Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19

Contents lists available at ScienceDirect

Process Safety and Environmental Protection

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

Adsorptive desulfurization of dibenzothiophene

from fuels by rubber tyres-derived carbons:
Kinetics and isotherms evaluation

Tawfik A. Saleh a,∗,1 , 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: The aim of this work was to investigate the utilization of waste rubber tyres as a low cost
Received 7 September 2015 adsorbent for adsorptive desulfurization of dibenzothiophene from fuels, as a double clean-
Received in revised form 27 January ing process. Thus, rubber tires were converted into activated carbon by pyrolysis, activation
2016 and chemical treatment with 4 M HNO3 for 3 h at 90 ◦ C for the enhancement of surface func-
Accepted 9 February 2016 tionalities. The effects of temperature and time on the yield of carbons were investigated.
Available online 17 February 2016 The optimized pyrolysis time and temperature yielded carbon with average BET surface area
of 493 m2 /g, a pore volume of 0.77 cm3 /g, and pore size of about 6 nm. The adsorbent was
Keywords: also characterized by thermogravimetric analysis and differential scanning calorimetry. X
Adsorptive desulfurization ray diffraction pattern indicates that the sample showed a broad diffraction peak at 2 values
Kinetics around 25◦ (0 0 2) and 43◦ (1 0 0). Fourier transform infrared spectrum showed peaks centered
Isotherms at 3430 cm−1 , 1720 cm−1 and 1640 cm−1 indicating the presence of hydroxyl and carboxylic
Dibenzothiophene groups on the carbon surface. The adsorbent was evaluated for the adsorptive desulfuriza-
Fuels tion of dibenzothiophene. Pareto chart was used to investigate the effect of the experimental
Activated carbon parameters. Adsorption kinetics and isotherm studies were performed, and the adsorption
Adsorption data fitted well to pseudo second-order model and Freundlich isotherm model. The adsor-
bent after adsorption was characterized by scanning electron microscopy equipped with an
energy-dispersive X-ray spectroscopy.
© 2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction management alternatives employed to curtail the impacts are

Rubber tires have become an indispensable part of our trans-
portation system. The tire industry has been continuously
developing, and the overall use of the product has increased
dramatically. One billion rubber tires were generated world-
wide, according to a report by world business council for
sustainable development (WBCSD, 2008). Substantial amounts
of these non-biodegradable products end up in the landfills
at the termination of their use, posing serious environmen-
tal, land management and health related impacts. The basic
to burn, retread, vulcanize and reclaim the tires.
Various thermochemical processes such as gasification,
combustion, and pyrolysis are used to curtail the impacts
of these materials. However, pyrolyzing these waste materi-
als, despite their recalcitrant nature is believed to be a viable
management alternative, because it leads to the production
useful raw materials such as gases, liquid hydrocarbon fuels,
and solid carbon black for industrial purposes (Ariyadejwanich
et al., 2003; Martinez et al., 2013; Antoniou et al., 2014). The car-
bon black is considered one of the most important products

