1232 Energy & Fuels 2000, 14, 1232-1239

Oxidative Desulfurization of Light Gas Oil and Vacuum

Gas Oil by Oxidation and Solvent Extraction
Shujiro Otsuki, Takeshi Nonaka, Noriko Takashima, Weihua Qian,
Atsushi Ishihara, Tamotsu Imai, and Toshiaki Kabe*
Department of Chemical Engineering, Tokyo University of Agriculture and Technology,
Tokyo 184-8588, Japan

Received May 15, 2000. Revised Manuscript Received September 5, 2000

The oxidation of model sulfur compounds (thiophene derivatives, benzothiophene derivatives,

and dibenzothiophene derivatives), straight run-light gas oil (SR-LGO, S: 1.35 wt %), and vacuum
gas oil (VGO, S: 2.17 wt %) were conducted with a mixture of hydrogen peroxide and formic
acid. The thiophene derivatives with 5.696 to 5.716 electron densities on the sulfur atoms could
not be oxidized at 50 °C. Benzo[b]thiophene with 5.739 electron density and other benzothiophene
and dibenzothiophenes with higher electron densities could be oxidized. The sulfur compounds
in SR-LGO and VGO appeared to be oxidized to a detectable levels (c.a., 0.01 wt % S) by GC-
FPD analysis. The IR spectra of oxidized SR-LGO and VGO showed that sulfones were formed
by oxidation. The removal of sulfur compounds by extraction became more effective for the oxidized
samples than for the original samples. Lighter sulfur compounds were preferentially extracted.
The extraction efficiencies of solvents, i.e., N,N′-dimethylformamide (DMF), acetonitrile (ACN),
methanol, varied greatly. The most effective solvent for the removal of sulfur compounds was
DMF. The recovery of oil was, however, lowest with DMF.

Introduction pounds for oxidation is increased with the increase of

electron density on sulfur atom. The reactivities of DBT
A new method to reduce the sulfur content in fuel oil
derivatives are influenced by the electron donation of
is needed today to meet the future legislation on a sulfur
substituted methyl groups, and; therefore, the reactivity
content, e.g., lower than 50 ppm. The conventional
decreases in the order of 4,6-DMDBT > 4-MDBT >
method for reducing sulfur is catalytic hydrodesulfur-
DBT, reversing the order of reactivities for HDS.7 After
ization (HDS) under severe conditions. It has been
oxidation, the sulfur compounds are transformed to
reported that methyl substitution at 4 and 6-positions
sulfones. The extraction of sulfones is considered to be
of dibenzothiophene (DBT) remarkably retards the rate
useful method for removal.13-17 Aida et al. have reported
of HDS and, thus, that 4-methyldibenzothiophene (4-
the removal of sulfur compounds to a very low level from
MDBT) or 4,6-dimethyldibenzothiophene (4,6-DMDBT)
fossil fuels by oxidation, distillation, extraction and
is very difficult to convert due to its steric-hindrance
adsorption. They reduced the sulfur content of light gas
even under deep desulfurization conditions.1,2 Namely,
oil from 0.56% to 0.018%. After adsorption with alu-
the reactivities of DBT’s decrease in the order of DBT
mina, the sulfur content decreased to 0.0038% after
> 4-MDBT > 4,6-DMDBT.
oxidation and extraction with N,N′-dimethylformamide.
Various studies on oxidative desulfurization (ODS)
However, the extent of the oxidation and removal of
have been reported.3-20 The reactivity of sulfur com-
oxidized sulfur compounds was not reported.7,18-20
(1) Kabe, T.; Ishihara, A.; Qian, W. Hydrodesulfurization and Herbstman et al. have reported that the sulfur content
Hydrodenitrogenation; KODANSHA WILEY-VCH: New York, 1999. of a 288 °C+ Atmospheric Reduced Arabian Crude was
(2) Kilanowski, D. R.; Teeuwen, H.; de Beer, V. H. J.; Gates, B. C.;
Schuit, G. C. A.; Kwart, H. J. Catal. 1978, 55, 129. decreased to 1.48% from 2.6%. That is, 43% desulfur-
(3) Ford, J. F.; Young, V. O. Prepr. Div. Petro. Chem., Am. Chem. ization was achieved by selective oxidation followed by
Soc. 1965, 10(2), C-111. a high temperature thermal or KOH treatment.21
(4) Heimlich, B. N.; Wallace, T. J. Tetrahedron 1966, 22, 3571.
(5) Paybarah, A.; Bone, R. L.; Corcoran, W. H. Ind. Eng. Chem. As mentioned above, various ODS methods have been
Process Des. Dev. 1982, 21, 426. reported. Nevertheless, the extent of the oxidation of
(6) Attar, A.; Corcoran, W. H. Ind. Eng. Chem. Prod, Res, Dev. 1978,
17(2), 102. (15) Tam, P. S.; Kittrell J. R. US Patent 4 485 007, 1984.
(7) Aida, T. Catalysts & Catalysis 1995, 37(3), 243. (16) Tam, P. S.; Kittrell, J. R.; Eldridge, J. W. Ind. Eng. Chem. Res.
(8) Zannikos, F.; Lois, E.; Stournas, S. Fuel Process. Technol. 1995, 1990, 29(3), 321.
42, 35. (17) Tam, P. S.; Kittrell, J. R.; Eldridge, J. W. Ind. Eng. Chem. Res.
(9) Smetana, R. D. US Patent 3 595 778, 1971. 1990, 29(3), 324.
(10) Takeyama, T. JP Patent 290 793, 1987. (18) Aida, T.; Yamamoto, D.; Sakata, K. Trans. Mater. Res. Soc. Jpn.
(11) Shiraishi, Y.; Hara, H.; Hirai, T.; Komasawa, I. Ind. Eng. Chem. 1993, 18A, 391.
Res. 1999, 38, 1589. (19) Aida, T.; Yamamoto, D. Prepr. Am. Chem. Soc. Div. Fuel Chem.
(12) Shiraishi, Y.; Hirai, T.; Komasawa, I. Ind. Eng. Chem. Res. 1994, 39(2), 623.
1998, 37, 203. (20) Aida, T.; Funakoshi, I. JP Patent 197 035, 1995.
(13) Guth, E. D.; Diaz, A. F. US Patent 3 847 800, 1974. (21) Herbstman, S.; Patel, J. Am. Chem. Soc., Div. Petro. Chem.,
(14) Guth, E. D.; Arledge, N. L. US Patent 3 919 402, 1975. Prep. 1982, 27, 826.

