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Journal of Environmental Chemical Engineering xxx (2014) xxxxxx

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

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

1 Requirements for effective photocatalytic oxidative desulfurization of a

2 thiophene-containing solution using TiO2
3 Q1 Gaetano Dedual a , Matthew J. MacDonald a , Abdullah Alshareef a , Zhijie Wu b ,
4 Daniel C.W. Tsang c, Alex C.K. Yip a, *
5 a
Department of Chemical and Process Engineering, University of Canterbury, Christchurch, New Zealand
6 b
State Key Laboratory of Heavy Oil Processing and the Key Laboratory of Catalysis of CNPC, China University of Petroleum, Beijing 102249, China
7 c
Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, China

A R T I C L E I N F O A B S T R A C T

Article history: Photocatalytic oxidative desulfurization (PODS) is an emerging sulfur removal technology that operates
Received 14 March 2014 at mild temperatures and pressures without the need for the hydrogen gas that is required in
Accepted 17 August 2014 hydrodesulfurization (HDS). This study investigated the desulfurization of a liquid containing 0.95% by
weight sulfur content (aromatic thiophene) in n-octane to simulate the characteristics of fuel. An 8 W
Keywords: mercury lamp was used as the source of irradiation (UV-C) and the reaction was catalyzed by the
Desulfurization photocatalyst TiO2. The optimal temperature, solution pH, catalyst loading, oxidizer dosage, solvent
Photocatalyst
requirement and oil/solvent ratio were investigated for the PODS process. The optimal operating
Oxidation
Kinetics
parameters for a 5500 ppm dibenzothiophene (DBT) (0.95 wt% sulfur content) solution were a
temperature of 40
C, pH of 4, 6 g/L TiO2 (with respect to oil), 0.7% v/v H2O2 and methanol as the
solvent. Prior to this work, an aqueous solvent has always been thought to be an essential ingredient in
the PODS process. This study found that no effective oxidation occurred when only water was used as the
solvent and that the use of methanol signicantly reduced the mass-transfer limitation in the batch
system to result in a much higher overall sulfur removal. At the optimum conditions, overall
desulfurizations of 91% and 64% were achieved after 3 h for DBT and benzothiophene (BT), respectively.
Kinetic studies determined that the reaction rate was highly dependent upon the solution composition.
The results also indicated that the PODS using TiO2 is more selective to DBT than BT.
2014 Published by Elsevier Ltd.

8 Introduction sulfur compounds within liquid fuels to 10 ppm (parts per 22

million) [13]. Such strict limits have been the motive behind the 23
9 The growing world population is placing an accelerating development of many industrial processes aimed at removing the 24
10 reliance on the different methods of public and private sulfur-containing compounds from the blending components of 25
11 transportation, subsequently increasing the amount of environ- liquid fuels. 26
12 mental contaminants released into the atmosphere from the A number of catalytic processes targeted at the removal of 27
13 exhausts of vehicles, buses and airplanes. Sulfur dioxide (SO2) is sulfur-containing compounds from light oil, which is the core 28
14 one of these contaminants that has received considerable amount blending component for liquid fuels, have been developed and 29
15 of scientic research and parliamentary regulations over the past some have been commercialized over the years. The commonly 30
16 decade. This is because when transportation fuels (for example, utilized process within the petroleum industry is hydrodesulfu- 31
17 diesel) are combusted inside engines and machinery, the large rization (HDS) in which light oil is contacted with hydrogen and 32
18 variety of sulfur compounds (thiols, suldes, disuldes and passed over a catalyst bed under a high pressure and high 33
19 thiophenes) within those fuels are converted to SO2 and other temperature reaction environment [2,4,5]. Although HDS is 34
20 airborne particulates and released into the atmosphere [1]. The currently the most widely used process for desulfurization, the 35
21 most recent environmental regulations limit the presence of technology encounters hindrances when oxidizing aromatic 36

thiophenes, such as dibenzothiophene (DBT) and benzothiophene 37

(BT). Difculties in treating the DBT molecules arise from the steric 38

hindrances and stabilization of the S C bond within the molecule 39

* Corresponding author. Tel.: +64 3 364 2534; fax: +64 3 364 2063.
E-mail address: alex.yip@canterbury.ac.nz (A.C.K. Yip). [1,6]. Deep desulfurization of these thiophene molecules can be 40

http://dx.doi.org/10.1016/j.jece.2014.08.012
2213-3437/ 2014 Published by Elsevier Ltd.

