1622

Energy & Fuels 2007, 21, 1622-1627

Aspects of Selective Adsorption among Oxidized Sulfur Compounds

in Fossil Fuels
Omid Etemadi and Teh Fu Yen*
Department of CiVil and EnVironmental Engineering, UniVersity of Southern California,
Los Angeles, California 90089-2531
ReceiVed January 11, 2007. ReVised Manuscript ReceiVed March 29, 2007

Solid adsorbents were tested for adsorbing oxidized sulfur compounds to identify a selective adsorbent for
completion of an oxidative process that was enhanced by ultrasound irradiation. Therefore, the advantages of
both oxidative and adsorptive desulfurization have been put together for an upgraded system. Gas chromatograms
from a gas chromatograph-sulfur chemiluminescence detector (GC-SCD) evaluate the efficiency and selectivity
of different adsorbents on different model sulfur compounds. As a single adsorbent, acidic alumina adsorbs
5.7 mg sulfur/g of alumina from an oxidized refractory sulfur compound. Acidic alumina is capable of
maintaining its capacity at more than 98% after calcining for regeneration. Adsorption studies were carried
out to find the effect of particle size and surface area along with the pore size of each adsorbent. Acidic
alumina shows promising results as an adsorbent in the ultrasound-assisted oxidative desulfurization (UAOD)
process to achieve ultralow sulfur fuel (ULSF).

1. Introduction
Application of a selective solid adsorbent is an important
phase in novel desulfurization techniques. The sulfur content
limits of fossil fuels are shifting to a further level of ultraclean
fuel. New emission regulations have raised the demand for
ultradeep desulfurization technologies. Scarce global resources
demand higher efficiency improvements along with reduction
in pollutants and new emission control standards. The maximum
level of sulfur compounds in the U.S. for diesel and gasoline
has been reduced from 500 to 15 and 30 ppmw, consecutively
in June of 2006.1,2 The conventional desulfurization methods
are facing challenges to reach this very low sulfur content in
fossil fuels in a feasible way. Organic sulfur compounds (OSCs)
in fossil fuels are converted to SOx upon combustion. These
compounds are sources of secondary pollutants that produce
acid rain. Due to their higher selectivity, SOx are adsorbed to
catalytic converters and occupy the sites that are designed for
CO and NOx reduction. Moreover ultradeep desulfurization
produces a fuel that can be reformed to a sulfur-free hydrogen
source for fuel cell systems.
Hydrodesulfurization (HDS) is the major process in refineries
for sulfur removal through hydrotreating of fuels. Therefore in
order to reach new sulfur content limits, severe conditions are
necessary to produce ultralow sulfur fuel (ULSF). Higher
temperature and pressures, along with more catalysts and longer
residence time, lead to higher operation costs in the refining
process. Deep HDS will at the same time reduce the lubricity
of the treated fuel. A sulfur removal method with a technique
of selective oxidation and adsorption for producing ULSF has
various advantages over HDS, one being the elimination of
hydrogen consumption. Oxidative desulfurization has been
* Corresponding author. E-mail: TFYen@usc.edu.
(1) U.S. EPA. June 1 Marks Historic Milestone in Clean Diesel; June
2006.
(2) U.S. EPA. Program Update: Introduction of Cleaner-burning Diesel
Fuel Enables AdVanced Pollution Control for Cars, Trucks and Buses;
October 2006.