∗
Corresponding author. Tel.: +966 13 860 1734; fax: +966 13 860 1734.
E-mail addresses: tawfik@kfupm.edu.sa, tawfikas@hotmail.com (T.A. Saleh).
1
Home Page: http://faculty.kfupm.edu.sa/CHEM/tawfik/.
http://dx.doi.org/10.1016/j.psep.2016.02.005
0957-5820/© 2016 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
10 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19
since it accounts for 30–40% weight of the rubber tyres and it
is used for activated carbon production.
Activated carbon (AC) is amorphous and possesses a micro-
crystalline structure with large surface area and high porosity.
The physical production of AC from rubber tyres involves
carbonization of the tyres followed by physical or chemi-
cal activation of the material formed (Srinivasakannan and
Abu Bakar, 2004). In carbonization, the rubber tyres are sub-
jected to pyrolysis at a temperature ≤800 ◦ C under controlled
conditions of the atmosphere and heat. At this stage, the
elemental composition of the rubber tyres used will be decom-
posed, leaving behind only the aggregates of carbon that are
randomly linked together forming residual pores which are
used for adsorption. The activation of the material formed by
pyrolysis involves modification at 800 ◦ C to 900 ◦ C in a con-
trolled atmosphere. This will improve the surface area of the
AC (Williams and Brindle, 2003; Cunliffe and Williams, 1993).
Studies on the utilization of this form of adsorbent (AC from
rubber tyres) focus more on the removal of dyes, pesticides,
and heavy metals from waste water (Zabaniotou et al., 2014;
Saleh and Al-Saadi, 2015; Saleh et al., 2015).
The removal of sulfur is an important step in the refining
of crude oil since the combustion products of sulfur com-
pounds are the main reason for acid rain and environmental
pollution. In addition, sulfur poisons catalysts and corrode
refining equipment. Hence, ppb levels of sulfur contaminants
are required to achieve a commercially viable operation life.
Those problems are the reasons for an ongoing effort to lower
the legal limits of sulfur in various kinds of petroleum prod-
ucts. In Germany, transportation fuels with a residual sulfur
content of more than 10 ppm are taxed to encourage refiners
to further reduce their diesel sulfur content to 10 ppm wt. In
the US, the Environmental Protection Agency (EPA) has man-
dated 15 ppm wt, highway diesel since 2006 (Triantafyllidis
and Deliyanni, 2014).
Achieving near-zero sulfur levels are technically challeng-
ing. Hydrodesulfurization (HDS) has been widely used sulfur
abatement technology in refining. Even though the major-
ity of low-sulfur hydrocarbon fuels are derived through HDS,
there are limitations like the requirement of large catalyst
volumes. In oxidative desulfurization (ODS), an aqueous oxi-
dant reacts with the sulfur contaminant in the fuel phase. The
thiophene contaminants are oxidized to sulfones, which are
easily removed from the fuel because they are no longer sol-
uble in the fuel phase. With ODS, the sulfur contaminants,
that are most resistant to HDS, are reactive under ODS condi-
tions (Sundararaman et al., 2010). However, a major problem
with the ODS processes is that it employs an aqueous oxi-
dant (hydrogen peroxide with a catalytic amount of an acid
such as acetic acid) that must react with the sulfur contam-
inants in the fuel phase. Such process has some constraints
like the requirements of hours of stirring at elevated tempera-
tures and pressure, the cost of H2 O2 , the generation of water as
a byproduct driving the need for molecular efficiency because
excessive water in the fuel is detrimental to an engine.
Adsorptive desulfurization, another alternative to HDS, can
take the form of H2 S removal after initial HDS, or it can
involve direct adsorption of the most recalcitrant compounds
(Song et al., 2011; Gaddafi and Saleh, 2016). Direct adsorp-
tion of the recalcitrant sulfur compounds is an appealing
process because it can be carried out at ambient tempera-
tures and pressures. There has been much recent interest
in desulfurization of fuels at ambient temperature and pres-
sure using a variety of adsorbents for selective sulfur removal,
such as activated carbon, modified carbons, NaY and other
type-Y zeolites, and Ag-doped on mesoporous supports (Song,
2003). However, there are some requirements for sorbents to
be used in desulfurization by adsorption, including low-cost
and fast adsorption process. The present study, therefore,
aims to study the efficiency of rubber-derived activated car-
bon for adsorptive desulfurization of dibenzothiophene. The
work includes an initial optimization study for the produc-
tion of the best adsorbent, characterization of the synthesized
adsorbent, a Pareto chart generated by experimental design
using Minitab software to understand the important factors
affecting DBT adsorption, and kinetics and isotherm studies.
2. Experimental
2.1. Preparation of activated carbons
Pieces of waste rubber tyres were collected from the dumping
site, cleaned, thoroughly washed with deionized water, and
then dried in an oven at 120 ◦ C for 4 h. Then, they were divided
into small chunks for carbonization (to convert organic mat-
ter to elemental carbon at high temperature in the absence
of oxygen). The dried materials, with an initial mass of 20 g,
were subjected to pyrolysis by heating at temperatures ranging
from 250 to 550 ◦ C and for different intervals, in inert (nitrogen)
atmosphere. Then, to oxidize adhering organic impurities, the
obtained materials were treated with hydrogen peroxide solu-
tion.
Physical and chemical activation were performed in this
study. For physical activation, the obtained material was acti-
vated at different temperatures: 400, 500, 600, 700, 800 and
900 ◦ C at a fixed time 5 h in a muffle furnace in a steam as an
oxidizing agent. This is followed by chemical activation where
the material was treated with 4 M HNO3 for 3 h at 90 ◦ C to
activate and develop oxygen functional groups on the surface
of the adsorbent. The adsorbent was washed with deionized
water and dried. The following formulas were used for the
calculation of percentage yield and recovery percentage:
actual yield
% Yield = × 100
theoretical yield
amount of pure product recovered
% Recovery = × 100
amount of crude material used
2.2. Characterization
2.2.1. BET surface area
The porous structure of the synthesized materials was char-
acterized by adsorption/desorption of nitrogen at (−196 ◦ C) on
a Micromeritics ASAP 2020 surface area and porosimetry ana-
lyzer (Micromeritics, USA) to determine the surface area (BET),
pore volume and pore size distribution of the treated sorbents.
2.2.2. XRD
The X-ray diffraction pattern of the adsorbent was taken using