Please cite this article in press as: G. Dedual, et al., Requirements for effective photocatalytic oxidative desulfurization of a thiophene-
containing solution using TiO2, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.08.012
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41 achieved by HDS at high reaction temperatures and pressures, with also been reported as successful oxidants for the oxidation process, 73
42 5- to 15-fold larger process units required [7,8]. This implies with overall desulfurization levels of 98% being reported for 5 h 74
43 that using HDS to eliminate the refractory sulfur group is not trials [8,13,14]. 75
44 cost-effective. The investigation into photocatalyst structures and their 76
45 To meet the economic and environmental demands for low compositions has received much interest in the recent years [8]. 77
46 sulfur fuel, many oxidative technologies have been investigated. In Li et al. reported a mixed-phase Fe2O3 catalyst prepared by 78
47 recent years, biological oxidative desulfurization (BODS) has solution combustion method that gave 92.3% sulfur removal of DBT 79
48 reported desulfurization levels of 100% [9]; however, BODS is in n-octane using airow and simulated sunlight [13]. Wang et al. 80
49 hindered by very long reaction times (>24 h) and slow kinetics [1]. prepared TiO2 in ionic liquid via microwave radiation for 81
50 Oxidative desulfurization (ODS) using chemical oxidants is also a PODS and achieved 98.2% of DBT removal from model oil after 82
51 highly researched process because of its mild operating temper- 10 h UV irradiation [14]. More complicated photocatalysts 83
52 atures and pressures (<100
C and 1 atm) and the absence of structures such as anatase nanocomposite polyoxometalate 84
53 hydrogen gas [1,10,11]. Desulfurization levels of 98% have been (Bu4N)7H3[P2W18Cd4(Br)2O68]-TiO2 [15] and titanium silicalite-1 85
54 reported following the use of this technology, which involves short [16] were also reported to be able to increase the overall sulfur 86
55 reaction times of 2 min [10]. Traditionally, ODS operates at removal efciency. PODS using advanced catalytic material, such as 87
56 temperatures between 60 and 80
C [1012]. At these temper- those mentioned above, appear to be a promising method for deep 88
57 atures, the oxidation of desired fuel constituents, such as alkenes desulfurization; nonetheless, the complexity in the synthesis of 89
58 and aromatics, can occur, which consumes part of the oxidant and these photocatalysts and their costs make commercialization and 90
59 decreases the overall octane rating of the fuel [8,11]. Unlike ODS, scaling up very difcult. Therefore, PODS using simple reagent is 91
60 photocatalytic oxidative desulfurization (PODS) can be conducted still considered the best approach from industrial perspective. 92
61 at ambient temperature and atmospheric pressure with high However, systematic evaluation on the optimum reaction con- 93
62 Q2 product selectivity. PODS is essentially an advanced version of ODS ditions for PODS and the effect of the presence of multiple 94
63 with a photocatalyst and UV light that are used to increase the thiophenes are still insufcient. In this study, TiO2 was used as the 95
64 oxidation rate. It is a desirable process because of its low operating photocatalyst, and the effects of catalyst loading, pH, temperature, 96
65 costs and the potential for a free source of radiation (natural the oxidant dose (H2O2) and solvent use were investigated. DBT 97
66 sunlight) [8]. PODS is characterized by three phases: oil, solvent and BT were used as model aromatic sulfur compounds, as 98
67 and catalyst (solid). Thiophene molecules in the oil phase are these compounds are not easily treated using HDS. The reaction 99
68 oxidized at the catalyst surface increasing the molecular polarity, rate constants were calculated for the reactions of DBT and BT. The 100
69 thus causing extraction into the solvent phase (polar) [8]. To effect of DBT and BT co-existence on the overall sulfur removal was 101
70 increase the oxidation of thiophenes, oxidants are generally added also investigated. To remove any matrix effects that may be 102
71 to increase the concentration of hydroxyl radicals, subsequently experienced by the application of real fuel, n-octane was used as 103
72 increasing the sulfone production rate. Pure oxygen and air have model oil. 104

From Power Source Temperature

Probe

Holding Tube Aluminum Foil

UVC Lamp

Quartz Quartz
Reacting Reacting
Vessel Vessel

P-23

Constant Temp Water

Bar Mixer Bar Mixer
Bath

Magnetic Stirrer Plate

Heater

Scheme 1. Reactor setup for the liquid phase PODS process.