studied extensively in recent years.3-6 Sulfur compounds have

more affinity to oxidation than their analogue hydrocarbons in
fossil fuels. High conversions of sulfides to sulfones and
sulfoxides provide a difference in polarity that can be used for
selective removal of OSCs with solid adsorbents. Oxidation and
adsorption in ultrasound-assisted oxidative desulfurization
(UAOD) processes at ambient temperature and atmospheric
pressure can provide a clean fuel that meets the new emission
control standards with minimum harm to membranes and
catalytic converters.7
Slightly more polar OSCs are selectively oxidized through
UAOD processes with high yields. These oxidized compounds
of sulfur can be removed at low temperature and ambient
pressure by solid adsorption. Solid adsorption has been developed for desulfurizing diesel fuels at lower temperature and
pressure than hydrotreating technologies.8 The S Zorb SRT
process can achieve ultralow levels of sulfur in lighter portions
of the fluid catalytic cracker (FCC) stream. Hydrogen consumption is still needed along with the sorbent in the S Zorb SRT
process but in lower amounts than the conventional hydrotreating methods. Another adsorption process was developed at
Pennsylvania State University, termed PSU-SARS, by using a
composite metal catalyst on porous substrate. Selective adsorp(3) Attar, A.; Corcoran, W. H. Desulfurization of Organic Sulfur
Compounds by Selective Oxidation. 1. Regenerable and Nonregenerable
Oxygen Carriers. Ind. Eng. Chem. Res. 1978, 17, 102-109.
(4) Zannikos, F.; Vignier, V. Desulfurization of Petroleum Fractions by
Oxidation and Solvent Extraction. Fuel Process. Technol. 1995, 42, 3545.
(5) Otsuki, S.; Nonaka, T.; Takashima, N.; Qian, W. H.; Ishihara, A.;
Imai, T.; Kabe, T. Oxidative Desulfurization of Light Oil and Vacuum Gas
Oil by Oxidation and Solvent Extraction. Energy Fuels 2000, 14 (6), 12321239.
(6) Collins, F. M.; Lucy, A. R.; Sharp, C. Oxidative Desulphurization
of Oils via Hydrogen Peroxide and Heteropolyanion Catalysts. J. Mol. Catal.
A: Chem. 1997, 117, 397-403.
(7) Etemadi, O.; Yen, T. F. Aspects of Selective Adsorption UltrasoundAssisted Oxidative Desulfurization Process of Diesel Fuels. Prepr. Pap.s
Am. Chem. Soc., DiV. Fuel Chem. 2006, 51 (2), 820.
(8) Covert, C. How Philips S ZORB Sulfur Removal Technology Quickly
Came to Life. World Refin., Pet. Refin. Sect. 2001.

10.1021/ef070016b CCC: $37.00 2007 American Chemical Society

Published on Web 05/03/2007

Aspects of SelectiVe Adsorption

Energy & Fuels, Vol. 21, No. 3, 2007 1623

Table 1. Physical Properties of Adsorbents

type

particle size
(m)

pore size
()

surface area
(m2/g)

acidic alumina
activated carbon
zinc oxide

104
45-150
44

58
2
N/A

155
1500
N/A

Table 2. Physical Properties of Alumina Powders

type

particle size

pore size
()

surface area
(m2/g)

acidic alumina
basic alumina
neutral alumina
nanopowder alumina
(whiskers)

104 m
104 m
104 m
2-4 nm

58
58
58
N/A

155
155
155
350-720

tion in this process is at low temperature and atmospheric

pressure without hydrogen consumption.9 Adsorption capacity
and regeneration of adsorbents are matters to be considered for
scaleup techniques in refineries. It has been reported that for a
CuY adsorbent with an activated alumina guard bed, sulfur
compounds will burn off at 350 C and Cu2+ will reduce to
Cu+ at 450 C.10 Experimental results on oxidized forms of
OSCs in this paper clarify the advantages of solid adsobents
for further use in UAOD processes. Acidic alumina as a single
adsorbent has capacities as high as 5.7 mg sulfur/g of alumina.
As an adsorbent, alumina can be regenerated through calcining
at temperatures between 400 and 550 C while maintaining 98%
of its original capacity.
2. Experimental Methods
2.1. Materials. Benzothiophene sulfone (BTO) was purchased
from Alfa Aesar. Dibenzothiophene (DBT) and dibenzothiophene
sulfone (DBTO), aluminum oxide (activated, acidic, Brockmann
I, standard grade, 150 mesh, 58A), aluminum oxide (activated,
basic, Brockmann I, standard grade, 150 mesh, 58A), aluminum
oxide (activated, neutral, Brockmann I, standard grade, 150 mesh,
58A), aluminum oxide (nanopowder, whiskers, 2-4 nm), activated
carbon (Darco KB-B, pore size 2 cm3/g pore volume), and zinc
oxide (>99%) were obtained from Aldrich Chemical Inc. Toluene,
N,N-dimethyl formamide (DMF), and hydrogen peroxide (30
vol %) were obtained from VWR Inc.
2.2. Instruments. The gas chromatograph (GC) used is a 6890N
Agilent Series with a flame ionization detector (FID). This
instrument is coupled with a sulfur chemiluminescence detector
(SCD) Sievers model 355. This sulfur-in-oil analyzer (SLFA-20)
is manufactured by Horiba, Inc.
2.3. Analysis. On the basis of ASTM method D4294-83,
nondispersive X-ray fluorescence (NDXRF) was used to determine
the total sulfur contents. The sulfur concentration of samples was
determined with the sulfur-in-oil analyzer (SLFA-20). This instrument measures the total sulfur concentration for samples with sulfur
content ranges of 0.002-5 wt %. For products with a total sulfur
content of 20 ppmw (0.002 wt %) and less, the concentration of
each sulfur compound was quantified with a GC-SCD. Sulfur
compounds in the feed and product were analyzed by gas chromatography (6890N Agilent Series) with an FID, coupled with a
SCD Sievers model 355 for simultaneous injection of fuel samples
to identify both sulfur and nonsulfur containing compounds.
The chromatograph was fitted with a 60 m HP-5 fused-silica
column that was installed directly into the discharge tube. The
(9) Ma, X. L.; Sun, L.; Song, C. S. A new approach to deep desulfurization of gasoline, diesel fuel and jet fuel by selective adsorption for ultraclean fuels and for fuel cell applications. Catal. Today 2002, 77 (1-2),
107-116.
(10) Yang, R. T.; Hernandez-Maldonado, A. J.; Yang, F. H. Desulfurization of Transportation Fuels with Zeolites Under Ambient Conditions.
Science 2003, 301, 79-81.