10.1021/ef000096i CCC: $19.00 © 2000 American Chemical Society

Published on Web 10/14/2000
Oxidative Desulfurization of Gas Oil Energy & Fuels, Vol. 14, No. 6, 2000 1233

Table 1. Properties of Feed SR-LGO and VGO added. The mixture was stirred for 12 h at 25 °C. The mixture
feed SR-LGO VGO was heated to 50 °C, added with 160 mL of H2O2 and 30 mL
of formic acid and stirred for 12 h at 50 °C. The last 120 mL
sulfur (%) 1.35 2.17 of H2O2 and 40 mL formic acid were added, and the mixture
nitrogen (%) 0.011 0.0518 was further stirred for 12 h before it was cooled to room
density at 15 °C (g/mL) 0.8580 0.9161
temperature.
IBP (°C) 245.5 206.5 The extraction of SR-LGO was conducted by using a 300
5 vol % (°C) 275.5 mL separatory funnel. 150 mL of SR-LGO and 150 mL of
10 vol % (°C) 284.5 378.0
solvent were charged, and, then, the mixture was shaken for
20 vol % (°C) 407.5
30 vol % (°C) 300.5 424.5 10 min at room temperature before the oil and solvent layers
50 vol % (°C) 313.5 449.0 were separated.
70 vol % (°C) 329.5 474.0 Oxidation and Extraction of VGO. The oxidations of
80 vol % (°C) 488.5 VGO were conducted in the same way as SR-LGO. The first,
90 vol % (°C) 356 508.5 200 mL of H2O2 and 35 mL of formic acid were added to 800
95 vol % (°C) 367.5 mL of VGO and stirred for 12 h at 25 °C. After that, the
EP (°C) 375.5 557.0 mixture was heated to 70 °C, 160 mL of H2O2 and 30 mL of
formic acid were further added and stirred for 12 h at 70 °C.
sulfur compounds and the existence of difficult-to- The last, 120 mL of H2O2 and 30 mL formic acid were added
extract sulfur compounds have not been reported. It is and stirred for 12 h, and, then, the mixture was cooled to room
desirable to find whether the incomplete removal of temperature. The oil layer was washed with 150 g of water 3
sulfur compounds from oil is attributed to incomplete times and evacuated at 10-3 Torrs at 100 °C for 0.5 h to dry
oxidation of sulfur compounds involved or to ineffective the sample.
extraction. The extractions of VGO were conducted by mixing in a two-
neck glass flask with a stirrer. 100 mL of VGO sample and
In this study, the relationship between the electron
100 mL of solvent were combined with stirring at 50 °C, and,
densities of sulfur atoms and reactivities was investi- then, oil and solvent were separated. The recovered oil was
gated for the oxidation of model sulfur compounds with further extracted with 150 mL of solvent up to 10 times.
hydrogen peroxide and formic acid. Then, the oxidation γ-Al2O3 Adsorption of Oxidized SR-LGO after Solvent
of real feeds, i.e., SR-LGO and VGO, was carried out to Extraction. Adsorption of sulfur compounds remained in oil
determine the extent of the oxidation of sulfur com- layer after solvent extraction using γ-Al2O3 was carried out
pounds and the extent of sulfur removal by extraction. in a glass flask with a stirrer. 60 g of oil layer and 10 g of
γ-Al2O3 were mixed at room temperature for 10 h, and, then,
Experimental Section oil and adsorbent were separated by filtration. The γ-Al2O3
after adsorption was extracted with CCl3 by Soxhlet extraction
Materials. The feeds used in this study were SR-LGO and method to recover the adsorbed sulfur compounds.
VGO, and their properties are given in Table 1. The model Analysis. The reaction products were analyzed by a gas
sulfur compounds, i.e., methyl phenyl sulfide, thiophenol, chromatography, i.e., GC/MS (Shimadzu GCMS-QP5050) and