Please cite this article in press as: G. Dedual, et al., Requirements for effective photocatalytic oxidative desulfurization of a thiophene-
containing solution using TiO2, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.08.012
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G. Dedual et al. / Journal of Environmental Chemical Engineering xxx (2014) xxxxxx 3

105 Experimental

106 Materials

107 The following reagents and chemicals were used as received

108 without further purication: methanol (Fisher, Scientic, 99%),
109 titanium dioxide (commercial Degussa P-25), zeolite Y (Zeolyst,
110 ammonium form, Si/Al = 2.55), iron (III) nitrate nonahydrate
111 (SigmaAldrich, 99.99%), benzothiophene (SigmaAldrich, 98%),
112 dibenzothiophene (SigmaAldrich, 98%), n-octane (SigmaAldrich,
113 98%), hydrogen peroxide (Thermo, Fisher Scientic, 30% v/v.),
114 sulfuric acid (SigmaAldrich, 98%) and sodium hydroxide
115 (SigmaAldrich, 97%, pellets).
116 The zeolite-Y-supported Fe catalyst (Fe/zeolite-Y) was prepared
117 using an ion exchange method according to the procedure
118 described by Li et al. [17].

119 Photocatalytic oxidative desulfurization (PODS)

120 A 5500 ppm solution of DBT was produced by adding 0.505 g of

121 DBT in 1 L of n-octane, producing a 0.95 wt% sulfur solution.
122 Initially, 10 mL of sulfur solution was added to 10 mL of solvent
123 Fig. 1. Linear relationship between the amount of DBT in n-octane (mmol) and the
(except for the solvent trials where the ratios of oil/solvent were amount of DBT/DBT sulfone in methanol (mmol) during the reaction. The reaction
124 altered) in a quartz reactor, followed by the addition of titanium conditions were 40
C, 6 g/L TiO2, 1:1 v/v methanol to n-octane ratio, 0.7% H2O2 and
125 dioxide (TiO2) or Fe/zeolite-Y. The temperature was maintained by pH 4.
126 a heated water bath equipped with a temperature probe. An 8 W
127 UV-C lamp (Philips TUV 8 W) was used as the source of irradiation from the oil phase during the reaction. The experiments were 167
128 (l = 253.7 nm, 21 mW/cm2 at 1 m). The lamp was enclosed in a duplicated where necessary and the uncertainty was calculated 168
129 quartz tube and was submersed between the two quartz tube from the mean deviation from the average. 169
130 reactors as shown in Scheme 1. The solution pH was adjusted by
131 adding drops of 0.1 M H2SO4 or 0.1 M NaOH. A magnetic stirrer was Results and discussion 170
132 maintained at 500 rpm for the duration of the experiment to
133 ensure adequate mixing. The initial extraction was performed by Solvent requirement of PODS 171
134 mixing the system at the targeted reaction temperature for 10 min
135 Water and methanol were used to determine the inuence of the 172
[18]. The starting time of the catalytic reaction was dened
136 immediately, and the required amount of hydrogen peroxide solvent on the desulfurization rate. Initially, the effectiveness of 173
137 water as a solvent was investigated, and the conditions 0.06 g of TiO2, 174
(H2O2) solution was added to the system subsequent to the initial
138 extraction step. The reaction was performed for 3 h, unless 10 mL of DBT solution, pH of 4 30
C and various H2O2 concentrations 175
139 were used. Another trial was conducted with the identical 176
otherwise specied. Individual experiments were performed to
140 measure the nal sulfur removal after 3 h for different reaction composition but methanol was used as the solvent, as shown in 177
141 Fig. 2. The level of sulfur removal was very low (<10%) when water 178
