Fuel 237 (2019) 793–805

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Full Length Article

Ultra-fast and highly efficient catalytic oxidative desulfurization of T

dibenzothiophene at ambient temperature over low Mn loaded Co-Mo/
Al2O3 and Ni-Mo/Al2O3 catalysts using NaClO as oxidant
⁎
Sidra Subhana,b, Ata Ur Rahmana, Muhammad Yaseena,b, , Haroon Ur Rashidb,c,
⁎
Muhammad Ishaqa, Maria Sahibzadad, Zhangfa Tongb,
a
Institute of Chemical Sciences, University of Peshawar, 25120, KP, Pakistan
b
School of Chemistry and Chemical Engineering, Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, Guangxi University,
Nanning 530004, China
c
Department of Chemistry, Sarhad University of Science & Information Technology, Peshawar, Pakistan
d
Department of Chemistry, Umea University, Stockholm, Sweden

G R A P H I C A L A B S T R A C T

Ultra-fast Highly Efficient Oxidative Desulfurization of Dibenzothiophene at room Temperature over

Mn-Co-Mo/Al2O3 Catalyst using NaClO as Oxidant

A R T I C LE I N FO A B S T R A C T

Keywords: This study reports the ultra-fast and highly efficient oxidative desulfurization (ODS) of dibenzothiophene (DBT)
Oxidative desulfurization at room temperature over low Mn (0.5 wt%) incorporated Co-Mo/Al2O3 and Ni-Mo/Al2O3 catalysts using NaClO
Dibenzothiophene as oxidant. The effect of disparate operating parameters i.e. mode of catalyst preparation, DBT initial con-
Low Mn promoted catalyst centration, reaction time, temperature, catalyst and oxidant dose, oxidant type and reaction pH on oxidation
NaClO oxidant
process was investigated. Results revealed that remarkably high and ultra-fast A DBT conversion of 100% was
Textural characterization
achieved within 5 min utilizing 15 mL sample of 2000 ppm (347 ppm sulfur), 0.1 mL of 0.138 M NaClO (O/S-
6.6 mol/mol), 0.1 g Mn-Co-Mo/Al2O3 catalyst at pH 12, and 25 °C reaction temperature. A reaction mechanism
for the highly efficient ODS activity of Mn promoted catalysts accredited to the synergistic effect of Mn active
phase and high oxidizing power of NaClO was proposed. An overall ODS catalytic activity order of: Mn–Co–Mo/
Al2O3 > Mn–Ni–Mo/Al2O3 > Co–Mo/Al2O3 > Ni-Mo/Al2O3 > Mo/Al2O3 was observed. Discernment of the

⁎
Corresponding authors at: Institute of Chemical Sciences, University of Peshawar, 25120, KP, Pakistan.
E-mail addresses: myyousafzai@gmail.com (M. Yaseen), zftong@sina.com (Z. Tong).

