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Advanced Chemical Engineering Research Volume 3, 2014

Photo Degradation-Adsorption Process as a

Novel Desulfurization Method
Hossein Faghihian*, Reza Sadeghinia
Department of Chemistry, Shahreza Branch, Islamic Azad University
311-86145 Shahreza, Iran
faghihian@iaush.ac.ir
Abstract
The main goal of this research was to desulfurize an organic
solution containing dibenzothiophene. We prepared a
nanocomposite containing polyethylene glycol (PEG) and FeTiO2 as photocatalyst for degradation of dibenzothiophene.
The presence of Fe3+ and PEG in the TiO2 structure
respectively broadened the light absorption zone and altered
the surface structure of the photocatalyst. The synthesized
photocatalyst was characterized by XRD, SEM, EDX, BET
and TG techniques and used for degradation of dibenzothiophene in n-hexane solution. The effect of different
experimental conditions on the degradation efficiency was
studied and optimized. The degradation products were
identified by GC-Mass techniques. The adsorption method
by using mesoporous SBA-15 adsorbent was applied to
remove the sulfur containing products. The results showed
that the synthesized photocatalyst was an efficient composite
for degradation of dibenzothiophene and that the
mesoporous SBA-15 was a good candidate for removal of
sulfur containing degradation products.
Keywords
Desulfurization; Nanocomposite;
Dibenzothiophene; SBA-15

Photocatalyst;

Degradation;

Introduction
Nowadays, the production of transportation fuels
without polluting compounds is required worldwide.
Sulfur compounds in transportation fuels are
converted to SOx by combustion, leading to acid rain
and air pollution. In many countries, the average
sulfur content in diesel has been restricted to 10g/ml,
even zero level in the near future. Hydro desulfurization (HDS) process is a very efficient technique for
removing simple sulfur compounds, but not effective
for dibenzothiophene (DBT) and its derivatives. The
method is neither suitable for deep desulfurization of
diesel, because it requires severe operation conditions,
high energy and hydrogen consumption. Therefore,
other deep desulfurization techniques including
adsorptive desulfurization, oxidation desulfurization,
biodesulfurization extractive desulfurization with

18

ionic liquids and alkylation precipitation are

considered. Recent studies indicated that advance
oxidation processes (AOPs) are capable to destroy
environmentally persistent pollutants, due to their
ability to generate the highly oxidizing species, OH
radical. Titanium dioxide is largely utilized as a
photocatalyst because of its high photocatalytic
activity, photochemical stability, non-toxicity and low
cost. However, the efficiency of TiO2 is limited by its
relatively large band gap energy (3.2 eV), matching to
the wavelength of 370 nm where just 3-5% of solar
energy is practical and also by the high recombination
rate of the electron-hole pairs formed in the
photocatalytic processes. Many techniques have been
examined to increase the photocatalytic activity of TiO2
such as, dye sensitized, transition metals doping noble
metal deposition combination with semiconductor
supports such as (TiO2/Fe2O3, TiO2/WO3), anions
doping such as (C, N, S, F, B), addition of polymeric
fugitive agents such as polyethylene glycol (PEG). In
this study, Fe3+ ion was selected as a doping transition
metal due to the similarity in the ion radius (Fe3+=
0.69A, Ti4+= 0.745A). To increase the number and size
of pores of the photocatalyst, PEG was also added to
the FeTiO2 composite. The synthesized photocatalyst
was then used for degradation of dibenzothiophene
under different experimental conditions. The degradation
products were identified and their adsorption from
organic media was examined by SBA-15 mesoprous.
Experimental
Catalyst Preparation
Titanium tetraisopropoxide (Ti (OC3H7)4, 99.5 %,
Aldrich), hydrogen peroxide (H2O2, 30%, Qualigen),
ferric nitrate (Fe (NO3)39H2O, Qualigen), and
polyethylene glycol (average molecular weight: 4000,
Qualigen), were used as starting materials. TiO2 doped
with Fe (III) and polyethylene glycol was synthesized
by sol-gel method. Firstly, the titanium tetraisopropoxide
(1.77 g) was hydrolyzed by 100 mL of water and the