parameters. For example, 4 individual experiments were per-
142 formed at pH 2, 4, 6 and 7 to study the effect of solution pH. The was used, regardless of the H2O2 concentration. For example, the 179
143 highest concentration of H2O2 (30% v/v) only desulfurized 9% of the 180
volumes of the oil phase and the solvent phase were measured. For
144 kinetic experiments, 0.5 mL of sample was removed from the DBT solution. The overall extent of desulfurization at 3% H2O2 was 2% 181
145 and 62% for the use of water and methanol as the solvent, 182
reactor at the specied time intervals and diluted by adding 2 mL of
146 n-octane and 2 mL of water. To determine the overall removal of respectively. These results disagree with previously published work 183
147 in which a 50% extraction of DBT was achieved with 9% H2O2 and 0.1 g 184
sulfur from the oil, the oil phase was centrifuged for 5 min at
148 2500 rpm. The oil phase was then diluted with n-octane and of Ti-containing zeolite catalyst using water as the solvent and 185
149 owing air [19]. The disagreement could be attributed to a different 186
analyzed using a Varian CP-3800 gas chromatograph. The column
150 used was an EquityTM-1 fused silica (30 m  0.25 mm  0.25 mm design of reactor used in which the reaction conducted with Q3 187
151 188
lm thickness) capillary column. The chromatograph was set to continuous airow provided ideal mixing that was able to offset the
152 hold the oven temperature at 50
C for 1 min then the temperature mass-transfer limitation given by using water as the solvent. The 189
190
153 was increased to 340
C at a ramp rate of 15
C/min and kept for results in this study, therefore, suggest that methanol is a preferred
154 10 min, followed by cooling the oven to 50
C in 20 min. The solvent over water if the PODS reaction is to be carried out in a batch 191
155 mode without owing air. A trial was also conducted with a 192
chromatogram peaks were integrated using the Varian software.
156 The sulfur removal (%) in the oil phase was calculated by heterogeneous photo-Fenton catalyst (Fe3+) supported on zeolite-Y 193
157 {[DBT]t = 0[DBT]t = t}/[DBT]t = 0  100%. Notably, the sulfur re- (Fe/zeolite Y) which has been shown as an effective photo-catalyst 194
158 moval (%) calculated based on [DBT]t = t was consistent with the for oxidation of organics at high concentration through rapid 195
159 removal (%) calculated based on the sulfones concentration in the generation of hydroxyl radicals [20]. Fig. 2 shows that the use of 196
160 methanol phase. Fig. 1 shows a linear relationship (slope = 1) water as the solvent signicantly reduces the overall desulfurization 197
161 between the amount of DBT in n-octane (mmol) and the amount of evenwith high concentration of H2O2 (30%), regardless of the catalyst 198
162 its sulfone in methanol (mmol) at different time intervals. There type or mechanisms of oxidation (TiO2 photocatalytic mechanisms 199
163 was no DBT present in the methanol phase during the reaction or photo-Fenton mechanisms). This result suggests that the low 200
164 except a trace amount at t = 0 min which was resulted from initial sulfur removal possibly results from the reaction being constrained 201
165 extraction prior to the reaction. Based on this analysis, the decrease by mass transfer limitations between the liquid phases rather than 202
166 in DBT concentration in n-octane represents the sulfur removal the low activity of TiO2 or Fe/zeolite-Y. 203