diphenyl sulfide, DBT, benzo[b]thiophene (BT), 2-methylth- GC-FID, GC-FPD (Shimadzu GC-14A). An identification of the
iophene (2-MT), 2,5-dimethylthiphene (2,5-DMT), thiophene sulfur compounds in SR-LGO was carried out using a GC-AED
(commercial GR grade), 31% H2O2, formic acid and a mixture as reported previously.27 The total sulfur contents of SR-LGO
of cis- and trans-decahydronaphthalene (decalin) were ob- and VGO were analyzed by XRF (Rigaku Co.Ltd.). The total
tained from Kishida Chemicals. The concentration of H2O2 was sulfur contents of VGO were also analyzed by a GC-FPD
determined by iodometric titration before use.3,22 DBT deriva- (Shimadzu GC-14A). Infrared spectroscopy analyses of SR-
tives including 4-MDBT, 4,6-DMDBT, dibenzothiophene-1, LGO and VGO were carried out by using FT/IR-5300 (Japan
1-dioxide (DBT sulfone), 4-methyldibenzothiophene-1,1-dioxide Spectroscopic Co. Ltd.).
(4-MDBT sulfone), 4,6-dimethyl- dibenzothiophene-1,1-dioxide Calculations of Electron Density on Sulfur Atom. The
(4,6-DMDBT sulfone) were synthesized by reported Computer Aided Chemistry (CAChe) worksystem provided by
methods.23-26 Polar solvents for extraction, i.e., N,N′-dimethyl- CAChe Scientific Inc. was used to calculate the electron density
formamide (DMF), acetonitrile, methanol, dimethyl sulfoxide of the sulfur atom in the sulfur compounds by using the Sony
(DMSO), and sulfolane (commercial GR grade), were obtained Tektronixs CAChe system (CAChe, 1995) and the Molecular
from Kishida Chemicals. Orbital Package (MOPAC, Version 6.00). The PM3 (Modified
Oxidation of Model Sulfur Compounds. The oxidation Neglect of Diatomic Overlap, Parametric Method 3) semiem-
of model sulfur compounds was conducted in a flask with a pirical Hamiltonian developed by Stewart (1989) was employed
magnetic stirrer. A 100 mL portion of decalin solution contain- to solve the Schrödinger equation to calculate the optimum
ing 10 representative model sulfur compounds and 5 mL of geometry and electronic properties of the sulfur compounds
formic acid were added to the flask. The mixture was stirred using the standard parameters.
and heated to 50 °C, and, then, 10 mL of 31 wt % H2O2 was
added. H2O2 /sulfur ratio was 160 mol/mol. The reaction was
Result
continued for 360 min.
Oxidation and Extraction of SR-LGO. The oxidation of Oxidation of Model Sulfur Compounds. The
SR-LGO was conducted in a glass flask. An excess amount of electron densities on the sulfur atom of sulfur com-
H2O2 and formic acid was used to oxidize the sulfur compounds
pounds, i.e., thiol, sulfides, thiophenes, and their ben-
thoroughly. The first, 800 mL of SR-LGO was charged, and,
then, 200 mL of 31 wt % H2O2 and 35 mL of formic acid were
zene and/or dimethyl-substituted derivatives, are shown
in Table 2. The electron densities are in the range of
(22) Ali, P.; Russel, L. B.; William, H. C. Ind. Eng. Chem. Prod, Res, 5.696 to 5.915. Figure 1 shows the relationships between
Dev. 1982, 21, 426. the sulfone yields of model compounds and reaction
(23) Gilman, H.; Jacoby, A. L. J. Org. Chem. 1938, 4, 108. time. The electron densities of thiophenol and two
(24) Campaigne, E.; Hewitt, L.; Ashby, J. J. Heterocyclic Chem.
1969, 6, 553.
(25) Gredil, R.; Lucken, E. A. C. J. Am. Chem. Soc. 1965, 87, 213. (27) Kabe, T.; Ishihara, A.; Tajima, H. Ind. Eng. Chem. Res. 1992,
(26) Gilman, H.; Esmay, D. L. J. Am. Chem. Soc. 1952, 74, 2021. 31, 1577.
1234 Energy & Fuels, Vol. 14, No. 6, 2000 Otsuki et al.