(Rigaku Miniflex II desktop X-ray diffractometer) using Cu-K␣
radiation and an X-ray gun operated at 40 kV (voltage), 200 mA
current and  = 1.54 Å using powdered samples. Data was col-
lected from 2 = 0–80◦ at a scan rate of 4◦ /min to understand
the atomic and molecular structure of the adsorbent. The
atoms present in the adsorbent were determined and the rela-
tive intensities were also taken. The microcrystalline structure
of the adsorbent was examined by determining the crystallite
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19
thickness (Lc ) and average interlayer spacing (d), the formulas
used were Bragg and Scherrer and they are given as follows:
 the volume required to reach the endpoint was noted. For
d=
2 sin 
K
Lc =
FWHM cos 
where  is the Bragg angle of peaks (◦ ),  is the wavelength
(0.154 nm), FWHM is the full width at half maximum (rad)
and K is a factor with a constant value of 0.89. The lattice
constant (a) and the graphitization degree (g) were calculated
using layer d spacing in the formulas below:
 5 h and treated with 4 M nitric acid for 3 h, showed the highest
a=d h2 + k2 + l2
0.3440 − d
g=
0.3440 − 0.3354
where 0.3440 stands for the layer spacing of not graphite car-
bon material completely (nm); 0.3354 is the layer spacing of
the ideal graphite crystal (nm); d is the layer spacing.
2.2.3. Scanning electron microscopy/elemental dispersive
spectroscopy
Scanning electron microscopy (SEM) analysis of the treated
samples was conducted using low vacuum JEOL (JSM-6610LV
Scanning Electron Microscope (SEM) equipped with tungsten
electron gun. The energy dispersive X-ray spectroscopy (EDX)
analysis was conducted to understand the composition of the
synthesized materials. EDX is an analytical technique used
for chemical characterization and elemental analysis based
on the fact that each element has unique characteristics and
composition that allow a unique set of peaks to appear upon
interaction with X-ray light.
2.2.4. Fourier transform infrared spectroscopy
The FT-IR spectrum of the synthesized adsorbent was
recorded using Nicolet 6700 spectrometer (Thermo elec-
tron, USA) with a resolution of 2.0 cm−1 well equipped with
Deuterated triglycine sulfate detector and an OMNIC pro-
gram. The experiments were conducted on the powdered
samples ground in an agate mortar to produce KBr pellets
and spectra were obtained by adding 64 scans and corrected
for the background noise. The spectra of the samples were
recorded in transmission mode and the wavenumber range of
4000–400 cm−1 .
2.2.5. Thermogravimetric analysis and differential
scanning calorimetry (TGA and DSC)
These analyses measure the heat flow and weight changes
associated with transitions and reactions in materials over
the temperature range ambient to 1500 ◦ C. The analysis was
conducted to understand the thermal stability of the adsor-
bent. SDT (Simultaneous DSC and TGA) Q600 T.A Instruments
was used for the analysis. The thermal stability of sorbents
was tested by heating to 800 ◦ C. About 10–15 mg of the sor-
bent was heated using a Platinum/Platinum–Rhodium (Type
R) thermocouples.
Boehm’s method (Boehm, 1966; Saleh, 2011; Saleh and
Danmaliki, 2015) was used for surface functional groups.
Briefly, 0.5 g of the carbon sample were added to a beaker con-
taining 25 ml of the following 0.05 M solution: NaOH, Na2 CO3 ,
NaHCO3 and HCl. The beaker was sealed and shaken for 24 h
and then 10 ml of the filtrate was pipetted in an excess of 20 ml
0.05 M HCl for the determination of acidic functional groups or
11
NaOH for the basic functional groups. The filtrate was titrated
with 0.05 M NaOH or HCl using phenolphthalein indicator and
Na2 CO3 reaction base, an excess of 30 ml 0.05 M HCl was added
rather than 20 ml due to the diprotic property of the base to
ensure complete reaction with acid. The number of acidic sites
was calculated under the assumption that NaOH neutralizes
carboxyl, phenolic, and lactonic groups; Na2 CO3 neutralizes
carboxyl and lactonic, and NaHCO3 neutralizes only carboxyl
groups. The number of surface basic sites was calculated from
the amount of hydrochloric acid required.
The obtained activated carbon, pyrolyzed at the 500 ◦ C for
total acidic functional groups of 2.4 mmol/g. Therefore, it was
used for the adsorptive desulfurization in this work. It should
be mentioned that the surface area of the H2 O2 -washed char
without nitric acid treatment was 362 m2 /g while the 493 m2 /g
surface area was for the nitric acid treated sample. There-
fore, the sample treated with acid was used for the adsorptive
desulfurization.
2.3. Adsorptive desulfurization experiments
The sulfur concentration in the model fuel was 150 ppm pre-
pared by dissolving 150 mg of DBT in 1 L of a mixture of 85%
hexane and 15% toluene. The adsorption experiment was con-
ducted both in batch mode. The amount of sulfur in DBT was
calculated using the formula below:
molecular weight of sulfur
DBT concentration (ppm) =
molecular weight of DBT
2.3.1. Batch adsorption experiment
In a typical run in the batch mode adsorption studies, vari-
ous amounts, in the range between 0.1 and 0.5 g of adsorbents
were introduced into 15 ml of the fuel solution. The total DBT
initial concentration was 50 ppm. The solution containing the
adsorbent and the refractory sulfur compound was stirred
at room temperature until equilibrium. After adsorption for
90 min, samples were collected using a syringe filter (poly-
tetrafluoroethylene) and the concentration of the DBT was
measured by gas chromatography coupled with sulfur chemi-
luminescence detector.
2.3.2. Column adsorption experiment
A glass column of length 11 cm and 0.5 cm internal diame-
ter, filled with weighed amount of the activated carbon as a
fixed bed adsorber was used for the column experiment. The
bed was supported and closed by a glass to prevent the flow of
adsorbent together with the effluent. The bed was then rinsed
with hexane and left overnight to ensure a closely packed
arrangement of particles without voids, channels and cracks.
Effluent flow was adjusted with a clip at the bottom of the
column. The column was then loaded with a DBT solution of
known concentration at a constant flow rate of 0.5 ml min−1
under the influence of gravity. It is important to point out that
the flow rate for column study in this article is low but is still
sufficient to demonstrate the mass transfer effect. The exper-
iments were carried out at room temperature. The column
runs were carried out till breakthrough was achieved. Sam-
ples of the effluent were collected at different time intervals
and injected to the GC-SCD for analysis.
12 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19