https://doi.org/10.1016/j.fuel.2018.10.067
Received 5 May 2018; Received in revised form 15 August 2018; Accepted 10 October 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
S. Subhan et al.
surface morphology and textural properties of fresh and spent catalysts were characterized using Scanning
electron microscopy (SEM), X-ray diffraction (XRD), Energy dispersive X-Ray (EDX), and BET surface area
analysis which helped in evaluating the catalytic activity results. Due to ultra-fast and highly efficacious nature,
simple and safe mechanization, cost effectiveness, and operation at ambient reaction conditions, this study can
be envisaged as an effective approach for the ODS of fuel oils on industrial level.
1. Introduction
Presence of sulfur compounds in fuel oil is highly obnoxious due to
their detrimental impacts on environment, and threat to the quality of
petroleum products by decreasing API gravity, poisoning catalysts,
corroding internal combustion engines, producing black exhaust gases,
and SOx [1]. To cope with these issues, increasingly stringent emission
control standards have been implemented. For example, European
Union has set maximum sulfur concentration limit up to 10 ppm in
diesel oil while the United States Environmental Protection Agency has
set this limit in gasoline and diesel oil up to 30 ppm and 15 ppm, re-
spectively [2].
Organic sulfur compounds present in fuel oils mainly exist as
Dibenzothiophene (DBT). Credited to the abundance of DBT in fuel oils,
it has been widely used as model to represent sulfur compound in real
oil. In order to remove DBT from fuel oils, many approaches including
hydrodesulfurization (HDS), extractive desulfurization, bio-desulfur-
ization (BDS), adsorptive desulfurization and oxidative desulfurization
(ODS) have been applied [3–5]. HDS operated at harsh operating
conditions, is effective only to aliphatic sulfur containing hydrocarbons
and less applicable to cyclic refractory sulfur derivatives like ben-
zothiophene, DBT and 4,6-dimethyl dibenzothiophene [6–8]. BDS ap-
plies biotic culture for sulfur removal and is a green approach, but
suffers from high selectivity of enzymes, slow reaction rates, high
sensitivity of microbial cultures to pH and low miscibility of reactants
[9]. On the contrary, ODS is an interestingly pragmatic catalytic ap-
proach which can efficiently deal with highly refractory DBT and its
derivatives, at mild operating conditions [10]. In ODS process, sulfur
compounds are oxidized to highly polarized sulfones by employing
suitable oxidants like ozone, per-chlorate, hypochlorite, potassium
permanganate, Nitrogen oxides or H2O2 [11,12]. These polarized sul-
fones are then removed from the products by extractants and ionic li-
quids (ILs) [13]. Over the years, researcher have been working on de-
signing catalysts based on polyoxometalates, molybdates supported on
Al2O3, Tungsten, Vanadium and Titanium in combination with cost-
effective and environment friendly oxidant at milder conditions
without compromising on the process efficiency [14,15].
The diverse nature of ODS creates a great room for researchers to
investigate various catalyst-oxidant systems. Sodium hypochlorite
(NaClO) is a strong oxidizing agent which has been widely used in
combination with H2O2 for desulfurization of fuel oils and coal [16,17].
Similarly, in case of catalyst selection, Mo supported over Al2O3 has
been the choice of researchers for many years with promising ODS
activity. Cedeno-Caero, L. et al. reported enhanced desulfurization ac-
tivity by 14 wt% Mo loaded over Al2O3 catalysts using H2O2 as oxidant
[18,19]. Some promoter metals like Mn and Fe to classical Mo/Al2O3
catalysts have also been extensively studied with enhanced catalytic
activity. Marina-Tepluchin, L. et al. reported Mn and Fe supported over
Al2O3 catalysts where the former exhibited higher activity than the
latter [20]. Amer-T Nawaf L. et al. reported the ODS activity of Mn and
Co over Al2O3 using air as oxidant [21]. Mn supported over other
supports like TiO2 and activated carbons has been reported with re-
markable activity as well [22]. Moreover, different Mn-based ILs have
also been reported as efficient extractants of sulfur compounds from
fuel oils [23]. These reports encompass the highly efficient nature of Mn
as a promoter with great affinity towards electron rich sulfur atom of
DBT.
Attributed to these reports about the effective contribution of Mn as
794
Fuel 237 (2019) 793–805
promoter to classical ODS catalysts, it is worth studying in a novel
catalyst-oxidant system where both can synergistically contribute to-
wards desulfurization activity of the process. Up to the authors’
knowledge, no reports on the combined application of low Mn em-
bossed Co-Mo/Al2O3 and Ni-Mo/Al2O3 catalysts and NaClO as oxidant
for the ODS of DBT has been reported so far. Thus, in this study, low Mn
promoted (0.5 wt%) Co-Mo/Al2O3 and Ni-Mo/Al2O3 catalysts were
tested using NaClO as oxidant in the ODS of DBT at mild operating
conditions. The proposed catalyst-oxidant system achieved remarkably
high DBT conversion (100%) in ultra-fast reaction time (5 min) at 25 °C.
Different experimental parameters including reaction time, tempera-
ture, oxidant and catalyst dose, oxidant type and pH were individually
optimized. The fresh and spent catalysts were characterized via scan-
ning electron microscopy (SEM), X-ray diffraction (XRD), energy dis-
persive X-ray (EDX) and Brunauer–Emmett–Teller (BET) surface area
techniques. Reaction products were quantitatively analyzed via high
pressure liquid Chromatography (HPLC) (Agilent 1100 equipped with a
Zorbax SB-C18 column having dimensions of 4.6 × 150 mm using UV
detector at a wavelength of 320 nm). Based on the electronic structure
of Mn and NaClO, a suitable reaction mechanism was proposed for the
catalytic ODS of DBT.
2. Experimental
2.1. Chemical reagents
All the reagents implied in this study were of analytical grade and
used without further purification. DBT, Al2O3 support, and Ammonium
heptamolybdate ((NH4)6Mo7O24·4H2O) were purchased from
Sinopharm chemical reagents Co., Ltd. Manganese chloride
MnCl2·6H2O, HCl, and NaOH were obtained from Tianjin guangfu fine
chemical research institute, China. Sodium hypochlorite NaClO
(12.915 wt%) was provided by Guangdong guanghua sci-tech Co.
Ltd·H2O2 (30 wt%), and Formic acid were provided by Merck Co.,
Darmstadt, Germany. Cobalt II Nitrate hexahydrate (Co (NO3)2·6H2O),
Nickel II Nitrate-hexahydrate (Ni (NO3)2·6H2O) and n-Heptane were
purchased from Guandong guanhua sci-tech. Co. Ltd. China.
2.2. Catalyst preparation
The catalysts were prepared via two well established i.e. successive
and simultaneous wet impregnation techniques [8,24]. For successive
wet impregnation, stoichiometric amount of powdered Al2O3 was
loaded with aqueous solution of (NH4)6Mo7O24·4H2O) and the mixture
was stirred for 7 h at 500 rpm over a magnetic stirrer. After stirring, the
solution was dried in oven at 120 °C for 12 h followed by calcination in
a muffle furnace at 500 °C for 7 h. The same procedure was repeated for
Co, Ni or Mn impregnated catalysts. After calcination, all the catalysts
were stored in inert N2 environment.
In the simultaneous impregnation method, powdered Al2O3 was
simultaneously impregnated with stoichiometric amounts of aqueous
solutions of Mo, Co or Ni and Mn followed by stirring, drying and
calcination steps as discussed above. A simplified schematic re-
presentation of both types of approaches for catalysts preparation is
shown in Fig. 1, while composition of each catalyst is shown in Table 1.
S. Subhan et al. Fuel 237 (2019) 793–805

where, Ci and Cf are DBT concentration before and after oxidation ex-
Al2O3
periments, respectively. Reaction parameters i.e. initial DBT con-
Pretreatment
centration, reaction time, temperature, catalyst and oxidant dose, pH of
the solution and oxidant type were separately optimized.