Please cite this article in press as: G. Dedual, et al., Requirements for effective photocatalytic oxidative desulfurization of a thiophene-
containing solution using TiO2, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.08.012
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80 80
70

60
60
Sulfur Removal (%)

Sulfur Removal (%)

50

40
40
30

20

10 20

0
3% 11% 19% 30%
0
H2O2 concentration in the aqueous phase
0 2 4 6 8 10
Water Solvent (TiO2) Methanol Solvent (TiO2)
Catalyst Loading (g/L)
Water Solvent (Fe/zeolite-Y) Fig. 3. Sulfur removal from the apolar phase at different TiO2 catalyst loading after
3 h. The reaction conditions were 30
C, 5500 ppm DBT in n-octane, 1:1 v/v
Fig. 2. Sulfur removal from the apolar phase after 4 h when various H2O2 methanol to n-octane ratio, 3% H2O2 and pH 4. (Note: lines are a guide for the ease of
concentrations were applied in the presence of a TiO2 or Fe/zeolite-Y catalyst. Water viewing.)
or methanol was used as the solvent. The reaction conditions were 30
C, 6 g/L
catalyst loading, 10 mL of 5500 ppm DBT in n-octane, 10 mL solvent (water or
the other reaction characteristics remained as previously stated. In 238
methanol) and pH 4.
these experiments, 29% of the DBT in the apolar phase was 239
204 extracted to the methanol phase in both cases without noticeable 240
The difference in the extent of desulfurization could be due
205 formation of the DBT sulfones. Hence, the inclusion of H2O2 did not 241
to the poor interaction between the oil and water phases. This
206 contribute to the desulfurization when TiO2 was absent. Ultimate- 242
effect was observed by the lack of an emulsion forming
207 ly, the saturation limit of DBT within the methanol phase was 243
between the two liquid phases, in which the water phase would
208 244
split after the reaction was nished. Conversely, methanol 1650 ppm, assuming that the system had reached equilibrium
209 after 4 h. 245
required a signicantly longer time to form a complete split
210 Fig. 3 shows the sulfur removal at different TiO2 loadings, in 246
between the oil and aqueous layers, indicating a better
211 solvent/oil emulsion. which the conditions of a constant temperature at 30
C, 10 mL of 247
212 methanol, 3% H2O2, 10 mL of 5500 ppm DBT solution and a pH of 248
Although other researchers have reported effective sulfur
213 249
removal from real fuel while using water as the solvent and owing 4 were used. The extent of desulfurization increases with
214 increasing TiO2 loading until approximately 67 g/L, at which 250
air as oxidant [13,14], our results suggest that the interaction of the
215 point the sulfur removal reached a maximum of 65%. These 251
solventandoil in a batch reactor isdirectly proportional to the relative
216 extraction characteristics could be due to the increasing hydroxyl 252
oxidation that is achievable, hence the nature of solvent should
217 radical production, as shown in Eqs. (1)(3). However, as the TiO2 253
be considered. The difference in thiophene oxidationwhen methanol
218 loading increases the turbidity of the solution also increases, thus 254
is used is inuenced by a number of different characteristics
219 decreasing UV-C light penetration [19]. This phenomenon has been 255
including the increased solubility of DBT in methanol compared
220 reported in previous investigations regarding optimal catalyst 256
with that inwater and a lower viscosity thanwater [21,22]. The stated
221 loading. The overall sulfur removal is likely decreased when a very 257
characteristics greatly increase the DBT diffusion rate into the solvent
222 high TiO2 loading (10 g/L) is used because of excessive light 258
phase as mass transfer limitations are reduced, facilitating the
223 scattering [5]. 259
photocatalytic reaction. This increased rate is supported by reports
224 that observed an enhancement in desulfurization upon the addition
225 TiO2 hv ! hVB e
CB (1)
of the surfactant Triton X-100, which increased the solubility of DBT
226 in water by one-order of magnitude [21]. Mass transfer limitations
227 have beenpreviouslyencountered forPODS processes, and a previous
228 H2 Oads @H 
ads OHads (2)
study determined that the only useful comparison of catalytic
229 activity could be made when the LL mass transfer effects were
230 eliminated [12]. In addition, no formation of formaldehyde was
231 detected whichsuggests that methanol isa stable solventand that the OH
ads @hVB $  OH (3)
232 oxidation of methanol is negligible during the PODS process.
Effect of the oxidant dosage 260
233 Effect of the TiO2 catalyst loading
Fig. 4 shows the sulfur removal with respect to the oxidant 261
234 Prior to investigating the catalyst loading effect on the system, 262
(H2O2) concentration where the conditions of constant tempera-
235 numerous control experiments were conducted. Two trials were ture at 30
C, 10 mL of methanol, 10 mL of 5500 ppm oil, 6 g/L of 263
236 conducted without TiO2: one with 3% v/v H2O2 (0 g/L catalyst 264
TiO2 and a pH of 4 were used. The maximum sulfur removal was
237 loading, the rst data point in Fig. 3) and another without H2O2; 265
obtained at a concentration of 0.7% v/v H2O2 in the aqueous phase.

Please cite this article in press as: G. Dedual, et al., Requirements for effective photocatalytic oxidative desulfurization of a thiophene-
containing solution using TiO2, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.08.012
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G. Dedual et al. / Journal of Environmental Chemical Engineering xxx (2014) xxxxxx 5

100

80
Sulfur Removal (%)

60

40

20

0
0% 1% 2% 3% 4% 5%
H2O2 Concentration
Fig. 4. Sulfur removal from the apolar phase at different H2O2 oxidant Fig. 5. Desulfurization data obtained after 3 h for DBT solution with different initial
concentrations after 3 h. The reaction conditions were 30
C, 6 g/L TiO2, pH values (prior to UV-C irradiation). The reaction conditions were 30
C, 6 g/L TiO2,
5500 ppm DBT in n-octane, 1:1 v/v methanol to n-octane ratio and pH 4. 5500 ppm DBT in n-octane, 1:1 v/v methanol to n-octane ratio and 3% H2O2.

