Mechanistic and Adsorption Equilibrium Studies of

Dibenzothiophene-Rich-Diesel on MnO2-Loaded-
Activated Carbon: Surface Characterization
Mohammad A. Al-Ghouti,a Yahya S. Al-Degs,b Ayman A. Issa,b Ramia Z. Al Bakain,c and
Majeda A. Khraishehd
a
Department of Biological and Environmental Sciences, College of Arts and Sciences, Qatar University, P.O. Box: 2713, State of
Qatar, Qatar; mohammad.alghouti@qu.edu.qa (for correspondence)
b
Chemistry Department, The Hashemite University, P.O. Box 150459, Zarqa 13115, Jordan
c
Department of Chemistry, Faculty of Science, The University of Jordan, Amman 11942, Jordan
d
Department of Chemical Engineering, College of Engineering, Qatar University, P.O. Box: 2713, State of Qatar, Qatar
Published online 19 January 2017 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.12539

In this work, the preparation and characterization of
MnO2-modified-activated carbon for selective removal of
organosulfur compounds including dibenzothiophene were
outlined. The deposited particles of the modifier were
entrapped within the micropores and the resulting adsorbent
was efficient to desulfurize in diesel with rich-sulfur (7055
mgS kg21). Removal of organosulfur compounds was posi-
tively correlated with the deposited MnO2 and the best
efficiency was observed at surface loading 30.6%Mn. The
comprehensive characterization tests indicated drastic
changes in the physicochemical properties of the modified
adsorbents. The main findings were: (a) particles of a-MnO2
were accumulated within the microspores and (b) less acidic
surface compared to activated carbon was created in all
modifications. Scanning electron microscope pictures indi-
cated the filling of the pores by particles of MnO2. The mech-
anisms of S-compounds removal by the modified adsorbent
were elucidated with the aid of Infrared spectral analysis.
Adsorption isotherms of dibenzothiophene were measured
and the data were presented by different models. Dubinin-
Radushkevich model confirmed that adsorption of dibenzo-
thiophene was exothermic and both Jovanovic and Langmuir
models indicated the homogeneity of the modified surface.
Jovanovic model gave the best prediction of the maximum
adsorption capacity. Combustion qualities of deeply desulfurized
diesel were found within the regulated limits. V C 2017 American
Institute of Chemical Engineers Environ Prog, 36: 903913, 2017
Keywords: activated carbon, adsorption isotherm, surface
characterization, dibenzothiophene, diesel, MnO2
INTRODUCTION
The level of sulfur in liquid fuel (expressed as ppmw S or
mgS kg21) is an important property which is dependent on
the origin of crude oil. A quick examination of the levels of
sulfur in crude oils taken from several regions in the world
Additional Supporting Information may be found in the online ver-
sion of this article.
C 2017 American Institute of Chemical Engineers
V Concentrated 6.0 mol L21 NaOH solution was prepared
showed that the Middle East oil has a high sulfur level with
a value of 1.71% [13]. In Jordan, diesel is rich with organo-
sulfur compounds (OSCs). The maximum level was 1.2 wt %
(12,000 mgS kg21) and reported in 2010 [4]. The authors
showed that 40% of OSCs were originated from dibenzothio-
phenes (DBT) [4, 5]. DBT and other derivatives including
4,6-dimethyldibenzothiophene are often making more than
50% of sulfur in diesel [6]. Adsorption was proved to be an
efficient method for selective removal of dibenzothiophene
and other derivatives from liquid fuel [712]. Both equilibri-
um and kinetics of dibenzothiophene adsorption were inves-
tigated in the literature [1019]. A full review about the
conventional and upcoming sulfur-cleaning technologies for
petroleum fuel is described in reference 2.
The preparation of MnO2-modiofied-activated carbon
(AC) as a selective adsorber for OSCs and particularly for
DBT was investigated in this work. Removal of OSC, DBT,
paraffins, aromatic hydrocarbons was also studied as a func-
tion of the mass of MnO2 by the porous AC. The prepared
adsorbents were characterized by conducting different physi-
cal and chemical standard tests. The effects of mass, particle
diameter, and temperature on the OSCs removal were
addressed using principal component analysis. Desulfuriza-
tion efficiency of MnO2-AC was assessed by monitoring the
net reduction of total sulfur level and DBT in commercial
diesel. The mechanism of DBT adsorption from complex die-
sel was studied by applying various adsorption models.
Assessment of the combustion quality of deeply desulfurized
diesel was also investigated.
EXPERIMENTAL PROCEDURES AND METHODS
Reagents and Solutions
Commercial AC was purchased from Gainland Chemical
Company (UK). All reagents were supplied from BDH chem-
icals (BDH Chemicals, UK). Double distilled water was used
to prepare solutions and washing of adsorbents. Standard
MnCl2 solutions (1.0, 2.0, 3.0, 4.0, and 5.0 mol L21) that used
in modification were prepared from pure MnCl2.2H2O.