Table 2. Electron Densities on Sulfur Atom and Rate Constants

Figure 2. Relationships between the rate constants, k of

model compounds, and the electron densities.

sulfones. The oxidation of every compound was treated

as a pseudo-first-order reaction, and the oxidation rate
Figure 1. Relationships between the sulfone yields of model constants were calculated and summarized in Table 2.
compounds and reaction time. These apparent rate constants decreased in the order:
methyl phenyl sulfide > thiophenol > diphenyl sulfide
sulfides, methyl phenyl sulfide, and diphenyl sulfide > 4,6-DMDBT > 4-MDBT > DBT > BT. The relation-
were relatively higher values among these sulfur com- ships between the rate constants of the oxidation of
pounds. The electron densities of thiophene derivatives these model sulfur compounds to corresponding sul-
were changed in the range from 5.696 (thiophene) to fones, and the electron densities are shown in Figure
5.760 (4,6-DMDBT). 2,5-DMT, 2-MT, and thiophene 2. This result indicates that rate constant increases with
have relatively lower electron densities, 5.716, 5.706, the increase of electron density.
and 5.696, respectively. The oxidation of these com- Oxidation and Extraction of SR-LGO. The mix-
pounds did not take place. BT (electron density ) 5.739) ture of SR-LGO and oxidant became three layers after
and other model compounds with higher electron densi- oxidation: oil layer (top), residual layer (bottom), and
ties than BT were oxidized to form corresponding aqueous layer (middle). The recovery and the sulfur
Oxidative Desulfurization of Gas Oil Energy & Fuels, Vol. 14, No. 6, 2000 1235

Figure 3. GC-FPD chromatograms of oil layers of SR-LGO before and after oxidation.