266 Fig. 5. The solution mixture of methanol, n-octane and the 297
The overall extent of desulfurization decreased with increasing
267 oxidizing agent (H2O2) solution has a natural pH of 4. The pH of the 298
concentrations of H2O2. H2O2 is a strong oxidizing agent that
268 system (pH 27) was altered by adding drops of 0.1 M H2SO4 or 299
produces hydroxyl radicals upon exposure to light (Eq. (4)) [5]. At
269 0.1 M NaOH. The results suggest that the photocatalytic oxidation 300
high dosages of H2O2 (>1%), the oxidation of DBT was hindered due
270 of DBT over TiO2 is largely pH-dependent because the radical 301
to the consumption of hydroxyl radicals by H2O2, as described by
271 formation mechanisms are governed by the redox of active species 302
Eq. (5) [19,23]. This inter-reacting scheme decreases the overall
272 that occurs at the conduction band bottom and the valence band 303
concentration of hydroxyl radicals, thereby decreasing the overall
273 top of TiO2, which is a strong function of the pH of the solution. The 304
reaction rate. High concentrations of H2O2 can lead to the
274 pKa values for H2O2 and hydroxyl radicals are 11.7 and 11.9, 305
poisoning of the catalyst, resulting in the deactivation of the
275 respectively [25]. At a near-neutral pH (pH 67), one-electron 306
TiO2 surface [24]. At lower concentrations of H2O2, the reaction
276 reduction that results in hydroxyl radical formation (Eq. (6a) 307
between the hydroxyl radicals and H2O2 is minimized, while
277 occurs at a higher potential than that resulting in H2O2 formation. 308
providing sufcient radicals to facilitate oxidation. The addition of
278 This reduction causes an increase in the formation of hydroxyl 309
high H2O2 volumes also causes the addition of excess water to the
279 310
system, decreasing the emulsion properties of the uid, as radicals at a rapid rate, which leads to the self-catalyzed oxidation
280 of H2O2. On the other hand, a solution with an initial pH of 3 does 311
described previously. The results indicated that an optimal amount
281 not favor the generation of hydroxyl radicals from H2O2 over TiO2. 312
of hydroxyl radicals produced for oxidation is reached at
282 Therefore, a decrease or increase in the solution pH from a pH of 313
approximately 0.30.7% v/v H2O2.
4 resulted in a remarkable decrease in the sulfur removal. 314
H2 O2 hv 2  OH (4) Operating at a pH of 4 was determined to have the highest overall 315

sulfur removal at 62%. This result agrees with the work performed 316

by Vargas and Nez in which sulfur extraction was found to be 317

H2 O2 OH ! H2 O O
2 H

(5) 318
hindered at high pHs, and an optimal pH of 3 with similar
operating conditions was reported [21]. 319

H2 O2 H e
CB
TiO2 OH H2 O (6a) 320
Effect of the reaction temperature
284
283 The trial also determined that when no H2O2 was added to the
285 system, sulfur removal decreased to 29%. This value coincides with The effect of temperature on desulfurization of the apolar phase 321
286 the sulfur removal found when investigating the TiO2 loading was conducted with the following reaction conditions: 1 mL of 322
287 at 0 g/L. As the overall sulfur removal values are identical, this H2O2 in 10 mL of methanol, 10 mL of 5500 ppm DBT solution, 6 g/L 323
288 result reects the contribution of hydroxyl radicals provided by TiO2 loading and a pH of 4. Fig. 6 shows that at an operating 324
289 direct photolyzis (Eq. (4)), and the oxidation (Eq. ((6a)) of H2O2 on temperature of 40
C, the sulfur removal was maximized at 325
290 the TiO2 surface signicantly outweighs the contribution of approximately 75%. At 40
C, the generation rate of hydroxyl 326
291 the free radicals generated from the route associated with the radicals was at an optimum in which the scavenging of radicals 327
292 adsorption of water, as indicated by Eqs. (2) and (3). Hence, the (self-oxidation) was minimized. At this optimum temperature, the 328
293 inclusion of H2O2 and TiO2 is justied for PODS. amount of DBT adsorbed on the TiO2 surface was larger than that at 329

temperatures above 45
C, which provides higher sulfur removal 330

294 Effect of the solution pH via oxidation on the catalyst surface [5]. Conversely, the oxidation 331

of DBT at 35
C or below was limited by kinetics due to the low 332

295 The inuence of the initial solution pH on sulfur removal from temperatures. The results do not agree with a previous study, in 333
296 the n-octane phase was investigated, and the results are shown in which Wang et al. reported an optimal operating temperature of 334

Please cite this article in press as: G. Dedual, et al., Requirements for effective photocatalytic oxidative desulfurization of a thiophene-
containing solution using TiO2, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.08.012
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6 G. Dedual et al. / Journal of Environmental Chemical Engineering xxx (2014) xxxxxx

increased. At a ratio of 4:1, only 1 mL of oil solution (n-octane) 346

100 347
remained after 4 h. Due to the signicantly increased extraction
potential of the solvent, a solvent/oil ratio of 1:1 was chosen, as 348

characteristics similar to those mentioned above were exhibited at 349

80 2:1 and 3:1 solvent/oil ratios. A solvent/oil ratio of 1:1 was used to 350

allow a thorough investigation of the photocatalytic reaction 351

Sulfur Removal (%)

behavior, as at higher ratios, the reaction was dominated by the 352

direct extraction of DBT into methanol. Sulfur removal decreases 353

60
with decreasing solvent/oil ratio due to the decreased capacity of 354

the solvent uid. With an increasing solvent/oil ratio, the turbidity 355

of the reacting uid was decreased, thus increasing UV light 356

40 357
penetration. These results agree with Trongkaew et al., who
identied that the sulfur removal potential decreased with 358