Environmental Progress & Sustainable Energy (Vol.36, No.3) DOI 10.1002/ep May 2017 903
from NaOH pellets and then standardized against 0.10
mol L21 HCl.
Conditioning and Surface Modification of AC
A 300 g AC was crushed and sieved into different particle
sizes:150300, 300500, and 500850lm using a standard
sieving system. Deposition of MnO2 on AC was outlined
elsewhere [19] and a short summary is provided herein. 15.0
gram of AC was soaked in 200 cm3 6.0 M sodium hydroxide
solution at 908C for 2 h at 258C. Carbon particles were
removed by filtration and then soaked in 100 cm3 manga-
nese chloride solution of certain concentration for 3 h at
258C. The amount of deposited MnO2 was dependent on the
concentration of manganese chloride solution [19]. Five mod-
ified adsorbents were prepared using the following manga-
nese concentrations 1.0, 2.0, 3.0, 4.0, and 5.0 M. The excess
manganese solution was removed and the manganese-
soaked carbon particles was added to 6.0 M sodium hydrox-
ide solution at 258C for 2 h to generate Mn(OH)2 on and
within the particles. Finally, carbon particles were removed
by filtration and exposed to flow of air for 24 h to facilitate
conversion of manganese hydroxide to manganese dioxide
MnO2. Finally, the adsorbent was washed several times with
distilled water, dried, and stored in closed bottle. The modi-
fied adsorbents were referred to as Mn-AC1, Mn-AC2, Mn-
AC3, Mn-AC4, and Mn-AC5; respectively, where the numbers
indicate the concentration of manganese chloride used in the
experiment. For example, Mn-AC1 indicates that 1.0 M man-
ganese chloride solution was used in the experiment. The
above procedure was repeated for different-sizes AC. As a
control sample, MnO2 was prepared using 4.0 mol L21
MnCl2 in the absence of AC.
Adsorptive Desulfurization Tests and Assessment of
Deeply Desulfurized Diesel
The overall efficiency of desulfurization process was
assessed by monitoring the reduction of total sulfur as fol-
lowing. The test was carried out by agitating 20.0 cm3 diesel
(density 835 kg m23 at 258C) with a fixed amount of adsor-
bent using a temperature-controlled shaker (GFL, Germany).
Agitation rate and time were 125 rpm and 24 h, respectively.
In fact, equilibrium time was estimated from earlier kinetic
tests [7, 19]. At the end of agitation, the adsorbent was
removed and the remaining S level was quantified using X-
ray fluorescence analyser (SLFA-2100/2800 X-ray Fluores-
cence Sulfur-in-Oil Analyser, Horiba). Influences of particle
diameter, temperature, and dosage of adsorbent on OSC
adsorption from diesel were examined. Surface concentration
of OSC (qe) was estimated as [12, 19]:
C0 2Ce m1
qe 5 (1)
m2
where C0, Ce, m1, and m2 are the initial OSC concentration
(mgS kg21), equilibrium OSC concentration (mgS kg21),
mass of diesel (g), and mass of carbon (g), respectively.
Adsorption of paraffins, mono-aromatic hydrocarbons, di-
aromatic hydrocarbons, and DBT was also studied. Quantifi-
cation of DBT was carried out using gas chromatograph cou-
pled with flame ionization detector FID (Hewlett Packard,
HP 6890 Series GCSystem) [12]. Paraffins, mono-aromatic,
and di-aromatic hydrocarbons were analyzed using GC
according to IP391-01 method [12]. Surface concentrations of
the earlier compounds were estimated by Eq. 1.
To assess the influence of desulfurization on the final
quality of diesel, a three-step desulfurization process was
conducted as following. 80.0 g of Mn-AC5 was added to
850 cm3 diesel and the mixture was mechanically stirred for
300 min. The exhausted adsorbent was separated and
replaced with another fresh one (80.0 g) and same
904 May 2017 Environmental Progress & Sustainable Energy (Vol.36, No.3) DOI 10.1002/ep
procedure was repeated one more time. The quality parame-
ters including density, cetane number (CN), flash point,
water content, kinematic viscosity, and higher heating value
(HHV) were tested as outlined in our previous work [4, 5].
Physicochemical Characterization of Adsorbents
The textural and chemical properties of AC, manganese
dioxide, and MnO2-loaded-AC were carried out by running
Boehms titrations and N2 adsorption tests as outlined in the
literature [12, 19, 20]. pHzpc (pH at zero point of change)
was estimated using pHdrift method [20]. In pH-drift meth-
od, 14 solutions (volume 100 cm3) were prepared in which
pH was varied from 1.0 to 14.0 over the solutions with 1.0
pH unit step. For each solution, 0.5 g adsorbent was added
and mixtures were agitated for 24 h. The solutions were fil-
tered and the final pH values were measured. pHzpc is the
point where the curve pHfinal versus pHinitial intersects the
line pHinitial 5 pHfinal [20]. The textural properties of adsorb-
ents including surface area, pore volume, and pore size dis-
tribution were determined using standard N2-adsorption
techniques (Nova 4200e, Surface Area and Pore Size Analy-
ser). The mineralogical composition and deposition of MnO2
on the surface or within the pores of activated were con-
firmed by running X-ray diffraction XRD analysis (Shimadzu
X-Ray Diffractometer XRD-6000, Japan).
The adsorbents were also characterized by electron
microscopy paired EDX detection for quantification of the
relevant elements using a FEI Quanta 200 FEG (Field Emis-
sion Gun) ESEM operated at 1520 kV and coupled to an
Oxford Inca 300 EDX system. The detection limit of EDX-
system was about 1 wt % and the penetration depth was
about 1 lm. The SEM of adsorbents was taken at different
magnification powers. FTIR spectra of adsorbents before and
after fuel desulfurization were recorded using a Shimadzu IR
Prestige-21/FTIR-8400S instrument with a resolution of
4.0 cm21 at 64 scans (Shimadzu, Japan). The measurements
were recorded over the range 4000400 cm21 and duplicate
spectra were obtained for each sample. IR spectra were
obtained for exhausted adsorbents after washing with petro-
leum ether and dried at 608C for 5 h.
RESULTS AND DISCUSSION
Level of Organosulfur Compounds in Commercial
Diesel
As indicated from GC analysis, commercial diesel is a
complex hydrocarbon mixture and many GC-peaks were
observed as shown in Figure 1A.
Chromatographic analysis indicated that paraffins, mono-
aromatic, and diaromatic hydrocarbons were making 61.7,
34.2, and 4.6% of diesel, respectively, and the reported
results agree with the known composition of petroleum die-
sel [21]. For diesel and desulfurized diesel (Figures 1A and
1B), separation of all components was accomplished within
17 min. The resolved peaks were attributed to paraffinic and
aromatic hydrocarbons in the matrix. Identification of all
OSC in diesel is a hard analytical task due to the lack of
standards in our laboratory. The most problematic OSC is
DBT, therefore, our GC analysis was limited to this com-
pound. Figure 1C indicates that the retention time of DBT is
7.26 min which is also observed in the GC-chromatogram of
commercial diesel (Figure 1A). The results indicated that
DBT is contributing to 35% of OSC in diesel. After deep
desulfurization using Mn-AC5, the peak of DBT (7.26 min)
was almost disappeared indicating the high selectivity of the
modified adsorbent toward this compound (Figure 1B). In
fact, it is also possible that the peak of DBT would be shifted
to 7.065 min as shown in Figure 1B. The calculations
revealed a 50% reduction in the peak intensity of DBT in
diesel which observed at 7.266 min (Figure 1A) compared to
Figure 1. Gas chromatograms of commercial diesel, diesel after desulfurization by Mn-AC5, and DBT. All chromatograms are
recorded at the same experimental conditions.

