherm, kinetic, and thermodynamic studies on Hg(II) adsorption from
aqueous solution by silica- multiwall carbon nanotubes. Environ Sci Pollut Res
2015;22(21):16721–31.
[42] Triantafyllidis KS, Deliyanni EA. Desulfurization of diesel fuels: adsorption of 4,
6-DMDBT on different origin and surface chemistry nanoporous activated car-
bons. Chem Eng J 2014;236:406–14.
[43] Saleh TA, Alhooshani KR, Abdelbassit MSA. Evaluation of AC/ZnO composite for
sorption of dichloromethane, trichloromethane and carbon tetrachloride: kinet-
ics and isotherms. J. Taiwan Inst Chem Eng 2015;55:159–69.