Advanced Chemical Engineering Research Volume 3, 2014

resulting titanium hydroxide was washed thoroughly

to remove alcohol formed in the hydrolysis process. 20
mL of aqueous H2O2 (15%) was slowly added to the
precipitate to dissolve it and a transparent orange sol
of titanium peroxo complex was obtained. During
dissolution 85 mL of distilled water was added to the
solution to avoid immediate dense gel formation. Then
6 mL of 10% PEG solution and 12.2 mL of 0.1 M iron
solution were added into the sol. The sol was allowed
to dry for 4-5 days at room temperature. The
photocatalyst was then dried at 100oC for 2 h and the
brown powder was calcined at 400oC for 3h.
Catalyst Characterizations
The phase transformation and crystallinity of the
samples were determined by X-ray diffraction method
(D8 Advanced Bruker diffractometer) with Cu K
radiation. The average size of the catalyst particles (D)
was determined based on the Scherers eq 1:
D= k ( / cos)

(1)

Where k is a constant which is equals to 0.89, () is the

X-ray wavelength and () is the full width at half
maximum and () is the half diffraction angle.
The thermal property of the as synthesized photocatalyst was examined by thermo gravimetric analysis (TG
Perkin Elmer-7) in the temperature of 25 to 700oC with
heating rate of 10oC/min. The specific surface area of
the photocatalyst was measured by BET (BrunauerEmmett-Teller) method using a Micromeritics Tri-Star
3000 instrument. The surface morphology and size of
nanoparticles were studied by scanning electron
microscopy (Seron Technology AIS-2100 SEM 2008
South Korea). EDX supported in the SEM was used to
determine the Fe content of the Fe-doped TiO2 samples.
Photocatalytic Decomposition of Dibenzothiophen
The photocatalytic activity of the catalyst was
examined under irradiation of two 30 w high-power
mercury lamps. 0.4 g of photocatalyst was added to
10ml of n-hexane dibenzothiophene solution (200 ppm)
and the mixture was placed on a magnetic stirrer in a
closed chamber with UV light sources, so that the
solution was illuminated from the top. The distance
between the UV light and the solution was 40 cm.
After irradiation, the sample was separated by
centrifugation and the solution was analyzed for
dibenzothiophene by a UV-visible spectrophotometer
(PG Instruments-T 70) at =235 nm.The degradation
percentage was calculated by the eq 2:

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% degradation= 100 (C0- Ct)/C0

(2)

Where (C0) and (Ct) are respectively the concentrations

of dibenzothiophene at initial and (t) time. To identify
the dibenzothiophene degradation products, the
mixture was centrifuged and the upper solution was
injected to a GC-Mass instrument (Model; Agilent GC
6890 N, Column; HP-5 ms). For adsorption of the
sulfur containing degradation products, 2 mL of the
centrifuged solution was shaken with 0.03 g of
mesoporous SBA-15 adsorbent at room temperature
for 24 h. The mixture was centrifuged and the upper
solution was analyzed by GC-Mass spectrometry. To
regenerate the photocatalyst for re-use, it was
repeatedly washed with n-hexane and then activated
at 400oC for 3 hours.
Results and Discussion
Characterization of the Photocatalyst
XRD patterns of two synthesized nanocomposites with
different thermal treatment are given in Fig. 1.
- Nanocomposite dried at room temperature for five
days followed by drying at 100oC for 2 h and calcined
at 400oC. Fig. 1a
- Nanocomposite dried at 100oC for 2h and calcined at
450oC. Fig. 1b
The diffraction line at 2 of 25.37, 38.01, 48.02, 54.01,
62.76, 75 and 76.02 are related to the anatase phase and
the lines at 2 of 27.61, 36.01 and 41.44 belonged to the
rutile phase. From the patterns, it was concluded that
the major phase in sample (a) was anatase. According
to the study reported by Sonawane27, transformation of
anatase to rutile phase occurred between 600oC to
700oC, and with the nanosize samples, the transformation began at lower temperatures. Similar behavior
was observed in this research while the major component of the sample treated at 450oC was rutile phase
(diffraction lines at 27.61, 36.01 and 41.44) in fig.1b.
The particle size of the photocatalyst calculated by the
Scherers equation was 12nm.
The thermal curve of the photocatalyst is given in Fig.
2. The weight loss peak observed around 53-115oC was
attributed to the evaporation of the absorbed water
and remaining alcohol generated during hydrolysis of
titanium alkoxide. The weight loss peak at about 200340oC was due to the decomposition of the remaining
polyethylene glycol and conversion of titanium
peroxide to titanium oxide. After 340oC, the product
was thermally stable up to 700oC.
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From the SEM image of the photocatalyst (Fig. 3), the