2.3.3. Factorial design for the fixed bed adsorption of DBT

Table 1 – Effect of pyrolysis temperature on the
Minitab software version 16 was used for the design of exper- production of carbon black, liquid and gas (%).
iments to understand the most significant factors affecting
Temperature (◦ C) Carbon Liquid Gases
the fixed bed adsorption experiment. Five factors: concentra-
black hydrocarbons
tion, flow rate, column length, dosage and contact time, were
selected with high and low values. Half factorial design 2(5-1) 250 83 13 5
300 72 18 10
with 16 experimental runs without a center point and ran-
350 65 20 15
domization were used for the analysis.
400 60 22 18
The sulfur removal efficiency of the AC treated samples was 450 54 27 19
calculated using the formula below: 500 51 28 21
550 51 27 22
(C0 − Ce )
%R = × 100%
C0
where %R = Sulfur removal percentage (%), C0 = Initial con-
centration of sulfur in model oils (ppmw), Ce = final sulfur
concentration
A number of sulfur compounds adsorbed per unit mass of
the 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 =
m

V(C0 − Ct )
qt =
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 equilibrium and at any time t, and m (g) is the Fig. 1 – Effect of temperature on the yield of carbon black,
amount of the adsorbent. liquid hydrocarbons and gases from waste rubber tyres.

2.4. GC-SCD analysis method and data analysis

of the adsorbent. There are fifteen different isotherm mod-
The concentration of the refractory sulfur compounds was els, but this work is restricted to the Langmuir and Freundlich
analyzed by GC-SCD (Model 7890A) system (Agilent) equipped isotherms.
with an auto sampler (7693) and splitless injector. The col-
umn used was Agilent 19091S-001: 2638-45555 50 m × 0.2 mm 3. Results and discussion
dimensions and a film thickness of 0.5 ␮m methyl siloxane
stationary phases. The injection volume was 1 ␮L with a flow 3.1. Preparation of activated carbons (AC)
rate of 0.839 ml min−1 . The maximum temperature was 325 ◦ C
and the oven temperature programming used was 60 ◦ C for The results of the effect of pyrolysis temperature on the yield
1 min, then 10 ◦ C/min to 230 ◦ C for 2 min. of carbon black, liquid hydrocarbons and gases are presented
in Table 1 and Fig. 1 respectively. It can be clearly seen that
2.5. Adsorption kinetics the yield of carbon black decreases with temperature, mean-
ing that the conversion of organic matter to elemental carbon
Adsorption kinetics is a useful tool for the determination of continued and increases by increasing the temperature from
adsorption mechanism and its pathways. It gives the rate of 250 till 500 ◦ C (Jasmin et al., 2006). Increasing the tempera-
solute uptake by the solid–solution interface. Contact time ture beyond that has no effect on the yield, which indicates an
and adsorbent dosage are useful tools in the determination effective conversion of the waste rubber tires to carbon black
adsorption kinetics of the refractory sulfur compounds from at 500 ◦ C.
model fuel. The kinetics of the refractory sulfur compounds The effect of pyrolysis time on the development of carbon
on the synthesized adsorbent was analyzed using pseudo first black was studied and the results are shown in Table 2 and
order, pseudo second order and intraparticle diffusion models. Fig. 2. The pyrolysis time was varied from 30 min to 5 h while
R-square values (correlation coefficients) were used to deter-
mine the level of conformity between the experimental data
and the predicted values. Table 2 – Effect of time on pyrolysis of waste rubber tyres.
Time (h) Initial weight (g) Final weight (g) % of recovery
2.6. Adsorption isotherms
0.5 20.6885 11.1792 54.0358
Adsorption is mainly described through isotherms, i.e. the 1 20.2956 8.0959 39.8884
2 20.7431 8.6383 41.6442
amount of adsorbate on the surface of the adsorbent as a
3 20.6584 7.9864 38.6593
function of pressure for gases or concentration of liquids at
4 20.6175 8.0348 38.9707
isothermal conditions. Comparison of different materials can 5 20.2755 8.3479 41.1724
then be carried out based on the quantity adsorbed to the mass
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19 13