3. Results and discussion

Preparation of
metal solutions
3.1. Textural properties and characterization of catalysts

Incipient wet Chemical composition, crystallinity and the crystal phase of metallic
impregnation species in different catalysts were analyzed by XRD using Rigaku
Smartlab X-ray diffractometer (Japan), operated at 9 KW with a scan
speed of 10°/min in 2θ angular range of 10–80°. In the XRD patterns
shown in Fig. 2, prominent peaks for Al2O3, Mo [25] and Co [26] were
observed. Similarly, Mn and Ni were found in Ni and Mn based catalysts
Successive Simultaneous
impregnation Drying impregnation
[27–29]. The weak intensities of XRD peaks for Co, Ni, Mo and Mn
could be credited either to their high dispersion or to the fact that
species with concentration less than 5 wt% (Table 1) are difficult to be
detected due to limitations of XRD instrument [30]. All the metals were
found in oxidic phase due to the calcination step in catalyst synthesis
i.e. cobalt oxide (Co3O4) at 2θ = 32°, 34°, 47°, 58° and 66°, NiO at
2θ = 37°, 44° and 63° and manganese oxide at 2θ = 18°, 22°, 31°, 36°,
40°, 54°, 60° and 74° [31].
Surface morphology and distribution of active species play a key
Calcination role in determining catalytic activity [32] and hence SEM analysis using
Nova Nano SEM-450 [Model No: S3400N] was performed. Fig. 3 shows
Fig. 1. Schematic representation of catalysts preparation procedure. SEM scans of various partaking catalysts before (a–e) and after ODS
process (f–i) which suggest porous structure without any agglomeration
and irregular distribution of support particles with average particle size
Table 1 of less than 2 μm and a packed particles structure. SEM scans further
Composition of various partaking alumina supported catalysts.
showed that particles of Co, Mo and Ni impregnated catalysts were
Type of catalyst Metal loading (wt%) more tightly packed than nascent support while Mn-promoted catalysts
exhibited higher porosity, and uniform particles dispersion which could
Co Mo Mn Ni
play key role in higher ODS activity of Mn-promoted catalysts. In post
Mo/Al2O3 – 5 – – reaction SEM scans, all the catalysts were observed with decrease in
Co-Mo/Al2O3 2 5 – – porosity though still maintained a proper particle structure and shape
Ni-Mo/Al2O3 – 5 – 2 [33] which can be recycled to minimize the overall catalyst cost. The
Mn-Co-Mo/Al2O3 2 5 0.5 –
packed particle structure of all the catalysts as compared to pure Al2O3
Mn-Ni-Mo/Al2O3 – 5 0.5 2
support observed in SEM results was further supported by their lower
surface area than Al2O3 as determined from BET results (Table 2).
2.3. Support and catalysts characterization Surface area and porosity of fresh and spent catalysts were de-
termined via N2-adsorption (Fig. S2) approach using BET surface area
Detailed information about textural properties, elemental compo- and porosity analyzer (Micrometrics Gemini-VI Unit 1). N2-adsorption
sition and distribution, and surface morphology of the prepared cata- isotherms depicted in Fig. S2 were of type-II for all the samples sug-
lysts were achieved via XRD, EDX and EDX-elemental mapping, SEM gesting the predominant presence of both mesopores and micropores
and BET techniques. while a sharp jump in all isotherms at P/P0 of 0.9 reveals the presence
of macro-pores [34]. The textural data shown in Table 2 indicate high
surface area of Al2O3 support (201.8 m2.g−1) with highly porous
2.4. Catalytic activity tests and product analysis structure, which can play a key role in overall catalytic activity by
controlling active phase distribution. Table 2 further suggests that
DBT (representative of sulfur in fuel oil) stock solution of 2000 ppm surface area and pore volume of alumina support decreased con-
was prepared in n-heptane, from which working solutions were pre- siderably with the impregnation of metallic species [35], which is more
pared in a range of 200–1000 ppm and were applied to draw calibration dominant in case of tri-metallic catalysts i.e. Mn–Co–Mo/Al2O3 and
curve (Fig. S1). Mn–Ni–Mo/Al2O3 than bi-metallic (Co–Mo/ Al2O3 and Ni–Mo/ Al2O3)
ODS experiments were performed using a solution of 0.03 g DBT in attributed to the presence of extra metal in the earlier ones resulting in
15 mL n-heptane (2000 ppm) in the presence of NaClO as oxidant. A more pore blockage [32,36]. The considerable loss in pore size, pore
standard ODS experiment utilized 15 mL DBT solution, 0.2 g catalyst volume and surface area of the post reaction catalysts compared to fresh
and 0.2 mL NaClO (0.138 M) corresponding to O/S of 6.6, which were samples could be due to the pore fillings by DBT or ODS reaction
sealed in flask and stirred on magnetic stirrers at 500 rpm. After re- products [37]. This decrease was much prominent in case of Mn pro-
acting for certain duration of time, the solution was filtered and the moted catalysts which could be a strong evidence of their enhanced
filtrate was analyzed by HPLC with a UV-detector at a λmax of 320 nm interaction with DBT molecules resulting in higher conversion than
for change in DBT concentration. Catalytic desulfurization activity was mere Co or Ni based catalysts.
calculated using Equation (1): The presence, relative abundance and dispersion of active metallic
species in various catalytic samples were further confirmed by EDX and
Ci−Cf ⎫
DBT conversion(%) = ⎧ × 100 EDX elemental mapping using SEM [Model No: S3400N]. Fig. 4 eluci-
⎨
⎩ Cf ⎬ ⎭ (1) dates the corresponding EDX spectra of different catalyst confirming the

