Applied Energy 88 (2011) 175179

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Oxidative desulfurization of diesel with TBHP/isobutyl aldehyde/air

oxidation system
Wei Guo, Chengyong Wang, Peng Lin, Xiaoping Lu *
Institute of Sonochemical Engineering, Nanjing University of Technology, Nanjing 210009, Jiangsu, China

a r t i c l e

i n f o

Article history:
Received 30 March 2010
Received in revised form 29 July 2010
Accepted 3 August 2010

Keywords:
Oxidative desulfurization
Diesel
Air
TBHP
Isobutyl aldehyde
Acetonitrile

a b s t r a c t
Oxidative desulfurization of hydrogenation diesel (40 mL) was studied using air as oxidant, tert-butyl
hydroperoxide (TBHP) as radical initiator at ambient pressure and moderate temperature in the presence
of isobutyl aldehyde. TBHP could accelerate the production of carbonyl radical and its peroxidation.
When the molar fraction of TBHP was 5 mmol, the conversion of DBT could reach 96.1% in the present
of 20 mmol isobutyl aldehyde and air, which was more than that of 85.5% without initiator. The air
was an effective oxidant and acetonitrile was an optimal solvent in this process. The sulfur content of
the hydrogenation diesel could be reduced from 403 to 13 ppm (96.8% removed) under the synergistic
effect of air, TBHP and isobutyl aldehyde.
2010 Elsevier Ltd. All rights reserved.

1. Introduction
It is well known that the sulfur compound in the fuels is an
important source of air pollution, which leads directly to emission
of SO2 and sulfate particulates. In order to reduce pollution, new
specications for sulfur in diesel have been established in many
countries, e.g., less than 15 ppmw in the United States, while in
Europe sulfur concentration below 10 ppmw have been projected
[1,2].
The hydrodesulfurization (HDS) is one of the largest scale
chemical processes to remove sulfur from diesel. Traditional HDS
is the hydro-treatment process that requires hydrogen and a catalyst to break up the sulfur-containing compounds in diesel in order
to form hydrogen sulde. It is highly efcient for removing suldes, disuldes and some thiophene derivatives. However, recent
studies on HDS indicate that organic sulfur compounds remaining
in low sulfur diesel fuel are dibenzothiophene (DBT) and alkyl-DBT
with alkyl substitutions at four- and/or six-position. The concentrations of these compounds are lower in HDS reactivity and are
classied as the most refractory compounds in conventional HDS.
Therefore, to meet the challenges of producing ultraclean fuels,
both investment and operational costs would be rather high due
to more severe operating conditions [35]. The reactivities of the
sulfur compounds in hydrodesulfurization process follow the
order of thiophenes > 2-methylthiophene(2-MT) > 2,5-dimethylthio* Corresponding author. Fax: +86 025 83588072.
E-mail address: xplu@njut.edu.cn (X. Lu).
0306-2619/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2010.08.003

phene(2, 5-DMT) > benzothiophene(BT) > DBT > 4-methyldibenzothiophene(4-MDBT) > 4,6-dimethyldibenzothiophene(4,6-DMDBT).
A new alternative technology, oxidative desulfurization (ODS),
has been applied to remove the refractory sulfur impurities in diesel fuel, especially the dibenzothiophene [611]. Otsuki et al. [12]
reported the following trend for the sulfur compound oxidation
reactivity in a formic acid/H2O2 system: 4,6-DMDBT > 4-MDBT >
DBT > BT > thiophenes. The thiophenic derivant could be oxidized
to sulfone more easily than thiophene because the electronic effect
of substituent are larger than the steric effect. Usually, hydrogen
peroxide and TBHP are used as the oxidizing reagents because of
its high oxidisability in the ODS process. Various studies of oxidation system on this process have been reported, such as H2O2/
formic acid [13], H2O2/inorganic solid acids [14], Mo/Al2O3 and
H2O2 [8], TBHP/Bi-Mo/Siral [15], CpMo(CO)3Cl/H2O2orTBHP [16],
(Me3TACN)Mn/TBHP [17], V-Mo/TBHP [18], Mo/Al2O3/TBHP [19].
Recently, the molecular oxygen has been used as the oxidizing
reagent in the ODS process because it is cheap, nonpolluting, not
strongly corrosive and commercially available. Some studies on
this process have been reported, such as: O2/aldehyde/cobalt catalysts [9], O2/aldehyde [10] and O2/FePc(NO2)4 [20]. In these processes, the sulfur compounds are oxidized by the oxidizing
agents to give rise to the corresponding sulfones which can be easily removed from the diesel by subsequent solvent extraction [21].
Rao [22] studied the oxidation reactions using aldehyde/molecular oxygen to proceed through autoxidation of aldehyde, forming
an acyl radical. Acyl radical on reaction with molecular oxygen
forms a peroxy radical. Peroxy radical abstracts a hydrogen atom