Table 3. Recoveries and Sulfur Contents in Three Table 4. Recoveries of Oils and Solvent Layers after
Fractions after Oxidation of SR-LGO and VGO Extraction of SR-LGO and Sulfur Contents
distribution recovery of oil sulfur content total yielda recovery of oilb sulfur contentc
of SR-LGO in (%) (wt %) (%) (%) (%)
oil layer 89.8 0.65 DMF
residual layer 9.0 8.8 extraction
aqueous layer 1.2 NDa SR-LGO 99.7 88.2 0.57
oxidized SR-LGO 99.5 85.9 0.11
distribution recovery of oil sulfur content acetonitrile
of VGO in %) (wt %) extraction
SR-LGO 99.7 96.2 1.13
oil layer 87.9 1.48
oxidized SR-LGO 99.8 90.1 0.10
residual layer 11.2 6.5
methanol
aqueous layer 0.90 NDa
extraction
a ND: non determination. SR-LGO 97.8 95.8 1.13
oxidized SR-LGO 99.5 90.5 0.18
DMSO
contents of these layers are summarized in Table 3. The extraction
recovery of the oil layer after oxidation was 89.8%. The SR-LGO 99.7 95.4 1.06
sulfur content of oil layer of the oxidized sample was oxidized SR-LGO 99.4 91.1 0.11
reduced to 0.65 wt % from 1.35 wt % in the original SR- sulfolane
LGO. In addition, the color of oxidized SR-LGO was extraction
SR-LGO 99.7 96.0 1.08
darker than fresh samples. oxidized SR-LGO 99.2 94.8 0.12
Figure 3 shows the GC-FPD chromatograms of oil a {(oil + solvent recovered)/(oil + solvent fed)} × 100. b {(oil
layers before and after oxidation. The GC peaks of sulfur recovered)/(oil fed)} × 100. c XRF analysis.
compounds in oil layers of oxidized samples were shifted
to the heavier direction. The content of sulfur was wt %. In the extraction of oxidized SR-LGO, all of the
reduced after oxidation, as determined by GC-FPD and solvents except for methanol were the effective solvents
XRF analyses. to extract the oxidized sulfur compounds up to c.a.
The recoveries of oil layers from the extractions of 0.10%. In the extraction of unoxidized SR-LGO, DMF
unoxidized and oxidized SR-LGO with DMF, acetoni- was the most effective solvent among five polar solvents.
trile, methanol, DMSO, and sulfolane are summarized Nevertheless, the recovery of oil layer extraction with
in Table 4. The recoveries of oxidized SR-LGO were in DMF was the lowest.
the range 1.2-6.1% lower than that of unoxidized SR- The concentrations of DBT derivatives, i.e., DBT,
LGO, and the extent decreased in the order: acetonitrile 4-MDBT, 4,6-DMDBT in unoxidized SR-LGO and DB-
> methanol > DMSO > DMF > sulfolane. The sulfur TO2, 4-MDBTO2 and 4,6-DMDBTO2 in oxidized SR-
contents of oxidized SR-LGO after extraction with the LGO, are shown in Table 5. In the extraction of oxidized
five solvents were in the range of 0.10 to 0.18 wt %, SR-LGO, the concentrations of DBT derivatives de-
whereas those of unoxidized SR-LGO were 0.57 to 1.13 creased to less than one ppm level, whereas the total
1236 Energy & Fuels, Vol. 14, No. 6, 2000 Otsuki et al.

Table 5. Concentrations of Dibenzothiophene Derivatives in Oil Layers

unoxidized oxidized
SR-LGO SR-LGO
dipole dielectric DBT 4-MDBT 4,6-DMDBT total S DBTO2 4-MDBTO2 4,6-DMDBTO2 total S
moment (µ) constant () [ppm]a [ppm]a [ppm]a [ppm]b [ppm]a [ppm]a [ppm]a [ppm]b
feed 1620 3350 525 1.35 19 67 19 0.65
DMF 3.24 36.71 26 71 16 0.57 <1 <1 <1 0.11
acetonitrile 3.53 35.94 165 567 101 1.13 1 <1 <1 0.10
methanol 2.87 32.66 315 769 112 1.13 <1 <1 <1 0.18
DMSO 4.06 46.45 28 169 48 1.06 <1 1 <1 0.11
sulfolane 4.81 43.26 34 163 40 1.08 <1 <1 <1 0.12
a Determined by GC-FPD analysis. b Determined by XRF analysis.