the one observed at 7.065. The earlier conclusion also con-
firmed the selective removal of DBT by MnO2-AC.
Characterization of AC on Surface Modification
The influence of surface modification on the selective
removal of OSC/DBT was carefully studied by monitoring
sulfur and non-sulfur compounds. The results of the tests
were presented in Figure 2 (XRD scans), Figure 3 (SEM), and
Table (1 and 2)-adsorption analysis).
The prepared MnO2 was identified by XRD analysis as
indicated in Figure 2. The XRD of MnO2 showed the
characteristics reflections of a-MnO2 at 2h of: 28 (the most
intense peak), 37, 43, 56, 59, 66, and 73, in agreement with
the reported results [22, 23]. The reflection planes of the
peaks were also provided in the XRD scan. Deposition of
MnO2 by AC was also confirmed by XRD pattern of Mn-AC5
with the peaks of 2h 5 28, 37, 43, 56, and 59 as indicated in
Mn-AC5 scan. As shown in Figure 2, the intensity of all peaks
was reduced and some peaks (43, 66, and 73) were disap-
peared and this was attributed to the lower content of the
deposited MnO2. Appearance, specific surface area, chemical
properties, and pHzpc of the deposited MnO2 were closed to

Environmental Progress & Sustainable Energy (Vol.36, No.3) DOI 10.1002/ep May 2017 905
those reported in the literature [24, 25]. It is interested to
note that no XRD evidence for AC and this may confirm the
amorphous nature of the used AC. The short peak appeared
around (2h) 20 may back to the crystals of AC, however, this
conclusion was not by the XRD instrument. The porous
nature of AC in confirmed by SEM, the porous nature of the
material is obvious in Figure 3A. Conversely, SEM picture
(taken at 3500X magnification power) of MnO2 (Figure 3B)
indicated the plate-like structures of a-MnO2 which is
Figure 2. XRD spectra of MnO2 and Mn-AC5.
Figure 3. SEM pictures of Activated carbon (A) manganese dioxide (B) and (C) MnO2-loaded-activated carbon (30.6Mn %).
906 May 2017 Environmental Progress & Sustainable Energy (Vol.36, No.3) DOI 10.1002/ep
already reported for this material [23]. Beside plate-like
shapes, needle-like crystal structure was also common for a-
MnO2. After MnO2 deposition on AC, pores of AC seems to
be filled by the particles of MnO2 as indicated in Figure 3C.
The existence of pores in Mn-AC5 (Figure 3C) is possible as
indicated from dark regions in the picture. In our view, the
formation of MnO2 was accomplished within the pores of
the AC. In terms of surface homogeneity, Mn-AC5 looks less
homogenous than MnO2 but more homogenous than AC.
The presence of developed porous structure of AC has end-
ed up with highly heterogeneous surface.
As indicated in Table 1, surface modification by MnO2 has
changed the intrinsic physical and chemical properties of the
substrate. Based on EDX analysis provided with SEM, both C
and Mn contents were monitored in prepared adsorbents.
The detection limit of EDX may reach down to 1% and this
acceptable taking the large contents of Mn and C in the
adsorbents. The amount of deposited Mn has increased from
7.4% in Mn-AC1 up to 30.9% in Mn-AC5. The amount of
loaded Mn is high and this was attributed to the high porosi-
ty of the AC. The reduction in micropore was consistent with
the loaded amounts of MnO2. At surface loading of 30.6%
Mn, the microporosity was significantly reduced (45% reduc-
tion compared to AC). However, the reduction in mesopore
volume was not correlated with deposited amounts of MnO2
(the results were not provided). Accordingly, the accumula-
tion of manages dioxide was in micropores and more tests
would be needed at this stage. Moreover, on surface modifi-
cation, micropore volume was reduced from 0.52 to 0.31 (for
Mn-AC5) and this contributed to 40% reduction in micropore
volume. The accumulation of MnO2 in mesopores (diameter
250 nm) is not possible as mesopore volume was not affect-
ed with loaded MnO2. The small reduction in Sex is attributed
to the deposition of MnO2 on the external surface of sub-
strate; however, the internal surface area was highly affected
on metal deposition. Average pore diameter of carbon was
slightly affected on modification and this is also attributed to