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S. Subhan et al. Fuel 237 (2019) 793–805

Co, Ni, Mn, Mo, Al2O3 Mn-Ni-Mo/Al2O3

Intensity Mn-Co-Mo/Al2O3

Ni-Mo/Al2O3

Co-Mo/Al2O3

10 20 30 40 50 60 70 80

2
Fig. 2. XRD patterns of different Mo/Al2O3 supported catalysts.

Fig. 3. SEM images of: fresh (a) Al2O3, (b) Co-Mo/Al2O3, (c) Ni-Mo/Al2O3, (d) Mn-Co-Mo/Al2O3, (e) Mn-Ni-Mo/Al2O3, and Spent (f) Co-Mo/Al2O3, (g) Ni-Mo/Al2O3,
(h) Mn-Co-Mo/Al2O3, and (i) Mn-Ni-Mo/Al2O3 catalysts.

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S. Subhan et al. Fuel 237 (2019) 793–805

Table 2 Table 3
BET surface area and porosity data of various alumina supported catalysts. EDX elemental compositions of various alumina supported catalysts.
Sample Pore volume Pore size (nm) Surface area (m2.g−1) Catalysts Active elements Elemental composition
(cm3.g−1)
Wt% At. %
Fresh Spent Fresh Spent Fresh Spent
Co-Mo/Al2O3 Co 03.14 05.02
Al2O3 0.3 – 6.02 – 201.8 – Mo 96.86 94.98
Ni-Mo/Al2O3 0.14 0.08 8.1 6.7 71.7 63.6
Ni-Mo/Al2O3 Ni 04.07 06.49
Co-Mo/Al2O3 0.14 0.08 8.09 5.2 71.4 50.07
Mo 95.93 93.51
Mn-Ni-Mo/ 0.13 0.07 9.1 5.3 60.7 45.5
Al2O3 Mn-Co-Mo/Al2O3 Mn 14.49 18.55
Mn-Co-Mo/ 0.13 0.08 8.8 6.2 59.1 50.6 Co 40.74 48.63
Al2O3 Mo 44.76 32.82

Mn-Ni-Mo/Al2O3 Mn 08.44 13.57

Ni 04.06 06.10
presence of Al, Ni, Mo, Mn and Co while their relative distribution data Mo 87.47 80.33
(%) are provided in Table 3 where Mo was found with maximum
abundance in all the samples due to its highest loading. Fig. S3 shows
EDX elemental mapping and relative dispersion densities of Co, Ni, Mn, (atoms/vol) compared to Co and Ni, confirming their respective theo-
Mo and Al2O3 in various synthesized catalysts. Overlay of Co (a1–a2) retical loadings used in the catalyst preparation. Moreover, atomic
and Ni (b1–b2) suggests smaller particle size and higher dispersion of density of Al (Fig. S3)(e) was much higher in support than other cata-
Co than Ni over Al2O3 support which will play a key role in ODS cat- lytic metals providing strong support to the impregnated metallic spe-
alytic activity of Co based catalysts. It can also be seen from Fig. S3 cies, hence increasing the final catalytic activity [38].
(c1–c2) that the addition of Mn elevated the dispersion of Co and Ni
species without any agglomeration intended to have intrinsic contact of 3.2. Catalytic activity tests
Co, Ni and Mo with Al oxide species, which can credit to the enhanced
ODS of DBT activity of Mn promoted catalysts. From elemental map- 3.2.1. Effect of catalyst preparation method
ping in Fig. S3, Mo can be observed with maximum atomic density Mode of catalyst preparation can affect the ODS activity due to the

Fig. 4. EDX scans of alumina supported catalysts: (a) Co-Mo/Al2O3, (b) Ni-Mo/Al2O3, (c) Mn-Co-Mo/Al2O3 and (d) Mn-Ni-Mo/Al2O3.