formation of homogeneous particles was clearly
observed. The homogeneity of the adsorbent was
attributed to the addition of PEG to the photocatalyst.25
The average particle size of the nanocomposite
obtained by the SEM image was between 10-20 nm and
near to the value obtained by XRD method.
The iron and titanium content of the sample were
measured by EDX technique (Fig. 4 and Table 1). The
iron content (2.18 %) was very near to the calculated
value 2 wt %.
The surface area, pore size and pore volume of the
sample were obtained by the BET method (Fig. 5, 6)
and the results are gathered in Table 2.
The surface area and pore volume of the synthesized
photocatalyst was higher than that of TiO2 itself and
even higher than of the PEG-Fe/TiO2 sample prepared
by Wantala through solvothermal method. The high
surface area is considered as the most advantageous
characteristic of a photocatalyst, therefore the sol-gel
method used in this research can be considered as an
efficient preparation.
Effect of Photocatalyst Amount
With the increasing of the photocatalyst amount, the
degradation of dibenzothiophen increased firstly
and then gradually decreased. Fig. 7. With high
concentration of the photocatalyst, the incident light is
partially scattered and lower free radicals are
produced. The particles are also agglomerated and the
specific surface area of the photocatalyst is reduced.

Advanced Chemical Engineering Research Volume 3, 2014

than that in the similar work performed by Matsuzawa

who studied the oxidation of dibenzothiophene in
acetonitrile and obtained 40% of degradation after 600
min irradiation.
Adsorption of Degradation Products
The degradation products were analyzed by GC-Mass
technique, Fig. 10. The degradation products were
identified and listed in table 3. Among the products,
thiophene, thiophene 2-isopentyl, thiophene 2-(3methylbutyl), thiophene 2-ethyl, thiophene 2-hexyl,
and thiophene 2-pentyl are sulfur containing
compounds. In order to achieve deep desulfurization,
adsorption of these compounds was examined by
mesoporous SBA-15 according to the procedure given
in photocatalytic decomposition of debenzothiphene
section.
After adsorption, the adsorbent was separated and the
solution was again analyzed by GC-Mass (Fig. 11 and
table 4). The results showed that all sulfur containing
compounds were adsorbed by the adsorbent and the
remaining compounds were; Tridecane; Tetradecane;
Pentadecane;
Phenol,
2,6-bis(1,1-dimethylethy);
Hexadecane.
Kinetics of Degradation
Kinetics studies were carried out under optimal
reaction conditions. The rate constant for the apparent
consumption of DBT was obtained from the pseudo
first-order eq 3:
Ln Ct/Co=-kpt

(3)

Effect of Initial Concentration

Where Co and Ct are the concentrations of time zero

and time t (s), and kp the first-order rate constant (s-1).

At higher concentration of dibenzothiophene, more

molecules were adsorbed on the photocatalyst surface
near the free radicals. Hence, the degradation of
dibenzothiophene increased (Fig. 8). At concentrations
above 200mg/l, the light diffusion was limited and the
degradation was decreased.

When (Ln Ct/Co) was plotted against t, a straight line

was fitted to the data Fig. 12, and the correlation factor
of (R=0.980) suggested that DBT photo degradation
reaction followed pseudo first-order kinetics,
indicating that the degradation rate depended on the
pollutant concentration.

Effect of Irradiation Time

Regeneration of the Photocatalyst

The effect of irradiation time on degradation efficiency

of dibenzothiophene is shown in Fig. 9. By increasing
irradiation time, the number of the receiving photons
and hence the hydroxyl radicals increased. After
appointed time amount of radicals reached maximum
with regard to solution concentration and the electronhole
recombination
increased,
therefore
the
degradation became constant. The degradation
efficiency obtained in this work (90.27%) was higher

The reusability of the photocatalyst was examined for

6 successive cycles. After each cycle the photocatalyst
was regenerated by washing with n-hexane solution
and activated at 400oC. After each regeneration, a
small reduction was observed in the degradation
efficiency, but the efficiency remained constant after
the fourth cycle (Fig. 13).The decrease on the
photocatalyst efficiency was caused by deposition of
degradation products on the catalyst surface.