176

W. Guo et al. / Applied Energy 88 (2011) 175179

Scheme 1. Oxidation of DBT by aldehyde/molecular oxygen.

from the other aldehyde molecule, forming peracid and another

acyl radical in the chain propagation step (Scheme 1). But the oxidation and removal effect of sulfur compounds in HDS diesel was
unobvious. Moreover, it was necessary to extract twice, increasing
the utilization quantity of the solvent.
We developed an efcient and simple ODS process for the production of ultra low sulfur diesel fuel using air as oxidant, TBHP as
initiator at ambient pressure and moderate temperature in the
presence of isobutyl aldehyde.

Hydrogen, nitrogen and oxygen gases were used as carrier and

the ow rates were all 35 mL/min. The sample volume of 4 lL
was injected without solvent dilution. The GCPFPD instrument
was calibrated with standard sulfur in diesel fuel obtained from
Research Institute of Petroleum Processing (RIPP) of SINOPEC
Group.
GCMS was used to detect the oxidized organic phase to analyze the composition and study the oxidation mechanism.
3. Results and discussion

2. Experimental
3.1. The mechanisms of aldehyde autoxidation desulfurization
2.1. Materials
Diesel obtained from SINOPEC Yangzi Petrochemical Co., Ltd. is
the hydrodesulfurization (HDS) one. However, it still has a high
sulfur content of about 400 ppm with the DBT as the main sulfocompound. The isobutyl aldehyde and acetonitrile were offered
by Shanghai Linfeng Chemical Reagent Company. TBHP was offered
by Sinopharm Chemical Reagent Co., Ltd. (SCRC).
2.2. Oxidative desulfurization procedure
A 100 mL round-bottom ask equipped with a condenser and
connected to an oxygen cylinder was placed in a water bath. About
5 mmol TBHP, 20 mmol isobutyl aldehyde and 10 mL acetonitrile
were added in and the mixture was stirred for 30 min at 308 K under atmospheric pressure in atmosphere of oxygen which was provided by the cylinder. Then 40 mL HDS diesel were introduced into
the reaction system and stirred for 45 min at 333 K. After reaction,
the mixture was left at room temperature for 10 min to achieve
phase separation. Subsequently, the diesel phase was withdrawn
and the sulfur concentration was measured.
2.3. Analysis of sulfur content
A gas chromatography (GC) coupled with pulsed ame photometric detector (PFPD) was used to indentify the various sulfur
compounds and their concentration. The GC was equipped with a
split injection port and operated in split mode. A 30 m  0.32
mm  0.25 mm SE-54 capillary column was used for separation.

The TBHP could be used as oxidant in the presence of various

catalysts in ODS process [1519]. The oxidative desulfurization of
HDS diesel was carried out at 333 K using the TBHP as oxidant
only. And we found that almost no oxidation of DBTs was observed
in the absence of the catalyst in the process, which was consistent
with the result summarized by Wang [19]. However, the TBHP
could enhance the desulfurization effect in the absence of the catalyst under the synergistic effect of air, TBHP and isobutyl aldehyde
in our ODS process. Therefore, we concluded that the TBHP only
acted as radical initiator to increase the aldehyde autoxidation
speed in the rst reaction step in our process and the probable
brief mechanisms were as follows (Scheme 2). Firstly, the TBHP
is decomposed to release initiator free radical under 308 K. Further
increase in temperature is not preferred due to TBHP losses. Secondly, the initiator free radical reacts with aldehyde, forming an
acyl radical, in the aldehyde/air/solvent mixed liquid. On the effect
of air, acyl radical transforms to peroxy radical. The peroxy radical
abstracts a hydrogen atom from the other aldehyde molecule,
forming peracid and another acyl radical in the chain propagation
step, which agrees with Scheme 1. Finally, the DBT is oxidized to
DBT sulfone by the peracid, which was removed by entering the
solvent phase.
3.2. Effect of the temperature on oxidative desulfurization of HDS
Diesel
To study the effect of temperature on oxidative process, the oxidative desulfurization of HDS diesel were carried out at 298, 308,