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S. Subhan et al.
variation in degree of active phase formation and dispersion [39]. In
the current study, five different types of catalysts were separately pre-
pared by successive and simultaneous wet impregnation methods using
Al2O3 as support. Both sets of catalysts were tested in the ODS of DBT
under similar experimental conditions and the data are plotted in Fig. 5.
It can be seen that ODS of DBT activity by Mn-Co-Mo/Al2O3 prepared
via simultaneous impregnation (63%) was considerably enhanced by
those prepared via successive impregnation (100%) under similar ex-
perimental conditions of 15 mL of 1000 ppm DBT solution, 0.2 mL of
0.138 M NaClO (O/S-6.6), 0.2 g of catalyst, and 15 min reaction time at
30 °C. This could be accredited to the fact that in simultaneous im-
pregnation, active metals compete towards the support surface which
leads to their improper dispersion and impregnation [40], hence results
in lower DBT conversion (68%). On the contrary, successive impreg-
nation approach excludes this factor of competition and provides en-
ough duration and better chances for each active species (Co, Ni, Mo
and Mn) to be properly and evenly impregnated over the support sur-
face. This leads to better and even dispersion of active specie resulting
in outstandingly enhanced DBT conversion (100%) by Mn-Co-Mo/
Al2O3. Furthermore, Mo has been reported with good ODS activity over
Al2O3 support while better of Mn, and Co than that of Ni with NaClO
results in higher DBT conversion by the formers than the latter [41,42].
0.5 wt% Mn loaded catalysts showing tremendously high DBT conver-
sion than many of the previous reports with same Mn loading could be
attributed to the synergistic effect of Mn active phase with NaClO as a
strong oxidizing agent [21,43]. As catalysts prepared via successive
impregnation approach performed better than those prepared via si-
multaneous approach (Fig. 5), hence the formers were selected for
onward activity tests and parameter optimization.
3.2.2. Effect of initial DBT concentration
Catalytic activity is strongly affected by the interactions between
catalyst active sites and reactants where higher reactant concentration
provides more chances of such interactions [21]. In current study, effect
of initial DBT concentration in a range of 1000–2000 ppm was probed
110
Mo/Al2O3
Co-Mo/Al2O3
Mn-Co-Mo/Al2O3
90
DBT Conversion (%)
70
50
30
Simultaneous
Fig. 5. Effect of catalyst synthesis approach on DBT conversion employing 15 mL of 1000 ppm DBT solution, 0.2 mL of 0.138 M NaClO (O/S-6.6), 0.2 g of catalyst,
and 15 min reaction time at 30 °C.
Fuel 237 (2019) 793–805
over five types of catalysts at fixed amount of oxidant (0.1 mL), catalyst
(0.1 g), 5 min reaction time and 25 °C temperatures. Data in Fig. 6
suggest a firsthand relationship between initial DBT concentration and
DBT conversion which reaches 100% at 2000 ppm.
A balanced chemical reaction for the complete oxidative desulfur-
ization of DBT can be written as Eq. (2):
2NaClO + C12 H8 S → C12 H8 O2 S + 2NaCl (2)
According to the reaction stoichiometry, 0.0003 mol of oxygen are
required to completely oxidize 15 mL of 2000 ppm DBT (0.03 g/15 mL).
As obvious from Table S1, net oxygen production from 0.1 mL of
0.138 M NaClO (O/S-6.6) is 0.00138 mol, which is multiple times more
than the required one (0.0003) for the complete oxidation of most
concentrated DBT solution (2000 ppm). This is suggestive of the fact
that in the current experimental set up, the oxygen supply was always
in excess throughout the course of reaction. Having said this, a lower
DBT concentration (1000 ppm) will provide lesser chances of oxygen-
DBT interaction due to phase transfer limitations among molecules of
DBT and oxygen [36] over fixed amount of catalyst, and hence lower
DBT oxidation is observed. These limitations are decreased with in-
creasing DBT concentration i.e. 2000 ppm, hence resulting in higher
DBT conversion.
As obvious from Table S1, net oxygen production by 0.1 mL of
0.138 M NaClO solution is far greater (0.00138) than the demand
(0.00015, 0.00018, 0.00021, 0.00024, 0.0003 mol for DBT solution
ranging from 1000 to 2000 ppm respectively). It is also possible, that a
DBT concentration beyond 2000 ppm may lead to decreased DBT con-
version due to utilization of all active sites in the catalyst while still
having un-oxidized DBT leading to decrease in overall DBT conversion.
However, as DBT concentration in fuel oil rarely exceeds 2000 ppm, we
did not analyze effect of concentration beyond 2000 ppm. Based on the
results in Fig. 6, 2000 ppm concentration was employed in investigating
other parameters.
Ni-Mo/Al2O3
Mn-Ni-Mo/Al2O3
Successive
Type of impregnation
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S. Subhan et al. Fuel 237 (2019) 793–805

120
Blank Mo/Al2O3 Ni-Mo/Al2O3
Co-Mo/Al2O3 Mn-Ni-Mo/Al2O3 Mn-Co-Mo/Al2O3

100

DBT Conversion (%)

80

60

40

20
1000 1200 1400 1600 2000
Concentration/ppm
Fig. 6. Influence of initial DBT concentration on catalytic activity employing 15 mL DBT solution, 0.1 mL of 0.138 M NaClO (O/S-6.6), 0.1 g catalyst, and 5 min
reaction time at 25 °C.

3.2.3. Effect of reaction time
Catalytic activity and kinetics of the oxidation process are usually
favored at longer reaction time as it unclogs DBT-catalysts interactions,
leading to higher conversion [18,44], though it can concomitantly lead
to time consumption and capital wastage. In order to cope with this
issue, ultra-short reaction intervals (0.5–5 min) were probed to test the
ODS catalytic activity of supported catalysts. The results in Fig. 7 sug-
gest that maximum DBT conversion is achieved in ultra-short reaction
duration of 5 min which is multiple times faster than many of previous
reports (Table 4), owing to the strong oxidizing power of hypochlorous
ions (OCl−) resulted from the dissociation of NaClO oxidizing DBT to
DBT-sulfone [16,17]. Secondly, Al2O3 displays an ideal coordination
with the braced active metals and oxidant system that further stimu-
lates the ODS process. Mn promoted Co catalysts are more active than
their counterparts due to better coordination chemistry between Mn2+
and Co2+ ions and their net effect on the Al2O3 surface [41]. This ultra-
fast and appreciably higher DBT conversion by the current proposed
oxidant-catalyst system could be deemed promising for industrial ap-
plications of fuel oil processing affecting the cost effectiveness of the
process in terms of capital and time savings.