Figure 4. IR spectra of SR-LGO before and after oxidation, extraction with acetonitrile, and Soxhlet-extracted compounds adsorbed
on γ-Al2O3.

sulfur content decreased to c.a. 0.1%. The DBT deriva- In addition, the IR spectrum of Soxhlet-extracted
tives became easier to remove by the increase in polarity compounds adsorbed on γ-Al2O3 is shown in Figure 4.
after oxidation to form sulfone. The spectrum shows that the sulfur compounds remain-
Figure 4 shows the IR spectra of SR-LGO before and ing in SR-LGO after acetonitorile extraction is sulfones.
after oxidation and extraction with acetonitrile. The Oxidation and Extraction of VGO. The product of
specific infrared absorption of sulfone (1165 cm-1, 1289 VGO oxidation became three layers; oil layer (top),
cm-1)28 was observed indicating that sulfone was formed residual layer (bottom), and aqueous layer (middle). The
by oxidation, and this sulfone was effectively removed recoveries and the sulfur contents are summarized in
with extraction. The colors of oxidized SR-LGO was Table 3. The recovery of oil layer was 87.9%. The sulfur
darker than fresh sample but became similar to that of content of oil layer was 1.48 wt % compared with 2.17
fresh sample after extraction. wt % of the original VGO.
γ-Al2O3 Adsorption of Oxidized SR-LGO after The extractions of sulfur compounds from the oxidized
Solvent Extraction. Figure 5 shows the four GC-FPD oil layer and the original VGO were conducted with
chromatograms such as (A) unoxidized SR-LGO, (B) acetonitrile, methanol, and DMF. Figure 6 shows the
oxidized SR-LGO, (C) the oil layer of the oxidized SR- changes in the recoveries of oil layers as a function of
LGO after extraction with acetonitrile, and (D) Soxhlet- number of extraction before and after oxidation. The
extracted compounds adsorbed on γ-Al2O3 in SR-LGO recoveries of oil layers decreased in the order: methanol
after acetonitrile extraction. The sulfur compounds > acetonitrile > DMF. The recoveries of oil layers
remaing in SR-LGO after acetonitorile extraction (peak decreased to about 10-15% lower than before oxidation.
D) shifted to the heavier direction. This result indicates Figure 7 shows changes in the sulfur concentrations
that most of the remaining sulfur compounds were in oil layers. The sulfur contents are summarized in
oxidized to sulfones. Table 6. The sulfur removal became more effective after
oxidation. After 10 times of extraction with acetonitrile,
(28) Nakanishi, K. IR Absorption Spectroscopy, Nankodo, Japan methanol and DMF, the sulfur content of oxidized
1960, p 58. sample decreased from 1.48 wt % of the original VGO
Oxidative Desulfurization of Gas Oil Energy & Fuels, Vol. 14, No. 6, 2000 1237

Figure 5. GC-FPD chromatograms of SR-LGO before and after oxidation, extraction with acetonitrile, and Soxhlet-extracted
compounds adsorbed on γ-Al2O3.

Figure 6. Changes in recoveries of oil layers as a function of Figure 7. Changes in sulfur concentration of oil layers as a
number of extraction before and after oxidation. (O-Unoxidized function of number of extraction before and after oxidation.
VGO extracted with acetonitrile; b- Oxidized VGO extracted (O-Unoxidized VGO extracted with acetonitrile; b- Oxidized
with acetonitrile; 4-Unoxidized VGO extracted with methanol; VGO extracted with acetonitrile; 4-Unoxidized VGO extracted
2-Oxidized VGO extracted with methanol; 9-Oxidized VGO with methanol; 2-Oxidized VGO extracted with methanol;
extracted with DMF). 9-Oxidized VGO extracted with DMF).