Fig. 2 – Effect of pyrolysis time on the % recovery of carbon

Fig. 4 – TGA and DSC curves of the synthesized AC from
black derived from used tyres.
rubber tyres.

Table 3 – Effect of activation temperature on the adhering organic impurities and 4 M HNO3 at 90 ◦ C for the
development of activated carbon. enhancement of surface functionalities. The surface area that
Temperature (◦ C) Initial Final % of recovery was measurded of the sample after the chemical treatment
weight (g) weight (g) was 493 m2 /g.

400 21.1291 8.4319 39.9066

500 20.2755 8.3479 41.1724 3.2. Characterization
600 19.8128 7.2219 36.4507
700 22.0971 7.9013 35.7572 3.2.1. TGA, DSC and FTIR
800 27.9802 8.5092 30.4115 The TGA and DSC analysis curves are given in Fig. 4 to under-
900 29.6855 8.0756 27.2039
stand the optimum temperature for pyrolysis, and the pattern
of decomposition the functional groups on the surface of the
AC employs. It can be clearly seen that there is around 8%
the pyrolysis temperature was kept constant at 500 ◦ C. It can weight loss between 20 ◦ C and 80 ◦ C signifying the desorption
be observed that though treatment for 30 min gave the high- absorbed water (Chang et al., 2013). The 10% weight loss was
est percent recovery, the time was not enough for effective recorded between 150 ◦ C and 450 ◦ C and this is due to CO2
conversion and some organic matter were not converted to desorption representing the decomposition of carboxyl, lac-
elemental carbon. By increasing the time from 1 to 5 h, the tone and lactol groups. The 80% weight loss was recorded
yield did not change significantly. However, we have selected between 450 ◦ C and 620 ◦ C signifying CO desorption corre-
the carbon produced after 5 h to ensure effective pyrolysis, and sponding to decomposition of carbonyl, ether, quinine and
to create more pores on the surface of the activated carbon. phenol groups on the carbon surface at higher temperatures.
The result of the physical activation carried out on the The result means that more CO was released from the decom-
pyrolyzed waste rubber tyre is shown in Table 3 and Fig. 3. position process signifying the relative abundance of carbonyl
The purpose of physical activation is to enhance porosity and and phenolic groups on the surface of synthesized AC. It can
surface area. The time was fixed for 5 h while the activation also be seen that AC completely decomposed after 600 ◦ C and
temperature was varied. Fig. 3 shows a continued reduction this may be due to the high temperature used during pyrolysis
in the percent recovery of the activated carbons. The surface and activation processes.
areas of the char prepared at different pyrolysis temperatures, The FTIR spectrum of the activated carbon obtained by
400, 500, 600, 700, 800 and 900 ◦ C were 164, 188, 247, 328, 355, pyrolysis at 500 ◦ C for 5 h and treatment with 4 M nitric acid
and 362 m2 /g respectively. Therefore, the activated carbon pro- for 3 h, showed bands at; around 3430 cm−1 which can be
duced by activation at 900 ◦ C was selected for the subsequent ascribed to O H stretching vibrations, 1720 cm−1 ascribed to
experiments, since it has the highest surface area. The acti- carboxyl groups, and 1640 cm−1 ascribed to carbonyl groups
vated carbon was treated further with H2 O2 to oxidize the (Paul Chen and Wu, 2004; Saleh, 2015a,b). The spectrum con-
firms the presence of the functional groups on the surface of
the AC.