Figure 1. Linear calibration curve of DBTO by the GC-SCD.

Figure 2. Breakthrough curves of acidic alumina, activated carbon,

and zinc oxide for DBTO (adsorbents were activated at 250 C).

column temperature was programed to first be retained at 80 C

for 1 min, was heated at the increasing rate of 30 C/min to
275 C, and kept at 275 C for 1 min. This gave an analysis time
of 7.5 min for target compounds. The burner temperature in the
detector was set at 800 C, air and hydrogen flow rates were 5.8
and 100 mL/min, consecutively. The ozone generator creates a flow
rate of 60 mL/min at 60 psig and 25 C. Model compounds, BTO,
and DBTO were identified and quantified with the standard samples.
The advantages of the GC-SCD are higher sensitivity and
selectivity toward sulfur compounds compared to other detectors.
Moreover, the linearity of the equation for quantifying sulfur
concentrations and no hydrocarbon quenching11 makes an SCD
more favorable compared to a pulsed flame photometric detector
(PFPD). Therefore, the SCD is a reliable instrument for detecting
ultralow sulfur concentrations as low as 0.1 ppmw. A dual plasma
burner in the SCD forms sulfur monoxide (SO) through hightemperature combustion of sulfur containing compounds. Combustion products in the SCD react with ozone under vacuum. This
creates excited (SO2*) which upon collapse to the ground state emits
light from the photons energy in reaction that is detected. Reactions
in the SCD are as follows:
S-compound + H2 + O2 f SO + products
SO + O3 f SO2*
SO2* f SO2 + h
2.4. Calibration Curve by SCD. Five samples of DBTO in
toluene were prepared from 1 to 25 ppmw sulfur concentration for
calibration curve preparation. Each sample was injected to the GC,
and the peak area was measured by the SCD.
2.5. Adsorbent Comparisons. In order to compare different
adsorbents and the adsorptive affinity for sulfide and sulfone
compounds, a model compound solution was prepared to mimic
the corresponding compounds in diesel fuel. All adsorbents to be
(11) Burmeister, M. S.; Drummond, C. J.; Pfisterer, E. A.; Hysert,
D. W.; Sin, Y. O.; Sime, K. J.; Hawthorne, D. B. Measurements of
Volatile Sulfur in Beer Using Gas Chromatography with a Sulfur Chemiluminescence Detector. ASBC J. 1992, 50 (2), 53-58.

1624 Energy & Fuels, Vol. 21, No. 3, 2007

Figure 3. Breakthrough curves of acidic alumina, activated carbon,

and zinc oxide for DBTO (adsorbents were calcined at 550 C).

Etemadi and Yen

Figure 5. Breakthrough curves of acidic, basic, and neutral alumina

for DBTO.

Figure 6. Effect of different grades of alumina in DBTO adsorption.

Figure 4. Comparison of adsorbents before and after calcining.