decreasing solvent/oil ratios [5]. 359

20
Kinetics of thiophenes oxidation 360

From the previously discussed experiments, all optimal 361

0
20 30 40 50 60 reaction characteristics were used in the system, i.e. 40
C 362

operating temperature, 0.7% H2O2, 1/1 (v/v) methanol/oil, 6 g/L 363

TiO2 and a pH of 4. Two separate trials were conducted, and the 364
Temperature (C) 365
extents of the desulfurization of DBT and BT were measured to be
Fig. 6. Effect of temperature on sulfur removal in n-octane after 3 h. The reaction 91% and 64% after 3 h, respectively (Fig. 8). The sulfur removal of 366
conditions were 6 g/L TiO2, 5500 ppm DBT in n-octane, 1:1 v/v methanol to n-octane DBT in n-octane (91%) achieved in this study is comparable to the 367
ratio, 3% H2O2 and pH 4. (Note: lines are a guide for the ease of viewing.) 368
DBT removal (92.3%) reported by Li et al. using a mixed-phase
Fe2O3 [13]. The results in Fig. 8 also show that the overall sulfur 369
335 60
C [26]. The difference in operating temperatures could be due 370
336 removal is highly dependent upon the thiophene that is targeted.
to the use of hexadecane as the solvent of the apolar phase, as 371
337 Q4 opposed to the n-octane used in this study. Due to this Based on previous studies, the pseudo-rst-order reaction has
been modeled [13,14,19,21], as shown in Eq. (6b): 372
338 inconsistency between model oil solutions, temperature trials
339
 
will need to be conducted on the fuel in which the technology is to Ct
340 ln kp t (6b)
be directly applied. Co
where Ct and C0 are the concentrations at time t and time zero, 374
373
341 Effect of the solvent/oil ratio respectively, and kp is the rst-order reaction rate constant (h1). 375

The reaction rate of BT under the same operating conditions is 376

342 Fig. 7 shows that the total sulfur removal increases with an
343
considerably lower, with a rate constant of 0.38 h1 compared with 377
increasing ratio of solvent/oil, with a maximum removal of 86% DBT, with a rate constant of 0.79 h1, as shown in Fig. 9. The half- 378
344 occurring at a ratio of 4:1. At the high solvent/oil ratios, the amount
345 of oil that was extracted into the solvent phase drastically

100

80
Sulfur Removal (%)

60

40

20

0
0 1 2 3 4

Solvent:Oil Ratio (v/v) Fig. 8. Comparison of PODS efciency for a solution containing DBT or BT at optimal
operating conditions: 40
C, 6 g/L TiO2, 0.95 wt% sulfur in n-octane, 1:1 v/v methanol
Fig. 7. Effect of the solvent/oil ratio on sulfur removal after 3 h. The reaction to n-octane ratio, 0.7% H2O2 and pH 4. (Note: lines are a guide for the ease of
conditions were 30
C, 6 g/L TiO2, 3% H2O2 and pH 4. viewing.)

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containing solution using TiO2, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.08.012
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G. Dedual et al. / Journal of Environmental Chemical Engineering xxx (2014) xxxxxx 7

Fig. 9. Plot of the pseudo-rst order kinetic model for the removal of DBT and BT by
the PODS process.

Fig. 10. Sulfur removal from the apolar phase of a mixture of BT and DBT in solution
379 life of the experiment was calculated by substituting Ct with C0/2. (0.96 wt% sulfur in total) at the optimal conditions: 40
C, 6 g/L TiO2, 1:1 v/v
380 methanol to n-octane ratio, 0.7% H2O2 and pH 4. (Note: lines are a guide for the ease
This substitution results in Eq. (7), where t1/2 is the half-life (h).
of viewing.)
0693
t1=2 (7) 417
kp oxidation reactivity to BT compared with DBT [26]. Desulfurization
rates of 48.2% and 55.5% were measured for BT and DBT, 418
382
381 From the kinetics study, the half-lives of the DBT and BT
respectively, from their work using TiO2. Although, in principle, 419
383 reactions were determined to be 0.9 and 1.8 h, respectively. These
the structure of the BT molecule possesses a relatively accessible 420
384 values show that the degradation rate of BT is signicantly slower
sulfur atom that could lead to a higher oxidation rate, the SC 421
385 than that of DBT, in agreement with the literature [6,26,27]. A
bond stabilization in the BT molecule offsets this advantage by 422
386 different set of optimal operating conditions may be required for
providing a lower electron density about the sulfur atom [28]. As a 423
387 efcient BT oxidation because the electron densities about the
result, decreased oxidation rates of sulfur with the photoholes 424
388 sulfur species in the DBT and BT molecules are considerably
during irradiation are experienced in the BT molecule (Eq. (8)). The 425
389 different [8]. This difference causes different interactions of DBT
symbol (*) represents the aromatic nature of the sulfur atom. 426
390 and BT with the hydroxyl radicals generated over TiO2.