Figure 4. %Removal-Adsorption capacity plots for activated
carbon (A) and Mn-AC5 (B) as a function of mass of adsorbent.
internal deposition of MnO2 particles. pHzpc of AC was
reduced from 9.3 to 7.8 indicating the influence of MnO2 on
the chemical nature of AC. Although a large amount of Mn
was deposited on the surface, the modified adsorbent (Mn-
AC5) still has a basic character with a pHZPC of 7.8.
Desulfurization by Mn-Modified-AC: Selectivity Studies
and Adsorption Mechanisms
On surface modification, MnO2-loaded-adsorbents become
more selective for OSC compared to other diesel constituents.
Initially, adsorption performance of MnO2 for paraffins and
other organics was modest compared to AC and this was
attributed to the intense surface area, developed porosity, and
high density of functional groups of the later adsorbent. The
interesting part in adsorption tests was the favorable uptake of
OSC by MnO2 against other cyclic compounds. In fact, AC was
effective for removing OSC and other cyclic compounds and
this reflecting the poor selectivity of the adsorbent toward
OSC. Deposition of MnO2 by the substrate had created new
active sites that are more selective for OSC as confirmed in
Table 1. As shown in Table 1, adsorption of OSC was positive-
ly correlated with the amount of deposited Mn, while a reverse
trend is observed for di-aromatic hydrocarbons. Surface modifi-
cation by 30.6% Mn was created a selective surface for OSC
with adsorption capacity of 14.3 mgS g21. At higher loadings
(>24.5 Mn %), a drastic reduction in non-S-compounds remov-
al was reported which indicated the weak interactions of the
earlier organics with MnO2. Before MnO2 deposition, adsorp-
tion trend of diesel constituents were decreasing in the follow-
ing manner: paraffins > mono-aromatic > di-aromatic > OSC.
Environmental Progress & Sustainable Energy (Vol.36, No.3) DOI 10.1002/ep
However, loading AC 30.6% Mn (i.e., Mn-AC5), OSC was favor-
ably removed over other constituents. The main conclusion
from the earlier observations was deposition of MnO2 has cre-
ated a selective adsorber for OSC, and more importantly,
removal of other constituents became insignificant. It is impor-
tant to mention that selective removal of DBT from complex
diesel matrix will be in the following sections.
Running FTIR spectra of AC and MnO2-loaded-AC (before
and after desulfurization) was useful for identifying surface func-
tional groups, identifying the adsorbed constituents, and elucida-
tion the mechanism of interaction. FTIR measurements were
used to elucidate adsorbateadsorbent interactions in many
adsorption studies [12, 14]. It was noticed that the FTIR spectra
for the AC, Mn-AC5, and OSC-Mn-AC5 were almost similar to
the FTIR spectra obtained for the AC and MnAC loaded with
OSCs in our pervious study [7]. The main characteristic bands
for AC, Mn-AC5, and OSC-Mn-AC5 are summarized in Table 2.
In fact, the peaks appeared at 2850 and 2900 cm21 were
also characteristics bands for CAH bond in alkanes. Howev-
er, adsorption of alkanes was highly reduced after MnO2
deposition on the surface (see Table 1), and hence, the earli-
er bands were attributed only to SAC bond. Accordingly, the
detected FTIR bands were mainly attributed to S-compounds
which adsorbed in higher amounts. The participation of
MnO2 in OSC removal was deduced from the disappearance
of 520 cm21 band after desulfurization which also reported
in our previous research [7]. In the previous study, the main
FTIR bands that reported for Mn-loaded-AC (7.3% Mn) were
1460, 1650, 2400, 2900, and 3400 cm21 which also confirmed
the deposition on MnO2 on the surface of AC [7].
Influence of Experimental Factors on OSC Adsorption
Assessment of desulfurization efficiency of AC and Mn-
AC5 was studied by monitoring OSC and DBT in two differ-
ent tests. Adsorption of OSC was treated as single-solute-
adsorption system assuming comparable adsorption rates of
all organosulfur compounds. This convention is hold true as
reported in the literature [6, 14]. The overall performance of
AC and Mn-AC5 toward OSC was evaluated by running prin-
cipal component analysis and generating Type-I plot.
Adsorption values of OSC at different experimental parame-
ters are shown in Table 3.
The combined influence of all experimental factors on OSC
removal was characterized by running principal component
analysis PCA. By conducting 11 adsorption tests, influence of
mass, temperature, and particle diameter on OSC adsorption
by both adsorbents was investigated. From the provided data
in Table 3, a matrix of dimension 11 3 3 (containing experi-
mental levels) and a response vector 11 3 1 (containing
adsorption capacities mgS g21) were generated. PCA analysis
was repeated for each adsorbent. PCA analysis was carried out
by estimating scores and loadings of the original experimental
matrix and then used these scores and loadings to find the
best correlation with the response vector (or S-adsorption
capacities in this work). PCA analysis was carried out for the
current adsorption systems at outlined in the literature [28].
The following equations were obtained which described OSC
adsorption under the studied experimental variables:
For AC:
OSC mgS kg21 5 2:66 Mass 2 0:05 PD 2 1:22 Temp
(r2 5 0.9752; PRESS 5 13.6) (2)
For Mn-AC5:
OSC mgS kg21 53:86 Mass 0:07 PD1:28 Temp (3)
(r2 5 0.9806; PRESS 5 8.4)
where r2 and PRESS are correlation coefficient between actu-
al and predicted adsorption capacities and prediction error
May 2017 907
Table 1. Physicochemical and adsorption properties of AC, MnO2, and MnO2-loaded AC.
Physical properties
21
Adsorbent* 2
SBET (m g ) Sexternal (m2 g21) Vtotal (cm3 g21) Vmic (cm3 g21) APD** (nm)
AC 985 135 0.52 0.48 2.1
MnO2 94 23 0.12 0.09 0.8
Mn-AC1 824 115 0.49 0.41 2.1
Mn-AC2 792 109 0.42 0.40 2.0
Mn-AC3 704 94 0.38 0.32 1.9
Mn-AC4 685 102 0.36 0.29 1.8
Mn-AC5 611 92 0.31 0.22 1.7
Chemical properties
21
Acidity (mmol g ) Basicity (mmol g21) pHZPC Mn (wt %) C (wt %)
AC 0.57 0.83 9.3 86.5
MnO2 0.15 0.10 5.4
Mn-AC1 0.56 0.79 9.0 7.4 76.3
Mn-AC2 0.51 0.71 8.6 12.4 71.0
Mn-AC3 0.48 0.65 8.1 19.6 65.2
Mn-AC4 0.41 0.59 8.0 24.5 59.4
Mn-AC5 0.38 0.51 7.8 30.6 56.8