Table 6. Sulfur Concentrations in Oil Layers of VGO

to 0.12, 0.21, and 0.01 wt %, respectively. DMF is the after Extractions
most effective solvent among the three solvents. None-
unoxidized VGO oxidized VGO
theless, we did not find a significant difference in 2.17 wt % 1.48 wt %
extraction among the solvents for the unoxidized VGO.
feed first 10 th first 10 th
GC-FPD chromatograms of unoxidized and oxidized extraction times (wt %) (wt %) (wt %) (wt %)
VGO after acetonitrile extraction are shown in Figure
acetonitrile 2.44 1.45 1.09 0.12
8. The GC peaks of sulfur compounds in the oxidized methanol 2.06 1.76 1.67 0.21
sample shifted to the heavier direction. The chromato- DMF 0.41 0.01
grams showed that lighter sulfur compounds were
preferentially removed by extraction. Especially, the sulfur compounds in VGO could be
As shown in Figure 8, after 10 times extractions with oxidized with hydrogen peroxide and formic acid down
acetonitrile the sulfur compounds remaining in the to the 0.01 wt % level (DMF extraction) as determined
oxidized VGO sample are much heavier than those in by GC-FPD.
the unoxidized sample. Further, similar results were Figure 9 shows IR spectra of oil layers before and after
obtained when DMF was used as extraction solvent. oxidation and extraction with acetonitrile. In these
1238 Energy & Fuels, Vol. 14, No. 6, 2000 Otsuki et al.

Figure 8. GC-FPD chromatograms of unoxidized and oxidized VGO after extractions with acetonitrile.

Figure 9. IR spectra of oil layers before and after oxidation and extraction with acetonitrile.

spectra, the sulfone was observed (1152 cm-1, 1298 reported by Aida et al.7,18-20 The divalent sulfur of DBT
cm-1) and this sulfone compounds decreased to unde- can be oxidized by the electrophilic addition reaction of
tectable levels by 10 times extraction with acetonitrile. oxygen atoms to the hexavalent sulfur of DBT sulfone.
In addition, it should be noted that colors of oxidized Hence, the reactivity of oxidation becomes higher for a
VGO were darker than fresh sample, but color of sulfur atoms with a higher electron density. Ford et al.
oxidized VGO after extraction turned to pale white. reported the similar results that the lower rate of
oxidation of thiophenic compounds than sulfides.3 The
Discussion observed trend of the rate with the structure is ac-
Relationship Between the Reactivities and Elec- counted for in terms of (a) reduced availability of the
tron Densities on Sulfur Atom. The oxidation of DBT lone pair electrons and (b) steric strain in the reaction
with hydrogen peroxide and formic acid has been products, sulfoxides and sulfones. The sulfur atoms of
Oxidative Desulfurization of Gas Oil Energy & Fuels, Vol. 14, No. 6, 2000 1239