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Advanced Chemical Engineering Research Volume 3, 2014

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Conclusion

combined UV-Visible light destruction of oxalic acid in

The nanocomposite prepared in this research showed

higher specific surface area compared to the composite
prepared by sol-gel method. Under optimized
conditions, the synthesized photocatalyst decomposed
more than 90% of dibenzothiophene. Application of
mesoporous SBA-15 absorbent was an efficient method
for removal of sulfur containing degradation products.
Since the conventional hydro desulfurization process
is not an effective method for dibenzothiophene and
its derivatives, the combination of photodegradationadsorption method used in this research can be used
for deep desulfurization of transportation fuels.

aqueous solution. Desalination 2010, 260, 101-106.

Li, F.; Zhang, Z.; Feng, J.; Cai, X.; Xu, P. Biodesulfurization of
DBT in tetradecane and crude oil by a facultative. J.
Biotechnol 2007, 127, 222-228.
Linsebigler, A.L.; Lu, G.; Yates, T.J. Photocatalysis on TiO2
surfaces: principles, mechanisms, and selected results.
Chem. Rev 1995, 95, 735-758.
Matsuzawa,

S.;

Tanaka,

Photocatalytic

oxidation

J.;

Sato,
of

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Ibusuki,

T.

dibenzothiophenes

in

acetonitrile using TiO2: effect of hydrogen peroxide and

ultrasound irradiation. J. Photochem. Photobiolo. A 2002,

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TABLE 1 THE COMPOSITION OF THE NANOCOMPOSITE CALCULATED BY

EDX MEASUREMENT

Element

Oxygen

Titanium

Iron

(wt.%)

27.97

69.85

2.18

TABLE 2 THE RESULTS OF BET MEASUREMENT

Samples

Surface area (m2/g)

Pore volume (cm3/g)

Pore size (nm)

TiO2

29

0.016

4.00

0.6 g PEG 2wt% Fe(III)TiO2

152

0.180

4.77

TABLE 3 DEGRADATION PRODUCTS OF THE IRRADIATED SAMPLE

Compounds

Retention time(min)

Dibenzothiophene

10.38

Thiophene, 2-isopentyl Thiophene, 2-(3-methylbutyl), Cyclohexane

11.85

Divinyldimethylsilane

11.98

2-Hexenoic acid, 2-hexenyl ester

12.07

1,2-Bis(N-butoxyimino)ethane

12.87

Thiophene, 2-ethyl

12.92

Thiophene, 2-hexyl Thiophene, 2-pentyl

13.06

Cyclohexane, 1,1-dimethyl

14.56
TABLE 4 THE REMAINING COMPOUNDS AFTER ADSORPTION

Compounds

22

by

Retention time(min)

Tridecane

7.28

Tetradecane

7.81

Pentadecane

8.38

Phenol, 2,6-bis(1,1-dimethylethy)

8.55

Hexadecane

8.99

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FIGURE 1 XRD PATTERNS OF NANOCOMPOSITES (a) calcined at 400oC and (b) calcined at 450oC.

FIGURE 2 TG CURVES OF NANOCOMPOSITE.

FIGURE 3 SEM IMAGES OF NANOCOMPOSITE.

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Advanced Chemical Engineering Research Volume 3, 2014

FIGURE 4 EDX MEASUREMENT

FIGURE 5 NITROGEN ADSORPTION ISOTHERMAL.

FIGURE 6 NITROGEN ADSORPTION-DESORPTION ISOTHERMAL.

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FIGURE 7 THE EFFECT OF PHOTOCATALYST AMOUNT ON DEGRADATION.

FIGURE 8 EFFECT OF INITIAL CONCENTRATION ON DEGRADATION OF DIBENZOTHIOPHEN.

FIGURE 9 THE EFFECT OF IRRADIATION TIME ON DEGRADATION OF DIBENZOTHIOPHEN.

FIGURE 10 CHROMATOGRAM OF THE SAMPLE AFTER IRRADIATION.

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FIGURE 11 CHROMATOGRAM OF THE SAMPLE AFTER ADSORPTION EXPERIMENT.

FIGURE 12 PSEUDO FIRST ORDER KINETICS OF PHOTO

DEGRADATION.

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FIGURE 13 THE EFFICIENCY OF THE PHOTOCATALYST

AFTER REGENERATION.