Adsorption tests (mg g21)

Paraffins Mono-aromatic Di-aromatic OSC
AC 255.7 281.7 71.5 10.1
MnO2 <1 <1 <1 4.7
Mn-AC1 208.4 168.4 55.3 11.3
Mn-AC2 173.6 108.0 38.7 11.6
Mn-AC3 94.2 68.6 <1 12.8
Mn-AC4 48.7 <1 <1 14.1
Mn-AC5 <1 <1 <1 14.3

Note: Uncertainties (estimated as RSD) in the reported results (n53) are: acidity-basicity 60.03 mmol g21, Mn % 6 0.2 wt %, adsorp-
tion values: Paraffins 6 (7.015.0) mg g21, mono-aromatics 6(6.018.0) mg g21, di-aromatics 610.0 mg g21, OSC 60.1 mg g21.
*Mn-AC1 indicates that initial concentration MnCl2 used in modification is 1.0 M.
**Average pore diameter.

As obtained from EDX analysis (detection limit 1%).

Adsorption conditions: DBT 11,890 mg kg21 or 1.2 wt %, OSC 7055 mg kg21, Paraffins 61.7 wt %, mono-aromatics 34.2 wt
%, di-aromatics 4.6 wt %, dp 5 300500 mm, T 5 258C, 1.0 g, diesel 20 ml, and shaking time 1.0 day. Equation 1 was used to
find adsorption value (mg g21).

sum of squares which also measures the closeness between
actual and predicted adsorption capacities, respectively. Esti-
mation of PRESS is outlined in Supporting Information. The
coefficients in Eqs. 2 and 3 can indicate the significance of
studied factors on OSC removal from diesel. Factor of higher
coefficient had more influence on the removal process. The
results confirmed that mass of adsorbent (in both systems) is
the most significant on OSC removal compared to temperature
and particle diameter. PCA analysis also confirmed that mass
of adsorbent is more significant on OSC removal in Mn-AC5
compared to unmodified AC. The low coefficients obtained
for particle diameter indicated that changing particle diame-
ter of adsorbent over the tests had a small (and negative)
effect of OSC removal. Furthermore, changing temperature
(from 25.0 to 458C) over the tests had a negative influence on
OSC removal by both adsorbents. Modeling of adsorption
data by PCA was satisfactory as indicated from the magnitudes
of r2 and PRESS.
As confirmed by PCA, mass of adsorbent was the most sig-
nificant factor on OSC removal. In a previous study, Mn-
loaded-AC (loading of 7.3%) showed comparable removal
performance for S-compounds [7]. The previous study indicat-
ed a better adsorption after modification and adsorption value
decreased by increasing mass and particle diameter of the
adsorbent [7]. Moreover, approximately similar PC-coefficients
were obtained for mass, diameter, and temperature but the
temperature coefficient reported for the modified adsorbent in
this study was lower compared to the value reported in the
literature [7]. In Figure 4, the %removal-adsorption capacity
plots were presented as a function of mass.
As shown in Figures 4A and 4B, increasing mass (for both
adsorbentS) increased the %removal of OSC from diesel
while decreased the amount removed by adsorbent
(mgS g21). In another words, as the mass of adsorbent
increased, the %removal of OSC from diesel has increased
while adsorption capacity of OSC (mgS g21) has decreased.
The higher %removal of OSC from diesel was attributed to
the higher active sites available for adsorption. Conversely,
the reduction in adsorption value at higher masses is related
to way of expressing adsorption-value where amount of
OSC removed is divided by the mass. The crossing point in
Figure 4 represents a balance point between adsorption capac-
ity and the %removal for OSC removal [29]. As shown in Fig-
ures 4A and 4B, the crossing points were observed at about
1.5 and 1.8 g (per 100 cm3 diesel) for Mn-AC5 and AC, respec-
tively. The reported adsorption values were compared to those
seen in the literature. The results are shown in Table 4.
The following conclusions were drawn from Table 4: (a)
many adsorbents ranging from carbonaceous AC to inorganic
metal-loaded zeolite are potential adsorbers for OSC removal