2,5-DMT, 2-MT and thiophene have electron densities of sulfones with lower molecular weight is greater than
of 5.716, 5.706 and 5.596, respectively. These low that with higher molecular weight. Figure 8 shows the
electron densities are not sufficient to be oxidized by GC-FPD chromatograms of unoxidized and oxidized
hydrogen peroxide and formic acid. Nevertheless, BT, VGO after consecutive extraction with acetonitrile.
of which the electron density is 5.739, and other model These results show that lower molecular weight sulfur
compounds with higher electron densities can be oxi- compounds were preferentially removed by extraction.
dized to form corresponding sulfones. Therefore, the The remaining sulfur compounds after repeated extrac-
minimum value to cause the oxidation under the condi- tion of oxidized sample appeared to be sulfones with
tions used for this study appears to exist between 5.739 higher molecular weight, which is lower polarity. The
and 5.716. incomplete removal of sulfur compounds is, therefore,
Generally, the oxidation of DBT is considered to be a not attributed to the insufficient oxidation but to the
consecutive reaction, i.e., sulfur-containing compoundsf insufficient extraction capacity of the solvent and low
sulfoxidefsulfone. In our study, no sulfoxide was polarities of higher molecular weight solfones. Hence,
detected by GC analysis under all reaction conditions. the removal of sulfur compounds can be improved by
Therefore, the rate-determining step is the “sulfidef using a solvent with higher polarity.
sulfoxide”, and sulfoxide formation is considered to The Side Reaction and Formation of Residual
dominate the reaction rate. In the present study, an Layer. Oxygen-containing functional groups such as
apparent rate constant was used to discuss the reactiv- ketone (1715 cm-1), aldehyde (1725 cm-1), ester (1735
ity of several sulfur compounds. cm-1), and epoxy (3000-3050 cm-1) were not observed
Identification of Sulfur Compounds in Oxida- in oil layer after oxidation of SR-LGO and VGO by IR
tion of SR-LGO. Alkyl-substituted BT’s and alkyl- analysis. Nevertheless, the sulfur compounds and ole-
substituted DBT’s are contained in SR-LGO.27 The finic compounds in SR-LGO and VGO are expected to
electron densities of these alkyl-substituted BT’s and oxidized selectively to form discolored gummy material
alkyl-substituted DBT’s in SR-LGO are higher than the via chain reactions induced by hydrogen peroxide.31
minimum value to cause the oxidation. Indeed, the GC- Residue was 9.0 wt % of the feed SR-LGO containing
FPD chromatogram of the oxidized oil layer shows that 8.8 wt % sulfur. Therefore, the sulfur contents of oil
sulfur compounds shifted to the heavier direction, layer were reduced to 0.65 wt % from 1.35 wt % sulfur
indicating the formation of corresponding sulfones, as in the original SR-LGO. Thus, 52% sulfur of the original
shown in Figure 3. The formation of sulfones are content was removed by oxidation via the formation of
detected by IR spectra (Figure 4). Moreover, Figure 4 sulfur-rich residue. In the same way, for VGO oxidation,
and Figure 5 show that the sulfur compounds remaining the residue with high sulfur concentration formed to
after acetonitorile extraction is oxidized to sulfones. reduce the sulfur contents of original VGO to 1.48 wt
Identification of Sulfur Compounds in Oxida- % from 2.17 wt %. Hence, 32% sulfur removal by
tion of VGO. Figures 8 and 9 show that the sulfur oxidation is due to the formation of residual layer.
compounds were oxidized to form sulfone derivatives.
Ma et al.29 performed identification and quantification
Conclusions
peaks of organic sulfur compounds in VGO. This paper
reported that the four types of sulfur compounds, e.g., (1) When the electron density on sulfur atom was
alkylbenzothiophenes with alkyl carbon atoms from 2 higher, the rate constant of oxidation was higher. The
to 16, alkyldibenzothiophenes with alkyl carbon atoms oxidation of model sulfur compounds with H2O2 and
from 0 to 6, alkylbenzonaphthothiophenes with alkyl formic acid showed the minimum value of electron
carbon atoms from 0 to 5 and alkylphenanthro[4,5-b,c,d]- density to cause the oxidation exists between 5.739 and
thiophenes with alkyl carbon atoms from 2 to 7, were 5.716.
basically present in the VGO. The electron densities of (2) The oxidation of the sulfur compounds in SR-LGO
these four types of sulfur compounds in VGO are more and VGO with H2O2 and formic acid took place to a 0.01
than the minimum value to cause the oxidation under wt S level as determined by GC-FPD, XRF, and IR
the conditions used for present study. Therefore, the analyses.
oxidation of this sulfur compounds is expected to take
(3) The solvent with higher polarity extracted oxidized
place.
sulfur compounds (sulfones) more effectively. DMF was
Effect of the Polarity of Solvent on Extraction.
the most effective polar solvent among the solvents
The dipole moment provides a means for measuring the
used. The sulfur content of oxidized VGO was reduced
polarity, or electrical dissymmetry, of a molecule.30 The
to 0.01 wt % S by consecutive 10-time extractions.
dipole moment of solvents used for this study decreases
in the order: sulfolane > DMSO > acetonitrile g DMF
> methanol. In addition, dielectric constant decreases Acknowledgment. Authors are grateful to Mr.
in the order: DMSO > sulfolane > DMF > acetonitrile Tatsushima, Mr. Iwasa, and Mr. Mizuno of Nikki-
> methanol as shown in Table 5. Therefore, the ap- Universal Co. Ltd. for conducting XRF analysis for the
proximate value of polarity decreases in the order: determination of sulfur contents.
sulfolane, DMSO > DMF, acetonitrile > methanol. EF000096I
The dipole moment, µ, is defined as follow.
(29) Ma, X.; Sakanishi, K.; Isoda, T.; Mochida, I. Fuel 1997, 76(4),
µ ) qr 329.
(30) Riddick, J. A.; Bunger, W. B.; Sakano, T. K. Organic Solvents,
4th ed; John Wiley & Sons: New York, 1986.
where q is the electric charge, and r is the distance (31) Collins, F. M.; Lucy, A. R.; Sharp, C. J. Mol. Catal. A: Chem.
between electric charges. Thus, the molecular polarity 1997, 117, 397.