177

W. Guo et al. / Applied Energy 88 (2011) 175179

333 and 353 K, respectively. Fig. 1 shows that the conversion rises
with the increase of time before 45 min. However, owing to the
low-boiler volatilizing, the conversion was declined at 60 min.
Fig. 1 also shows that the conversion reaches 90% at 45 min and
333 K, which was better than those at 298, 308 and 353 K. It is because that 353 K was higher than the boiling point of isobutyl aldehyde which led to the loss of isobutyl aldehyde.
3.3. Effect of the isobutyl aldehyde on oxidative desulfurization
Some aldehydes, such as n-octanal, benzaldehyde, cinnamaldehyde, isobutyl aldehyde, n-butyraldehyde, were studied in the ODS
process [9,22]. And the isobutyl aldehyde was the most suitable
because of the well desulfurization effect. The effectiveness of isobutyl aldehyde was studied in oxidative desulfurization of HDS
diesel under 333 K and atmospheric pressure in an oxygen atmosphere for 45 min; the results were presented in Fig. 2.
It shows that extraction by acetonitrile can reduce sulfur only
from 403 to 257 ppm (36.1% removal) in the absence of isobutyl
aldehyde. The conversion increased with the increase of the molar

Conversion (%)

Scheme 2. Peracid formation.

Isobutyl aldehyde (mmol)

Fig. 2. Effect of the isobutyl aldehyde on oxidative desulfurization of HDS diesel.

Conversion (%)

fraction of isobutyl aldehyde originally and reached 92.7% when

the molar fraction of isobutyl aldehyde was 20 mmol. However,
the desulfurization ratio declined a little when the molar fraction
of isobutyl aldehyde exceeded 20 mmol. It is because that the isobutyl aldehyde polymerized in the ODS process and the polymerization was detected by GCMS. The isobutyl aldehyde in the
system reduced because of the self polymerization, which led to
the reduction of its peroxidation. Therefore, the amount of isobutyl
aldehyde was not the more the better.
3.4. Effect of the TBHP on oxidative desulfurization

Time (min)

Fig. 1. Conversion % of the DBT in HDS diesel at different temperatures.

The initiator can provide the free radicals easily. TBHP was the
initiator of free radical reaction in the ODS process. As we can see
in Fig. 1, the oxidative time of the process was only 45 min and it
turned out to be an ideal result. However, the oxidative time of the
process without initiator was about 180 min [22]. We can infer
that the TBHP could accelerate the production and peroxidation
of carbonyl radical oxidation, thus reduced the oxidative time.

178

W. Guo et al. / Applied Energy 88 (2011) 175179

Conversion (%)

To study the effectiveness of TBHP, experiments were carried

out on oxidative desulfurization of HDS diesel under 333 K and
atmospheric pressure in an oxygen atmosphere for 45 min, these
results were presented in Fig. 3. It shows that when the molar fraction of TBHP is 5 mmol, the conversion reaches 96.1% which was
higher than that of 85.5% without TBHP. However, the conversion
declined instead when the molar fraction of TBHP exceeded
5 mmol. It is probably because that the excess TBHP inhibited
the chain reactions by scavenging carbonyl free radicals, which decreased the production of peroxide. Therefore, the desulfurization
ratio decreased with the increase of TBHP.
3.5. Effect of the air ow rate on oxidative desulfurization
The molecular oxygen was widely used as oxidant in the ODS
process [9,10,20]. However, using air as oxidant in the ODS system
was rare. Some researchers think that the oxidation susceptibility
of air is week because it only contains 21% molecular oxygen of total volume.
It was cheap, nonpolluting and commercially available to use
air as oxidant. Fig. 4 shows that air is effective oxidant in this
ODS system and the conversion can reach 80.8% when the air ow
rate was only 0.02 L/min. It also shows that the extent of sulde
oxidation is increased along with the increase of air ow rate
and the conversion reaches 97% when the ow rate was 0.1 L/
min. The variation of conversion was unobvious when the ow rate
exceeded 0.1 L/min. It implied that the air consumption was enough in the ODS process.
3.6. Effect of solvent on oxidative desulfurization