120
Blank Mo/Al2O3 Ni-Mo/Al2O3
Co-Mo/Al2O3 Mn-Ni-Mo/Al2O3 Mn-Co-Mo/Al2O3

100
DBT Conversion (%)

80

60

40

20
0.5 1 2 3 4 5
Time/min
Fig. 7. Influence of reaction time on DBT conversion employing 15 mL of 2000 ppm DBT solution, 0.1 mL of 0.138 M NaClO (O/S-6.6), 0.1 g catalyst and 25 °C
temperature.

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S. Subhan et al. Fuel 237 (2019) 793–805

Table 4
Comparative analysis of DBT conversion data via ODS from reported literature and current study.
S. No Catalyst type Oxidant type Reaction time (min) Reaction temperature (°C) Maximum DBT conversion (%) Reference No.

1 [EimC4SO3H]NTf2 NaClO/H2O2 180 60/30 99 [16]

2 NH3 NaClO 120 90 70 [17]
3 MoO3 H2O2 30 60 [19]
4 MnO2/Al2O3, Air 180 200 81 [21]
Co3O4/Al2O3
5 MoO2/Al2O3 H2O2 20 60 70 [31]
Co-Mo/Al2O3
6 MnO2/Al2O3, O2 480 180 90 [41]
Co3O4/Al2O3
7 MoO3/Al2O3 H2O2 40 60 100 [44]
8 MgAl-PMo12 H2O2 60 150 99 [46]
9 ([Bmim]3PMo12O40) H2O2 60 100 100 [47]
10 Mn-Co-Mo/Al2O3 NaClO 5 25 100 Current work

3.2.4. Effect of reaction temperature
Routine ODS of fuel oils is operated at temperature of 60–70 °C to
overcome the dissociation energies of disparate oxidants [5,45]. How-
ever, in order to keep cost and simplified mechanization of the process
in mind, we tested the effect of reaction temperature on DBT conversion
at room temperature (10–30 °C) and the results are compiled in Fig. 8. It
was found that Al2O3 supported catalysts achieved 100% DBT conver-
sion at extremely mild temperature (25 °C) accrediting the best fitted
catalyst-oxidant system. The five types of catalysts followed an overall
ODS activity order as: Mn–Co–Mo/Al2O3 > Mn–Ni–Mo/
Al2O3 > Co–Mo/Al2O3 > Ni-Mo/ Al2O3 > Mo/Al2O3. A DBT con-
version of 100% in ultra-fast reaction time of 5 min and at low tem-
perature of 25 °C in this study was much superior to some earlier re-
ported literature (applying higher temperature and longer reaction
time) as shown in Table 4 and hence scoring in favor of our proposed
study for practical implementation on industrial level.
3.2.5. Effect of catalyst dose
In a routine ODS process, higher catalytic dose provides more
chances of surface interactions between catalyst active phase and DBT
molecules leading to enhanced conversion [46,47]. However, in the
current study, crediting to the high activity of catalyst and strong
oxidizing power of oxidant (NaClO), both are required in a very low
amount to fulfill the oxygen needs (0.0003 mol) for the complete oxi-
dation of DBT to DBT-sulfone as shown by theoretical calculations in
Table S2. A sample containing 15 mL of 2000 ppm DBT (O/S-6.6) was
tested at low catalyst dose (0.02–0.2 g) using 0.1 mL of 0.138 M NaClO
for 5 min at 25 °C. Results compiled in Fig. 9 show an increase in ODS of
DBT with increase in catalyst dose from 0.02 to 0.1 g, attributed to the
ideal scenario of active sites-DBT interaction with excess oxygen species
present in the solution medium. Further increase in catalyst amount
(0.2 g) might provide more active phase but can concomitantly either
interact with counter metal ions leading to agglomeration/clotting or
can compete with oxidant molecules instead of oxidizing DBT [48]
leading to a decrease in DBT conversion. Furthermore, rich catalyst
active phase and strong oxidizing agent in the current set up led to the
best fitted chemistry in current oxidant-catalyst system which de-
creased the catalyst and oxidant contents requirements without com-
promising on the net DBT conversion [16]. Furthermore, consistent
ODS of DBT catalytic activity order of Mn-Co-Mo/
Al2O3 > Mn–Ni–Mo/Al2O3 > Co–Mo/Al2O3 > Ni-Mo/
Al2O3 > Mo/Al2O3 further validated the high degree of accuracy in the
experimental set up.

120
Blank Mo/Al2O3 Ni-Mo/Al2O3
Co-Mo/Al2O3 Mn-Ni-Mo/Al2O3 Mn-Co-Mo/Al2O3

100
DBT Coversion (%)

80

60

40

20
10 15 20 25 30
Temperature/oC
Fig. 8. Effect of reaction temperature on DBT conversion employing 15 mL of 2000 ppm DBT solution, 0.1 mL of 0.138 M NaClO (O/S-6.6), 0.1 g catalyst, and 5 min
reaction time.

800
S. Subhan et al. Fuel 237 (2019) 793–805

110
Mo/Al2O3 Ni-Mo/Al2O3 Co-Mo/Al2O3

Mn-Ni-Mo/Al2O3 Mn-Co-Mo/Al2O3

90
DBT Conversion (%)

70

50
0.02 0.06 0.08 0.1 0.2
Catalyst dose/g
Fig. 9. Effect of catalyst dose on DBT conversion employing 15 mL of 2000 ppm DBT solution, 0.1 mL of 0.138 M NaClO (O/S-6.6), and 5 min reaction time at 25 °C.