3.2.2. BET surface area and porosity studies

Fig. 3 – Effect of activation temperature on the
enhancement of surface porosity of AC derived from used
tyres.
Nitrogen adsorption desorption isotherm is a useful tool in
the characterization of amorphous materials. The nitrogen
adsorption isotherms of the synthesized AC sample are shown
in Fig. 5. The sample expresses Type IV isotherm according
to Gregg and Sing (1982). A hysterias loop can be observed
at the relatively high pressure (0.8–1) indicating the presence
of mesopores. In addition, a minor uptake of nitrogen can be
observed at relative pressures between 0 and 0.2 signifying the
presence of a few micropores within the samples. The average
surface area (the average surface area is used to ensure the
reproducibility of the BET measurements) is summarized in
Table 4. It can be clearly seen that the sample has an average
14 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19

Fig. 6 – XRD pattern of AC synthesized from waste rubber

tyres.

has a distinct pattern upon which it diffracts X-ray light. Fig. 6

Fig. 5 – Nitrogen adsorption desorption isotherm and pore shows the XRD pattern of AC sample. The sample showed a
size distribution of AC synthesized from rubber tyres. broad diffraction peak at 2 values of between 20 to 30◦ (0 0 2)
and 40 to 50◦ (1 0 0) signifying the presence of graphical carbon
Table 4 – Surface area and pore volume analysis of with the amorphous carbon (Xiaojun et al., 2014). The inten-
prepared activated carbon. sity, on the other hand, gives an account of the carbon and
Measurement BET surface Pore volume Pore size oxygen containing functional groups present in the sample.
area (m2 /g) (cm3 /g) (Å) The summary of the XRD parameters of the adsorbent is given
in Table 5, it can be clearly seen that the crystalline thickness
1 509 0.79 67.51
(LC ) at d002 plane is very small (1.046) and the degree of graphi-
2 473 0.76 60.22
3 497 0.77 64.08 tization (−1.488) is high signifying the presence of carbon at
high concentration in the adsorbent.
Average 493 0.77 63.94

3.3. Adsorptive desulfurization efficiency

The effect of the related parameters was optimized and the

surface area of 493 m2 /g and pore volume of 0.77 cm3 /g and a
pore size of 6.394 nm.
3.2.3. XRD
XRD is a useful characterization tool for the elucidation of the
elemental composition of a sample. Each atom of an element
Pareto chart of these experimental factors was obtained. The
significance of the Pareto plot (Fig. 7) is that it gives a sum-
mary of the whole factors that affect a particular experiment.
The bars that exceed the red line in the plot are said to be
of significant effect (higher than other parameters) in the
experiment and they should be taken into account with much

Table 5 – XRD parameters of AC synthesized from waste rubber tyres.

Plane 2 (◦ ) d (nm) FWHM (rad) A (nm) Lc (nm) g (%)

002 24.94 0.3568 0.1342 0.7136 1.046 −1.488

100 43.68 0.2071 0.1352 0.2071 1.091 15.91

Fig. 7 – Pareto chart for the removal of DBT obtained from Minitab software.
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19 15

in depth attention. The results obtained in this experiment

showed that dosage (D) had the highest effect on the percent-
age removal of the DBT followed by the interaction of column
length and dosage (CD) followed by column length (C) alone
and concentration (A) of DBT used in the experiment. The
other bars below the red line are presumed to be less signifi-
cant on the experimental results. The result indicates that the
parameters such as contact time showed no significant effect
due to a rapid adsorption process. The result can be explained
according to Lewis acid–base theory, DBT molecules are Lewis
base, which is easily adsorbed at Lewis acid sites on the surface
of the activated carbon.

3.4. Adsorption kinetics

In order to understand the adsorption process, the com-

monly used kinetic models including the pseudo-first order
model, the pseudo-second order model, and the intraparti-
cle diffusion model were examined to best describe the sulfur
adsorption kinetics of the new developments adsorbents.

3.4.1. Pseudo first order model

Pseudo first order kinetic model is used to describe the ini-
tial stages of the adsorption process, whereas pseudo second
order models give the description of the whole adsorption
process and overall adsorption capacity. Pseudo-first-order
equation was first given by Lagergren (1898). The equation is Fig. 8 – Langmuir (a) and Freundlich (b) isotherms plots for
as follows:ln(qe − qt ) = ln qe − k1 twhere qe (mg/g) and qt (mg/g) adsorption of DBT on the prepared activated carbon.
are the amounts of analyte adsorbed at equilibrium and time
t (min), respectively; and k1 (min−1 ) is the rate constant of
the Lagergren-first-order kinetics model. The k1 and qe were
the equation given by (McKay and Ho, 1999). The equation is
calculated from the slope and intercept of the plot ln (qe − qt )
given as:
versus t, respectively. The correlation coefficients for DBT in
the first order kinetic model were calculated to be R2 of 0.994.
In addition, the calculated qe values were not in accordance t 1 t
= +
with the experimental qe . It can, therefore, be concluded that
qt k2 q2e qe
the adsorption process does not obey the pseudo first order
kinetics. where qt is the amount of DBT (mg/g) at a time (min) and k2
(g/(mg min)) is the adsorption rate constant of pseudo-second-
order adsorption. The slope and intercept of the linear plots
3.4.2. Pseudo second order model of t/qt against t yield the values of 1/qe and 1/k2 q2e . The qe and
The pseudo second order model is based on the assumption k2 can be obtained from the slope and intercept. The exper-
that the rate limiting step of a reaction may be chemisorption imental maximum amount adsorbed is in agreement with
which involves valence forces by sharing or electron exchange calculated qe values of DBT using the second order kinetic
between the adsorbent and the adsorbate (Wang and Wang, model. The correlation R2 is close to the unity indicated that
2008). The pseudo second order kinetics can be expressed by the process follows the model.