Conversion (%)

The solvent could offer ideal autoxidation environment for aldehyde in this ODS process. To study the effect of solvent, oxidative
desulfurization of diesel was carried out using acetonitrile, dimethylformamide and methanol as solvents and the results are presented in Table 1. Among the solvents studied, acetonitrile was
found to be the most suitable solvent followed by dimethylformamide and methanol. The sulfur content was reduced from 403
to 13 ppm (96.8% removal) when the acetonitrile as solvent. And
the effectiveness of dimethylformamide was lower than that of
acetonitrile and its conversion was only 80%. Even though solubility of sulfones is more in dimethylformamide, acetonitrile is more

Air flow rate (L/min)

Fig. 4. Effect of the air ow on oxidative desulfurization of HDS diesel.

Table 1
Effect of solvent on oxidative desulfurization of HDS diesel.
Solvent
1
2
3
4

Diesel, no oxidation, no
extraction
Acetonitrile
Dimethylformamide
Methanol

Amount
(mL)

Sulfur content
(ppm)

Conversion
(%)

403

10
10
10

13
81
201

96.8
80
50.1

Table 2
Effect of acetonitrile on oxidative desulfurization of HDS diesel.

1
2
3

Acetonitrile (mL)

Conversion (%)

Recovery of diesel (%)

5
10
20

82.2
90.6
96.3

98
97
88

effective in overall oxidation and extraction process [22]. The solvent also could act as extractant to remove the sulfones in the oxidative system. This reactive extraction process transferred the
sulfones into the solvent, which could accelerate the reaction
speed and enhance the reaction fractional conversion. After reaction, the acetonitrile phase was detected by GCPFPD and the sulfur content was almost equal to that removed from the
hydrogenation diesel. The effects of the amount of acetonitrile on
oxidative desulfurization of HDS diesel were studied and the
results are presented in Table 2. It shows that the conversion
increases with the increase of the amount of the acetonitrile in this
oxidative process. And it reaches 96.3% when the acetonitrile was
added to 20 mL. However, the recovery of diesel was declined to
88% which was lower than that of 10 mL acetonitrile. It is because
that the part of the diesel was extract to the acetonitrile phase
which led to the loss of diesel.
4. Conclusion

TBHP (mmol)
Fig. 3. Effect of the TBHP on oxidative desulfurization of HDS diesel.

It can be concluded that the TBHP/isobutyl aldehyde/air system

is very efcient for oxidation of DBT in the HDS diesel and the
operation conditions are mild. Diesel with sulfur content of
403 ppm was oxidized at 333 K and ambient pressure, and a diesel
with total sulfur content of 13 ppm (96.8% removal) could be

W. Guo et al. / Applied Energy 88 (2011) 175179

obtained. TBHP could accelerate the production of carbonyl radical

and its peroxidation.
This oxidative desulfurization process has three advantages
compared with other reported oxidative desulfurization processes.
The rst one is that the reaction can be carried out at lower temperature and within a very short reaction time. The second is that
air can be used as efcient oxidant compared to costly oxidants,
such as H2O2, ozone and TBHP, which were reported in the literatures for the oxidative desuurisation processes. And the third
advantage is that this oxidative system could work very well in
the absence of metal catalyst, which could reduce economy cost
and metallic pollution.
References
[1] Venner SF. Hydrocarbon process. Int Ed 2000;51:510.
[2] Mayo S, Gudde NJ, Brevoord E, Plantenga F. Paper AM-02-38. National
Petroleum and Reners Association annual meeting, San Antonio, TX; 2002.
p. 179.
[3] Tailleur RG, Ravigli J, Quenza S, Valencia N. Catalyst for ultra-low sulfur and
aromatic diesel. J Appl Catal A: Gen 2005;282:22735.
[4] Garcia TV, Tapia JAO, Oehmichen RL. Conceptual design of a reactive
distillation process for ultra-low sulfur diesel production. J Chem Eng
2005;106:11931.
[5] Wei WM, Fu YT. Enhance efciency of tetraoctylammonium uoride applied to
ultrasound-assisted oxidative desulfurization (UAOD) process. J Appl Catal A:
Gen 2007;319:23745.
[6] Sampanthar JT, Xiao H, Dou J, Nah TY, Rong X, Kwan WP. A novel oxidative
desulfurization process to remove refractory sulfur compounds from diesel
fuel. J Appl Catal B: Environ 2006;63:8593.
[7] Gutirrez JLG, Fuentes GA, Murrieta F, Navarrete J, Cruz FJ. Ultra-deep oxidative
desulfurization of diesel fuel with H2O2 catalyzed under mild conditions by
polymolybdates supported on Al2O3. J Appl Catal A: Gen 2006;305:1520.
[8] Gutirrez JLG, Fuentes GA, Murrieta F, Navarrete J, Cruz FJ. Ultra-deep oxidative
desulfurization of diesel fuel by the Mo/Al2O3H2O2 system: the effect of
system parameters on catalytic activity. J Appl Catal A: Gen 2008;334:36673.