908 May 2017 Environmental Progress & Sustainable Energy (Vol.36, No.3) DOI 10.1002/ep
Table 2. The main FTIR characteristic bands for AC, Mn-AC5, and OSC-Mn-AC5.

Characteristic bands Assignment Comment

For AC: (1100 & 1650) and
3450 cm21
For Mn-AC5: peak at 520 cm21
Mn-AC5 after desulfurization (i.e.,
OSC-Mn-AC5) sharp peaks over
the region 24003000 cm21.
New peaks appeared at 1460, 2850,
and 2900 cm21
Alcoholic and carboxylic acid functional
groups, respectively [26].
MnO bending vibration of [MnO6]
octahedral in a-MnO2 [27]
C-H stretching either in aliphatic or
aromatic compounds [26].
Stretching and bending vibrations of SAC
bond
It is highly possible that particles of MnO2
were interacted with both alcoholic and
carboxylic acid groups and this was
attributed to the band shift (about
50 cm21) in the earlier groups.
This may confirm the direct interaction of
S atom with the polar surface functional
groups

Table 3. Adsorption of OSC (mgS g21) at different experi-

mental factors.*

Factor AC Mn-AC5
Mass (g)**
0.5 8.5 11.8
1.0 10.1 14.3
1.5 9.5 10.7
2.0 8.4 9.6
2.5 7.7 8.2
Particle diameter (mm)
150300 15.8 19.7
300500 10.1 14.3
500850 9.1 11.2
Temp (8C)
25.0 10.1 14.3
35.0 9.3 12.7
45.0 8.7 9.3
Figure 5. BDT adsorption isotherms at 258C. (Lines: Jova-
novic model).
*The provided results are averaged of three trials (RSD 60.1
mg g21).
**OSC level 7055 mgS kg21, Diesel 20 mL, particle size 300 Supporting Information). In the current system, measurement
500 mm, temp 5 258C, and shaking time 24 h. of DBT isotherm was possible as the concentration of this

OSC level 7055 mgS kg21, Diesel 20 mL, Temp 258C, mass compound was easily quantified using gas chromatography as
1000mg, and shaking time 24 h. outlined earlier. Adsorption isotherms of DBT were measured

OSC level 7055 mgS kg21, Diesel 20 mL, particle size 300
500 mm, mass 1000 mg, and shaking time 24 h.
from diesel, (b) Mn-AC5 was selective for OSC removal from
S-rich fuel 7055 mgS kg21, (c) Ni and Cu modified-zeolite
showed the highest adsorption for OSC with a maximum
retention value of 300 mgS g21, and (d) MnO2-loaded-AC
(Mn-AC5) showed a promising adsorption affinity 20.5
mgS g21 and outperformed zeolite [5] and activated benton-
ite [33]. In a previous research [7], adsorption value of 19.6
mgS g21 was reported for MnO2-loaded AC (loading value of
7.3% Mn) and the main finding in the current research was
the better adsorption of S-compound at higher Mn loadings.
For more details on the adsorption capacity of most known
adsorbents, the readers would consult the work of Al-Degs
and coworkers [2]. The reported capacities in this work and
in the previous work [7] were high when compared with oth-
er adsorbents [2].
Adsorption of DBT from Commercial Diesel: Modeling
of Isotherms
Adsorption behavior of DBT from diesel was studied by
analyzing adsorption isotherms obtained in Type-II plot (see
at 258C and the results were presented using seven isotherms
to get a better insight on DBT removal process from complex
diesel matrix. The reported isotherms are shown in Figure 5
and the modeling results are summarized in Table 5.
As shown in Figure 5, L2-shape for isotherms were
obtained according to Giles and Smith classification for iso-
therms [36]. In L2 isotherm, surface concentration is steeply
increased at low DBT concentration and gradually increased
at the higher concentrations [36]. This indicated the high
binding affinity between the surface and DBT. Similar L2
shapes were reported for DBT adsorption by AC and natural
zeolite [14, 37]. In general, L2 type isotherms are associated
with ionic solute adsorption with weak-solvent-competition
[14, 37]. Accordingly, the polar DBT favorably adsorbs over
non-polar organic molecules. The parameters of the adopted
models with statistical indicators were given in Table 5. In
general, Langmuir was workable for modeling adsorption
behavior of DBT with acceptable PRESS and X2 values (see
Supporting Information for details on these parameters). The
maximum adsorption values (Qmax) furnished by Langmuir
model were accepted when compared to those depicted in
Figure 5 (for both adsorbents). In fact, Qmax values also con-
firmed the enhancement of DBT removal on surface modifi-
cation, 25.4 and 34.5 mgDBT g21 for AC and Mn-AC5,