Table 6 – Adsorption capacity of DBT on different adsorbents.

Adsorbent Sulfur compound Adsorption capacity (mg/g) References

Alumina DBT 21.0 Srivastav and Srivastava (2009)

Commercial granulated AC treated with DBT 47.1 Yang et al. (2007)
steam at 900 ◦ C then washed by H2 SO4
Activated carbon fiber thermally treated DBT 14.0 Moosavi
Activated carbon fiber thermally treated DBT 19.0 et al.
and modified with copper cation (2012)
Iron oxide coated with silicon oxide DBT 63.3 Li et al. (2012)
nanoparticles coated with molecularly
imprinted polymer (Fe3 O4 @-SiO2 @MIPs)
Nanocrystalline NaY zeolite DBT 1.7 Tang et al. (2011)
Activated carbon prepared in this work DBT 8.6 This work
16 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19
Fig. 9 – SEM mapping image (a) and corresponding EDX
spectrum (b) of activated carbon before the adsorptive
desulfurization.
3.4.3. Intraparticle diffusion
The kinetic experimental results were also fitted to the
Weber’s intraparticle diffusion mechanism to gain insight,
understanding the mechanisms and rate controlling steps
affecting the adsorption kinetics (Weber and Morris, 1963). The
kinetic results were analyzed by the intraparticle diffusion
model to elucidate the diffusion mechanism. The following
equation was applied:
qt = kid t1/2 + C
where C is the intercept (mg/g) which is related to the bound-
ary layer thickness and kid is the slope which represents the
intraparticle diffusion rate constant (mg/g h1/2), which can be
calculated from the slope of the linear plot of qt versus t1/2 . The
correlation coefficient (R2 ) and intercept of DBT indicate the
greatest contribution of the surface sorption is the rate con-
trolling step in DBT adsorption. If the regression of qt versus
t1/2 is linear and passes through the origin, then intraparti-
cle diffusion is the sole rate-limiting step. However, the linear
plots at each dosage did not pass through the origin. The result
indicates that the intraparticle diffusion was not the only rate
controlling step (Hameed et al., 2008).
3.4.4. The mechanism
The adsorptive desulfurization of DBT on activated carbon was
found to be rapid at the initial period and then to become slow
and stagnate with the increase in contact time. The mecha-
nism for the DBT adsorption may be assumed to involve the
following steps (Kannan and Karuppasamy, 1998). The first
Fig. 10 – SEM mapping image (a) and corresponding EDX
spectrum (b) of activated carbon after the adsorptive
desulfurization of DBT.
step is the migration of DBT molecules from the bulk of the
solution to the surface of the activated carbon. The second
step is the diffusion of DBT through the boundary layer to the
surface of the adsorbent. The third step is the adsorption of
DBT at an active site on the surface of activated carbon. The
fourth is the intra-particle diffusion of DBT into the interior
pores of the adsorbent.
The boundary layer resistance is affected by the rate of
adsorption and increase in contact time, which reduces the
resistance and increases the mobility of DBT during adsorp-
tion. Since the uptake of DBT at the active sites of the
adsorbent is a rapid process; the rate of adsorption could be
governed by liquid phase mass transfer rate or intra-particle
mass transfer rate (Kannan and Karuppasamy, 1998).
3.5. Adsorption isotherms
Equilibrium study of adsorption provides information on the
capacity of the adsorbent. An adsorption isotherm is charac-
terized by certain constant values, which express the surface
properties and affinity of the adsorbent and can also be used
to compare the adsorptive capacities of the adsorbent for
different pollutants. Equilibrium data can be analyzed using
commonly known adsorption systems. Several mathematical
models can be used to describe experimental data of adsorp-
tion isotherms. The Freundlich and Langmuir models were
employed for the analysis of adsorption that occurred in the
experiment.
 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19
Fig. 11 – SEM map line of activated carbon after the adsorptive desulfurization.
3.5.1. Langmuir isotherm
This is the most common model used to quantify the amount
of adsorbate on the surface of the adsorbent as a function of
partial pressure or concentration at a given temperature. It
describes quantitatively the formation of a monolayer adsor-
bate on the outer surface of the adsorbent and no further
adsorption takes place after the monolayer formation. The
Langmuir isotherm is valid for monolayer adsorption onto
a surface containing a finite number of identified sites. The
model assumes uniform energies of adsorption onto the sur-
face and no transmigration of the adsorbate in the plane of the
surface. The Langmuir equation that governs the adsorption
of DBT is given as:
Ce 1 Ce
= +
qe KL qm qm
where qe (mg/g) is the amount adsorbed at equilibrium con-
centration Ce (mg/L), qm (mg/g) is the Langmuir constant
representing maximum monolayer capacity and KL is the
Langmuir constant related to the energy of adsorption. The
slope and intercept of linear plots of Ce /qe against Ce yield the
values of 1/qm and 1/KL qm .
The adsorption capacity qm for DBT on AC is showed in
Fig. 8. The dimensionless constant separation factor RL is
17
considered an integral part of Langmuir isotherm. The equa-
tion is given below:
1
RL =
1 + KL C0
where C0 = is the initial concentration of the analytes (mg/L),
and KL (L/mg) is Langmuir constant. The shape of the isotherm
can better be represented by RL value where RL > 1 indicates an
unfavorable process, RL = 1 indicates linearity and RL < 1 but
>0 indicates a favorable process. The results obtained from
Fig. 8 shows n = 0.2 indicating the adsorption of DBT on the
adsorbent is a favorable process.
3.5.2. Freundlich isotherm
Freundlich isotherm is an empirical equation employed
to describe heterogeneous systems or multilayer sorption
(Freundlich, 1906). The Freundlich isotherm can be expressed
by the following equation:
1/n 1
qe = KF Ce → ln qe = ln KF + ln Ce
n
where qe (mg/g) is the amount of absorbed material on
absorbent surfaces, KF and n are Freundlich constants with
KF (mg/g) is the adsorption capacity of the sorbent and n giv-
ing an indication of how favorable the adsorption process.
The magnitude of the exponent, 1/n (g/L), gives an indica-
tion of the variability of adsorption. Values of n > 1 represent
18 Process Safety and Environmental Protection 1 0 2 ( 2 0 1 6 ) 9–19