used for the columns were soaked in toluene to avoid air pores
and channeling inside the media. Soaked adsorbents were then
packed in the columns. The experiments were conducted at room
temperature and atmospheric pressure.
Three different adsorbents were tested for an adsorption capacity
of 0.05 wt % concentration of sulfur in the DBTO solution in
toluene. Acidic alumina (mesh 150), activated carbon with a pore
volume of 2 cm3/g of dry basis, and zinc oxide (mesh -325)
were used for the experiment. The three adsorbents that were used
in the comparison experiment are shown in Table 1. All adsorbents
were equal in volume (3 cm3).
Acidic alumina, activated carbon, and zinc oxide were heated
for 4 h at 250 and 550 C, consecutively, and packed in separate
columns. Effluents were collected from each column.
Alumina is the solid adsorbent of choice for removing model
sulfur compounds. A series of initial experiments were carried out
to compare the adsorbent capacity among different grades of
alumina. Physical characterizations of different types of alumina
are shown in Table 2. The three grades of alumina have the same
particle size and surface area to study the grade effect. Nanopowder
alumina is used to clarify the pore size, particle size, and surface
area as important parameters for adsorption.
Three grades of activated alumina were heated overnight at
200 C. A solution of DBTO in toluene was prepared with 0.05 wt
% sulfur content and passed through each column to collect effluent
samples.
Acidic alumina (mesh 150) and nanopowder alumina (2-4 nm)
were heated overnight at 200 C. Soaked activated alumina in
toluene was then packed in the column. A solution of DBTO in
toluene with known sulfur content was passed through each column
and effluent samples where collected. Both aluminas were calcined
through a temperature program up to 550 C for regeneration.
2.6. Selectivity among Sulfide and Sulfone. Separation of DBT
and DBTO through a solid phase was developed whereas the sulfone
was preferentially adsorbed to alumina in a packed column. In order
to present a feasible method, the recovery of the media is followed

after separation by using DMF as a polar solvent for leaching out

the remaining sulfur compounds in the media. Later, heating the
adsorbent for calcining and regeneration of the solid adsorbent will
be discussed to replace the DMF wash out. Equal mixtures of DBT
and DBTO in toluene were passed through the column and effluent
samples were collected. Samples were injected to the GC-SCD.
The second part of the experiment focused on recovery of the
media. Most of the DBT in the mixture had already passed through
the column, and therefore, not much was retained on alumina. In
order to wash out DBTO that was adsorbed completely to the media,
DMF was used. The effluents where collected for sulfur concentration measurements by a sulfur-in-oil analyzer (SLFA-20).
The DBT concentration was calculated after each injection in
the GC, by comparing the sample peaks to the DBT calibration
curve peaks. The same samples where injected to the GC to measure
the DBTO concentration in comparison with the DBTO calibration
curve. It is not possible to inject the samples that were collected
from DMF washout into the GC due to the polarity of DMF since
the HP-5 column in the GC is used for the detection of nonpolar
compounds. The concentration of sulfur was measured using a
sulfur-in-oil analyzer (SLFA-20).
2.7. Competitive Adsorption among Sulfones. A stock solution
of BTO and DBTO with sulfur content of 0.05 wt % of each
compound was prepared in toluene. A packed column of acidic
alumina was prepared to observe the adsorption affinity of
benzothiophene sulfone (BTO) and dibenzothiophene sulfone
(DBTO). The column contains 2.5 g of adsorbent.
2.8. Regeneration of Adsorbent and Sulfone Removal. A
solution of DBTO in toluene is measured (10 mL) and poured into
5 g of acidic alumina in a beaker. A shake table is used for better
mixing and adsorbance of DBTO to alumina. The mixture is air
blown to evaporate toluene (this sample is kept at ambient
temperature). A similar sample is prepared and dried alumina is
heated in the furnace for 2 h at 100 C. Adsorbed DBTO in alumina
is extracted with toluene and DMF consecutively and shaken with
the shake table. Extraction samples where measured with a sulfurin-oil analyzer (SLFA-20). Similar samples were prepared, and
experiments were run in higher temperatures up to 600 C.

Aspects of SelectiVe Adsorption

Energy & Fuels, Vol. 21, No. 3, 2007 1625

Table 3. Percentage of Retained Capacity after Regeneration of
Adsorbents at 550 C

type

recovered
effluent after
250 C (mL)

recovered
effluent after
550 C (mL)

% capacity after
regeneration

acidic alumina
activated carbon
zinc oxide

34.0
21.4
0.0

33.2
9.2
0.7

97.6
57.0
0.0

Table 4. Effect of Calcining on Adsorption Capacities of Alumina

Phases with Different Particle Size

Figure 7. Effect of particle size and calcining (550 C, 24 h) on

adsorption capacity and alumina phase.

Figure 8. Breakthrough curve for DBT from the DBT + DBTO

solution.