3.2.6. Effect of oxidant dose
ODS of DBT is strongly affected by both, type as well as amount of
oxidant as high oxidant dose provides more oxidizing species which can
lead to higher conversions. According to the stoichiometry of the re-
action in this study (Eq. (2)), a 15 mL sample containing 0.03 g of DBT
(2000 ppm) needs 0.0003 mol of oxygen for the complete oxidation to
DBT-sulfone. Theoretical findings summarized in Table S3 show that
(except 0.02 mL of NaClO being producing 0.000276 mol oxygen), the
net production of oxygen i.e. 0.0008, 0.001104, 0.00138, and
0.00276 mol using 0.02, 0.06, 0.08, 0.1 and 0.1 mL of oxidant respec-
tively are far greater than the demand (0.0003 mol). The high oxygen
content (more than required for complete oxidation of 15 mL of
2000 ppm DBT) produced from as low as 0.06 mL of NaClO is a con-
clusive evidence of its strong oxidizing power [16,17]. Fig. 10 shows an
increase in DBT conversion with increasing oxidant dose from 0.02 to
0.1 mL, which could be justified by the data in Table S3 in terms of
more oxygen produced at higher dose of oxidant, completely oxidizing
DBT to DBT-sulfone. Further increase in oxidant dose (0.2 mL) could
impose detrimental impacts on catalytic activity as the excessive OCl-
ions can compete with DBT towards active species on the catalyst
surface rather than oxidizing DBT and hence net DBT conversion de-
creases. Along with remarkably high efficiency (100%) in ultra-fast

110
Mo/Al2O3 Ni-Mo/Al2O3 Co-Mo/Al2O3
Mn-Ni-Mo/Al2O3 Mn-Co-Mo/Al2O3
DBT Conversion (%)

90

70

50
0.02 0.06 0.08 0.1 0.2
Amount of oxidant/ml
Fig. 10. Effect of oxidant dose on DBT conversion employing 15 mL of 2000 ppm DBT solution, 0.138 M NaClO, 0.1 g catalyst, and 5 min reaction time at 25 °C.

801
S. Subhan et al.
reaction time (5 min) over a low-cost Mn loaded catalyst utilizing a very
low oxidant dose (0.1 mL), the proposed process poses great challenges
to the existing methods for the ultra-deep desulfurization of fuel oils on
industrial level. In Fig. 10 overall activities order of: Mo/
Al2O3 > Mn–Ni–Mo/Al2O3 > Co–M/Al2O3 > Ni-Mo/ Al2O3 > Mo/
Al2O3 was observed.
3.2.7. Effect of pH
Investigating pH values in any oxidation reaction is of great im-
portant as it can alter the activity of ODS process by affecting the extent
of surface charges, oxidizing species and catalyst active phase avail-
ability. Most of oxidants reported in ODS of DBT possess strong acidic
nature and favor a low solution pH for their dissociation [49]. Hypo-
chlorite ion is the deprotonated form of hypochlorous acid (HOCL),
which is a weak acid with Pka value of 7.53. NaClO, provides ClO− ions
upon dissociation, which usually requires higher pH for dissociation
[17], making the current oxidation process strongly pH dependent. The
effect of pH in a range of 2–12 (tuned via HCl or NaOH) on catalytic
activity of different supported catalysts is shown in Fig. 11. Increase in
net DBT conversion with increasing pH (increasing alkalinity of the
medium) is due to the enhanced dissociation of NaClO at higher pH and
hence increased presence of OCl− ions which facilitates higher DBT
oxidation chances. On the contrary, acidic pH readily converts OCl− to
HOCl due to the presence of excessive H+ ion in the vicinity [17]
hindering the oxidation reaction of DBT and hence decreased DBT
conversion.
3.2.8. Comparison of oxidation activity of NaClO with other oxidants
Various oxidants due to the variations in their degree of oxidizing
power affect ODS of DBT to variable extents. Fig. 12 compiles the ac-
tivity results of NaClO compared with classical oxidants used in ODS of
DBT i.e·H2O2 and Formic acid using 2000 ppm DBT solution, 0.1 mL
oxidant, 0.1 g catalyst, 5 min contact time, pH-12 and 25 °C reaction
temperature. Results suggest that NaClO exhibited almost two times
higher DBT conversion than that of H2O2 and Formic acid due to high
oxidizing power of hypochlorite ions resulting from its dissociation
[16,17]. Another reason could be the weak dissociation of H2O2 and
HCOOH in strongly basic medium (pH-12) which might have affected
acid strength and in turn catalytic activity [50,51]. We further
110
Mn-Ni-Mo/Al2O3
90
DBT Conversion (%)
70
50
30
2 4
Fig. 11. Influence of pH on DBT conversion employing 15 mL of 2000 ppm DBT solution, 0.1 mL of 0.138 M NaClO (O/S-6.6), 0.1 g catalyst, and 5 min reaction time
at 25 °C.
Fuel 237 (2019) 793–805
compared the results reported in literature with those of the current
study as shown in Table 4 which indicated superior nature of our results
in terms of oxidant dose, reaction temperature, reaction time and net
DBT conversion. These results suggested that NaClO as oxidant coupled
with Mn-Co-Mo/Al2O3 catalyst system is a promising alternative for the
ODS of DBT with high activity (100% DBT conversion) in ultra-short
reaction time (5 min) at mild operating temperature. Furthermore, the
cost effective and environment friendly nature and ease of availability
of NaClO compared to other reported oxidants, could also be of great
interest in practical implementation of the proposed approach for the
ODS of DBT on industrial level.
3.2.9. Catalyst recycling
Catalyst recycling is crucial for controlling process cost in terms of
practical applications. In the current study, 0.1 g catalyst was tested for
six consecutive cycles under similar optimized experimental conditions.
At the end of each catalytic DBT oxidation reaction, catalysts were re-
covered by filtration, successively washed with n-Heptane to dissolve
un-oxidized DBT molecules and acetonitrile to remove any left-over
DBT-sulfone. At the end, product was thoroughly washed with me-
thanol several time to remove other impurities and then dried in oven
at 110 °C for 12 h [52,53] and tested in next cycle. The data presented
in Fig. 13 suggest marginal decrease in activity after six consecutive
cycles which is practically benign to adjust the process cost. The loss in
activity (4–5%) after sixth consecutive reuse was comparable to some
earlier reports (utilizing high temperature for catalyst regeneration)
[54,55], which were avoided in this study keeping the greenness, safety
and cost of the process in mind. An HPLC analysis peak for the product
in Fig. S4 confirmed the formation of DBT-sulfone after 6th consecutive
cycle. Moreover, low oxidant and catalyst dose and operation at mild
operating conditions of temperature and pressure can greatly contribute
in controlling process cost, and possibly diminishes the extra step of
catalyst recycling in practical implementation of the proposed study.
3.3. Proposed reaction mechanism for ODS
ODS proceeds via oxidation of sulfur atom in DBT to DBT-sulfone,
which was facilitated by NaClO over Mo/Al2O3 based catalysts in the
current study. A simplified reaction mechanism shown in Fig. 14
Mn-Co-Mo/Al2O3
6 8 10 12
pH
802
S. Subhan et al. Fuel 237 (2019) 793–805