Environmental Progress & Sustainable Energy (Vol.36, No.3) DOI 10.1002/ep May 2017 909
Table 4. Parameters of different isotherms for modeling DBT adsorption by activated carbon and Mn-AC5.
Adsorbent OSC (mgS kg21)
Na-zeolite 1800 (258C)
Ni-zeolite 1800 (258C)
Cu-zeolite 1800 (258C)
Ni-zeolite 150300
Cu-zeolite 150300
Modified Commercial AC 220
Prepared AC 10870 (238C)
Commercial AC 200
AC/8008C 200
Ni/AC 200
Activated Jordanian Bentonite 50010,000 (258C)
Natural Jordanian zeolite 50010,000 (258C)
Commercial AC 040 (508C)
Commercial AC 400
S-modified activated carbon 442.5 (308C)
Mn-modified-AC (7.3% Mn) 7055 (258C)
Commercial AC
Mn-modified-AC (26.8% Mn)
*The provided data were extracted from [7].
**Experimental conditions: OSC level 7055 mgS kg21, Diesel 20 ml, Temp 258C, mass 1000 mg, and shaking time 24 h.
respectively. Conversely, the values of KL (L mmol21) were
reflecting the high affinity of DBT to the solid medium. For
both adsorbents, KL values were higher than unity (90.2 for
AC and 133.6 for Mn-AC5); indicating the high affinity
toward the surface and particularly after surface modification.
Although Langmuir isotherm was workable for presenting
DBT, the need for checking up other isotherms is still neces-
sary at this stage.
As shown in Table 5, Freundlich model was not as effec-
tive as the earlier model for presenting DBT adsorption as
confirmed for the higher chi-square values (12.4 for AC and
13.8 for Mn-AC5). The workability of Langmuir model for
presenting DBT adsorption was attributed to the homoge-
nous distribution of active sites in the surfaces, as Langmuir
isotherm assumes homogenous active sites for adsorption
[38]. Although it is not highly applicable to the current sys-
tem, n values (i.e., the exponents in Freundlichs model)
indicated a favorable DBT uptake by both surfaces (n > 1).
With extremely high PRESS (117133) and X2 (59.468.9)
values, Harkin-Jura has a very limited application for present-
ing the DBT adsorption for both adsorbents. This conclusion
supported the fact that multilayer adsorption of DBT was not
achieved and adsorption proceeded with one molecular lay-
er. Similar situation was observed in Halseys model as the
model showed limited applicability for presenting DBT
adsorption. The reason behind the modest modeling in this
case is because it assumed a multilayer adsorption which
was not achieved herein. The magnitudes of PRESS and X2
were higher than the rest of the models (except Harkin-Jura)
which reflected its poor fitting to adsorption data.
As indicated in Table 5, Dubinin-Radushkevich model
provides better agreement with DBT adsorption data for
both adsorbents and hence outperformed Freundlich,
Harkin-Jura, and Halsey models. In fact the values of X2 for
Dubinin-Radushkevich model were acceptable; however,
Qmax values were not in agreement with experimental ones.
For example, the predicted Qmax of DBT adsorption by Mn-
AC5 was 58.4 mg g21 and this value is significantly higher
than the experimental value 30 mg g21 (Figure 5). In fact,
Langmuir model was more accurate in predicting Qmax for
DBT adsorption in both systems.
910 May 2017 Environmental Progress & Sustainable Energy (Vol.36, No.3) DOI 10.1002/ep
Adsorption value (mgS g21) Reference
54.0 30*
58.0 30*
63.1 30*
300.0 31*
300.0 31*
47.1 32
42.6 15
0.45 16
1.5 16
0.81 16
4.8 33
7.15 5
0.41 34
17.1 12
20.0 35
19.6 7
16.1** This work
20.5** This work
The energy parameter of Dubinin-Radushkevich model
BDR also confirmed the better affinity for DBT toward Mn-
AC5. Temkin isotherm, in fact, was found excellent for pre-
senting DBT adsorption as confirmed by X2 values (1.11.2).
Moreover, the variation in adsorption energy in the model
(i.e., b parameter) was positive for both adsorbents. The ear-
lier conclusion indicated that DBT adsorption is an exother-
mic process. The obtained adsorption energies of DBT were
22.34 and 53.24 kJ mol21 for AC and Mn-AC5, respectively.
Heat of DBT adsorption could be taken as the sum of three
energies as following: energy needed to break the intermo-
lecular forces between DBT and other constituents in diesel
(DHDBT-Diesel), energy needed to break the intermolecular
forces between DBT molecules (DHDBT-DBT), and the
released energy due to bond formation between DBT
and the surface (DHDBT-surface). Accordingly, DHprocess5
DHDBT-diesel 1 DHDBT-DBT 1 DHDBT-surface
The first two terms are positives (endothermic processes)
while the last one is negative (exothermic process). As the
whole process was exothermic (see above), then the last
term in the above relation (DHDBT-surface) was higher than
the term (DHDBT-diesel 1 DHDBT-DBT). In fact, the high energy
observed for DBT-Mn-AC5 (see parameters of Dubinin-
Radushkevich in Table 5) is attributed to the high (and nega-
tive) magnitude of DHDBT-surface due to surface modification.
As shown in Table 5, the lowest PRESS and X2 values
were observed for Jovanovic model. The high applicability
of Jovanovic model indicated that DBT adsorption was eluci-
dated by the localized monolayer approximation without lat-
eral interaction. In fact, Jovanovic model keeps the same
assumptions in Langmuir model in addition to the probability
of certain mechanical contacts between the adsorbing and
desorbing molecules. Jovanovic, Langmuir, and Temkin are
the best models (generated the lowest PRESS and X2) for
presenting DBT adsorption from diesel. The excellent perfor-
mance of Jovanovic and Langmuir models was ascribed to
the homogeneity of surface and the probability of some
mechanical contacts between adsorbate and desorbate mole-
cules due to the existence of polar SAC bond. It seems that
the homogeneity of the surfaces (AC and Mn-AC5) cannot
explain the excellent performance of Jovanovic and
Table 5. Adsorption capacity of selected adsorbents for OSC.