carbonization temperature and timing were varied from 250

Table 7 – EDX elemental analysis of the prepared carbon
before the adsorptive desulfurization. to 550 ◦ C for 0.5–5 h, respectively, and the optimum carboniza-
tion temperature for the production of carbon black was found
Element Apparent k ratio wt% wt % sigma
to be 500 ◦ C for 5 h. The carbon black produced was activated
concentration
further at a temperature range between 400 and 900 ◦ C and
C 42.25 0.42252 83.52 1.48 treated with HNO3 for the enhancement of surface function-
O 4.38 0.01473 16.48 1.48 alities responsible for adsorption of most compounds. The
Total 100.00 FT-IR and TGA results revealed that phenols, lactones and car-
boxylic acids were the major functional groups found on the
surface of the prepared AC. The nitrogen adsorption desorp-
Table 8 – EDX elemental analysis of the prepared carbon tion isotherm of the adsorbent revealed type IV isotherm
after the adsorptive desulfurization. possessing mesopores and micropores structures and the BET
Element Apparent k ratio wt% wt % sigma
surface area was 493 m2 /g. The Pareto chart revealed that the
concentration dosage of the adsorbent, column length and concentration
of the sulfur compound is the significant factors affecting
C 30.96 0 83.38 1.71
the adsorption. Electrons in the benzene ring of dibenzoth-
.30961
iophene are said to interact with the surface of the AC by
O 3.56 0 15.29 1.71 pi-electrons interaction aiding in a much better adsorption
.01197 efficiency. Pseudo second order kinetic model and Freundlich
isotherm fit the experimental data. The outcomes support the
S 1.16 0 1.32 0.24 feasibility of preparing high quality activated carbon as low
.01001 cost-materials from rubber tyres by physical and chemical
activation for the adsorptive desulfurization.
Total 100.00
Acknowledgement
favorable adsorption condition (Poots et al., 1978). To deter-
mine the constants KF and n, the linear form of the equation The authors would like to acknowledge the support provided
may be used to produce a graph of ln (qe ) against ln (Ce ). Values by King Abdulaziz City for Science and Technology (KACST)
of KF and n are calculated from the intercept and slope of the through the Science & Technology Unit at King Fahd Univer-
plot. sity of Petroleum & Minerals (KFUPM) for funding this work
Results in Fig. 8 showed the value of n is more than one, through project No. 13-PET393-04 as part of the National Sci-
which means that it is a favorable adsorption process. The ence, Technology and Innovation Plan.
adsorption capacity of the AC toward DBT is high. The compar-
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