110
Mo/Al2O3 Ni-Mo/Al2O3
Co-Mo/Al2O3 Mn-Ni-Mo/Al2O3
Mn-Co-Mo/Al2O3
90
DBT Conversion (%)

70

50

30
Formic Acid Hydrogen Peroxide NaClO
Oxidant type
Fig. 12. Influence of oxidant type on DBT conversion employing 15 mL of 2000 ppm DBT solution, 0.1 mL of each oxidant, 0.1 g catalyst, and 5 min reaction time at
25 °C.

suggests consecutive attacks of oxygen from hypochlorite ion (OCl−) on starts next catalytic cycle [56]. All these factors synergistically count for
the electron rich sulfur atom of DBT leading to DBTO2 molecule [16]. the excellent and ultra-fast ODS of DBT activity of Mn-Co-Mo/Al2O3
OCl− ions produced from the dissociation of NaClO possess very strong catalyst at mild operating temperature.
oxidizing power and hence readily oxidizes sulfur atom leaving simple
Cl− ion, which reacts with Na+ ion to produce NaCl [17]. Outstanding
4. Conclusions
activity of Mn-Promoted catalysts can be explained by the fact that
Mn2+ promotes the conversion of MO2 [M = Co, Mo, Ni, Mn] into MO3
This study focused on developing a novel and highly efficacious
species which then facilitate the oxidation of DBT to DBT-sulfone
catalyst-oxidant system (Mn-Co-Mo/Al2O3 and NaClO) for the ultra-fast
[22,41]. MnO3-Cl formed as a result of reaction between MnO2 and
and highly efficacious ODS of DBT at mild reaction temperature. The
OCl− readily loses Cl− to the solution medium and donates Oxygen
best-fitted chemistry of Mo/Al2O3 catalysts in synergism with NaClO
atom to sulfur in DBT while itself getting converted into MnO2 which
achieved 100% DBT conversion in 5 min at 25 °C. NaClO exhibited

110
Mn-Ni-Mo/Al2O3 Mn-Co-Mo/Al2O3

90
DBT Conversion (%)

70

50

30
1 2 3 4 5 6
Number of run
Fig. 13. DBT conversion for six consecutive cycles over 0.1 g/L catalyst using 15 mL of 2000 ppm DBT solution, 0.1 mL of 0.138 M NaClO (O/S-6.6), 5 min reaction
time and 25 °C temperature at pH 12.

803
S. Subhan et al.
Fig. 14. Proposed reaction mechanism for the catalytic oxidative desulfurization of DBT using NaClO as oxidant.
higher ODS activity than H2O2 and formic acid credited to the sy-
nergistic integration of the former with Mn active phase in Al2O3 sup-
ported catalysts. Textural characterizations of fresh and spent catalysts
helped in elucidation and interpretation of experimental results. Over
the course of all reaction parameters, catalytic activity followed an
order as: Mn–Co–Mo/Al2O3 > Mn–Ni–Mo/Al2O3 > Co–Mo/
Al2O3 > Ni-Mo/Al2O3 > Mo/Al2O3 suggesting high degree of re-
producibility in the current experimental set up. The catalysts remained
fairly active for six consecutive reuses. The present approach based on
the cost-effective nature of both catalyst and oxidant, simplified en-
gineering requirements and safety with 100% DBT conversion in ultra-
fast reaction time, could be sighted as an efficient alternative for the
processing of fuel oils on industrial level.
Conflict of interest
The authors declare no competing financial interest.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2018.10.067.
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