hVB S ! S (8)
391 Multicomponent PODS
Conversely, the inducing effect of the aromatic rings in DBT 428
427
causes an increase in the electron density about the sulfur atom. 429
392 To nalize the investigation into desulfurization, a trial was
This increased density allows oxidation to occur readily even 430
393 conducted where BT and DBT produced a total sulfur content of
though DBT contains a more sterically hindered sulfur atom. 431
394 0.96 wt% (0.48 wt% sulfur individually). Fig. 10 shows that the
Scheme 2 depicts the UV-assisted DBT/BT oxidation and the 432
395 sulfur removal efciency is heavily inuenced by the composition
excitation of electron within a TiO2 particle. As the photocatalyst 433
396 of the oil phase uid. This effect was observed by a decrease in the
receives 3.2 or more eV of energy, the electrons are excited from 434
397 sulfur removal of DBT and BT at 180 min to 84 and 48%,
the valence band to the conduction band, in turn facilitating the 435
398 respectively, compared with the oxidation of a single component
reaction of H2O2 and water that produces hydroxyl radicals. 436
399 (91% sulfur removal for DBT and 64% sulfur removal for BT). The
Although it is commonly accepted that the potential of the valence 437
400 oxidation of the two species resulted in a total sulfur removal of
band of TiO2 is low enough to oxidize water, which possibly 438
401 68%, which was signicantly lower than that achieved by pure DBT.
contributes to the formation of hydroxyl radicals, our results 439
402 The results show that the sulfur removal from both DBT and BT
suggest that this reaction from water is negligible as the PODS 440
403 increased simultaneously at a similar initial rate before the rst
process presented in this work is capable of achieving DBT 441
404 10 min. The sulfur removal of BT then increased at a much slower
405 rate compared to that of DBT from 25 min. This result suggests that
406 the photocatalytic oxidation is more selective to DBT than BT. Table 1
407 Table 1 shows that the reaction rate constant of the DBT Pseudo-rst-order kinetic parameters for the removal of DBT and BT via PODS
408 reaction decreased from 0.79 h1 (DBT only) to 0.55 h1 (DBT + BT process using TiO2.
409 system), indicating that the incorporation of other thiophene Species Rate constant, kp (h1) R2 Half life (h) Overall sulfur
410 compounds decreases the kinetics of PODS. In addition, because removal (%)
411 the reaction is, to some extent, limited by the external mass BT 0.38 0.85 1.8 64
412 transfer and the available catalyst surface, competitive adsorption DBT 0.79 0.98 0.9 91
413 and desorption of DBT and BT on the catalyst may also inuence the Combine (BT)a 0.15 0.66 4.6 48
414 kinetics, resulting in reaction rates that are different from reactions Combin (DBT)a 0.55 0.96 1.3 84
415 with only single component involved. The kinetic data (Fig. 10) a
Kinetic parameters for BT and DBT removal were calculated individually for the
416 agree with those reported by Wang et al. who reported lower combined mixture.

Please cite this article in press as: G. Dedual, et al., Requirements for effective photocatalytic oxidative desulfurization of a thiophene-
containing solution using TiO2, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.08.012
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8 G. Dedual et al. / Journal of Environmental Chemical Engineering xxx (2014) xxxxxx

Scheme 2. Illustration of the photocatalytic oxidation of DBT/BT with oxidants and UV irradiation catalyzed by TiO2. The PODS process could be useful in decreasing the
remaining sulfur content after the traditional HDS process to achieve deep desulfurization.

442 oxidation without the requirement/presence of additional water for supporting this work. We also wish to thank the technical 475
443 (except the small amount contained in the H2O2 solution). The support given by Michael Sandridge on sample analysis, and 476
444 radicals generated from TiO2 react with the DBT/BT molecules at Maryam A. M. Fuad and Alif Zainudin for their help on collecting 477
445 the oil-solvent interface near the catalyst surface and the resulting some useful experimental data. 478
446 products are then extracted into the polar phase. The molecular
447 structure of the oxidized species was not characterized in this References 479
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containing solution using TiO2, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.08.012
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containing solution using TiO2, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.08.012