AC Mn-AC5
Model Parameters PRESS X2 Parameters PRESS X2
Langmuir Qmax 25.4 6.4 1.3 Qmax 34.5 7.1 1.4
KL 90.2 KL 133.6
Freundlich KF 1.2 12.4 8.2 KF 1.9 13.8 8.3
n 3.03 n 3.23
Harkin-Jura B 4.3 117 59.4 B 6.2 133 68.9
A 6231 A 7251
Halsey KH 0.01 88.3 38.3 KH 0.12 98.3 41.3
nH 21.8 nH 22.8
Dubinin-Radushkevich Qmax 36.3 8.6 2.1 Qs 58.4 7.4 2.4
BDR 155.3 BDR 233.4
Temkin KT 153 5.9 1.2 KT 242 5.1 1.1
b 22.34 b 53.24
Jovanovic Qmax 26.2 2.1 0.9 Qmax 31.1 3.0 1.0
KJ 88.9 KJ 136.2

Table 6. Influence of deep desulfurization on quality parameters of diesel.

Sulfur Water Kinematic

concentration Density HHV* Cetane Flash content viscosity
System (mg kg21) (kg m23) (MJ kg21) number point (8C) (mg kg21) (mm2 s21)
Diesel 7055 825 43.62 54 77 128 3.75
Treated Diesel 43.0 803 39.82 49 75 68 3.17
Analytical ASTM IP-190 Note* ASTM ASTM ASTM ASTM
Test D4294.03 D976.06 D 93.07 D6304.07 D445.09
Recommended 50 max 820 min Note* 51.0 min 55 min 200 max 2.0 min
limits** 845 max 4.5 max

*HHV was determined as outlined in the literature [21]. Typical HHV range for diesels 4044 MJ g21 [21].
**Obtained from EN 590 (UNE EN-590 2004) and ASTM (ASTM D 975-06).

Langmuir equations for presenting DBT adsorption. As
already known, both models assumes homogenous surface
but SEM indicated a high heterogeneity of AC compared to
Mn-AC5. This may explain why Freundlich is often applica-
ble for modeling adsorption behavior of many solutes by
porous AC [3638]. Jovanovic model gave the best prediction
of Qmax as the nearest to the experimental data compared to
the rest of models. Modeling of DBT adsorption isotherms
by Jovanovic model is depicted in Figure 5. In a previous
study, adsorption of OSC including DBT was investigated
and the results indicated a better presentation for adsorption
data by Langmuir and Freundlich models [7].
Regeneration and kinetic studies were reported in a previ-
ous research [19]. The results indicated a faster removal process
after deposition of MnO2 and 96% of the surface was occupied
within 30 min of interaction. Kinetic data were best presented
by reaction-based-models like second-order kinetic model
while diffusion-based-models showed limited applications [19].
MnO2-AC was satisfactorily regenerated using n-hexane at
658C.
Effect of Desulfurization on Quality Parameters of
Diesel
The important quality parameters of deeply desulfurized
diesel by Mn-AC5 were estimated using standard procedures.
Table 6 summarized the results along with the regulated lim-
its for comparison purposes.
In fact, the undertaken parameters were essential for
assessing combustion quality of diesel fuel. Density,
viscosity, CN, and HHV have immediate effect, while, sulfur,
water and flash point have a long term effect. Presence of
large amounts of OSC can end up with engine wearing and
unwanted consequences [12, 37]. The efficient desulfurization
procedure was demonstrated by the large reduction in S%
and this was achieved after three adsorption cycles using
fresh adsorbent in each one. The final S content is 43
mg kg21 and this level is acceptable according in many inter-
national standards [3941]. As indicated in Table 6, HHV
which is related to the fuel economy has been reduced by
9%. Moreover, density which is also related to fuel combus-
tion was also reduced. Even though HHV has been reduced
after treatment, the treated fuel still exhibited a reasonable
value and closed to those reported for commercial diesel
[40]. The reduction in HHV was attributed to the removal of
paraffins and other aromatics as discussed before. It is
important to mention that density of desulfurized fuel is not
within the international standards. CN (which measures com-
bustion quality of diesel inside engine) of desulfurized diesel
was within the regulated limits. Flash point is directly related
to diesel combustion and the optimum limit is 558C or more.
For desulfurized diesel, a flash point of 758C was obtained
which is acceptable. Transportation fuels free of water are
always recommended. After desulfurization, water content
was reduced from 128 to 68 mg kg21 and this was another
advantage of the proposed cleaning procedure. Fuel viscosity
in an important parameter to be investigated as it may affect:
(a) fuel spraying in the combustor, (b) fuel system lubrica-
tion, and (c) fuel leakage [40]. For most applications, the
optimum viscosity of diesel should be within 2.0

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