179

[9] Murata SK, Kidena K, Nomura M. A novel oxidative desulfurization system for
diesel fuels with molecular oxygen in the presence of cobalt catalysts and
aldehydes. J Energy Fuels 2004;18:11621.
[10] Bernal HG, Caero LC, Alejandre AG. Liquid phase oxidation of
dibenzothiophene with aluminasupported vanadium oxide catalysts: an
alternative to deep desulfurization of diesel. J Catal Today 2009;142:22733.
[11] Giuseppe AD, Crucianelli M, Angelis FD. Efcient oxidation of thiophene
derivatives with homogeneous and heterogeneous MTO/H2O2 systems: a
novel approach for, oxidative desulfurization (ODS) of diesel fuel. J Appl Catal
B: Environ 2009;89:23945.
[12] Otsuki S, Nonaka T, Takashima N, Qian W, Ishihara A, Imai T, et al. Oxidative
desulfurization of light gas oil and vacuum gas oil by oxidation and solvent
extraction. J Energy Fuels 2000;14:12329.
[13] Tam PS, Kittrell JR, Eldridge JW. Desulfurization of fuel oil by oxidation and
extraction. Enhancement of extraction oil yield. J Ind Eng Chem Res
1990;29:3215.
[14] Verduzco LFR, Garcia ET, Quintana RG, Guevara FM. Desulfurization of diesel
by oxidation/extraction scheme: inuence of the extraction solvent. J Catal
Today 2004;98:28994.
[15] Prasad VVDN, Jeong KE, Chae HJ, Kim CU, Jeong SY. Oxidative desulfurization of
4,6 dimethyl dibenzothiophene and light cycle oil over supported
molybdenum oxide catalysts. J Catal Commun 2008;9:19669.
[16] Gamelas CA, Costa AP, Simplcio AL, Roy B. Selective and mild oxidation of
suldes to sulfoxides or sulfones using H2O2 and CpMo(CO)3Cl as catalysts. J
Tetrahedron Lett 2008;49:470812.
[17] Barker JE, Ren T. Sulde oxygenation by tert-butyl hydroperoxide with
mononuclear (Me3TACN)Mn catalysts. J Tetrahedron Lett 2005;46:68058.
[18] Qumica F, Ing D. V-Mo based catalysts for oxidative desulfurization of diesel
fuel. J Catal Today 2009;148:428.
[19] Wang DH, Qian EW, Amano H, Okata K, Ishihara A, Kabe T. Elucidation of
promotion effect of cobalt and nickel on Mo/TiO2 catalyst using a S tracer
method. J Appl Catal A: Gen 2003;253:919.
[20] Rui ZX, Juan L, Na WX, Kun J, Wei M. Oxidative desulfurization of
dibenzothiophene based on molecular oxygen and iron phthalocyanine. J
Fuel Process Technol 2009;90:31723.
[21] Rappas AS. Unipure Corporation. US Patents US 64,02,940, US 64,06,616,
Wachs WO 03/051,798.
[22] Rao TV, Sain B, Kafola S, Nautiyal BR, Sharma YK, Nanoti SM, et al. Oxidative
desulfurization of HDS diesel using the aldehyde/molecular oxygen oxidation
system. J Energy Fuels 2007;21:34204.