3. Results and Discussion

3.1. Calibration Curve by SCD. The linear equation for
quantifying the sulfur concentration by SCD is shown in Figure
1. This figure shows the sensitivity of SCD that can easily detect
sulfur concentrations at 1 ppmw detection limits and lower. This
detector was tested for 0.1 ppmw sulfur concentration and proves
to be a reliable way to study deep desulfurization of diesel fuel
samples for fuel cell applications.
3.2. Adsorbent Comparisons. Among the three adsorbents,
acidic alumina shows the best results for adsorbing DBTO and
zinc oxide has almost no affinity for adsorbing DBTO. The
polarity of DBTO is the reason for its adsorbing to the
adsorbents. Activated carbon has a water content of less than
30% which despite its higher surface area (almost 10 times more
than alumina) could be a fact for its lower adsorption capacity
than that of alumina. The purpose of this test is to show which
adsorbent maintains its adsorption sites after calcining and
regenerating at high temperatures.
Adsorption capacities of each adsorbent were calculated from
the breakthrough curves of DBTO adsorbance. Figure 2 clearly
shows that acidic alumina has the highest capacity for adsorbing
DBTO. All three adsorbents had the same volumes equal to 3
cm3 (C is the DBTO concentration in the effluent, and C0 is
the original concentration of DBTO).
The activated carbon sample has less than 30% water content
and possibly needs higher activation temperature for releasing
all the adsorbance sites. Another factor for the higher capacity
of alumina compared to the other two adsorbents could be the
pore size (58 ) in the amorphous alumina structure that is
shown to be a suitable size for capturing OSCs. Zinc oxide has
almost no affinity for adsorbing DBTO. A regeneration experiment is performed for all the three adsorbents by calcining the
samples up to 550 C. Figure 3 show that acidic alumina keeps

alumina phase

particle size

surface area
(m2/g)

capacity reduction
(%)

amorphous
R-monohydrate

104 m
2-4 nm

155
350-720

8.8
15.7

Table 5. Regeneration of DBTO-Loaded Alumina

temp
(C)

toluene
extraction
(ppmw)

DMF
extraction
(ppmw)

alumina
regeneration
(%)

ambient
100
150
200
250
300
400
500
600

101
26
11
8
2
12
10
20
26

212
248
262
223
254
237
25
28
14

32
40
41
50
44
46
92
90
91

97.6% of its original adsorption capacity for DBTO after

regeneration. Zinc oxide is still not a good adsorbent for OSCs.
The slight affinity toward adsorbing DBTO by zinc oxide after
calcining can be studied and characterized for deagglomeration
and possible adsorption sites. Activated carbon at 550 C has
already been denatured and has lost 43% of its adsorption
capacity.
Usually solvents like N,N-dimethyl formamide are used for
regeneration of adsorbent, but if the use of solvents is to be
avoided, heating the adsorbents up to 550 C will be another
way of recovering the adsorbent. Figure 4 demonstrates the
stability of alumina after calcining. Despite the high adsorption
capacity of activated carbon per gram of adsorbent, only alumina
can keep its adsorption sites after regeneration at 550 C. In
this manner, alumina among the above-mentioned adsorbents
will be the adsorbent of choice for our process.
Table 3 shows the adsorption loss of each adsorbent due to
calcining at 550 C. Alumina among these three adsorbents
maintains 97.6% of its original capacity after calcining.
For three grades of alumina (acidic, basic, and neutral),
adsorbent capacities were calculated from the breakthrough
curves of DBTO adsorbance. Figure 4 clearly shows that both
acidic and basic alumina have higher capacities for adsorbing
DBTO. All three aluminas have an amorphous phase, according
to the manufacturer.
Ideal adsorption sites on alumina are the exposed cationic
centers (acid sites), exposed oxide species (basic sites), and
exposed hydroxyl groups (acid/base sites). Figure 5 clearly
proves the effect of the acidobasicity characteristics of the
alumina surface for higher adsorption capacity. This affinity
toward oxidized compounds can be used in fossil fuels to leave
behind the nonpolar hydrocarbons. Figure 6 shows the difference
in adsorption capacity of DBTO for three grades of alumina
with same surface area and particle size. Acidic alumina has
the highest capacity (5.7 mg sulfur/g of adsorbent) among the
three and therefore is considered for further experiments.
The adsorption capacity comparison between two different
particle sizes of alumina is performed between an acidic alumina

1626 Energy & Fuels, Vol. 21, No. 3, 2007

Etemadi and Yen

Figure 9. Gas chromatogram of the BTO + DBTO solution in toluene from the GC-SCD.

(104 m particle size) and a nanopowder alumina (2-4 nm

particle size). The acidic alumina has an amorphous phase, and
the nanopowder is R-monohydrate (boehmite). After running
the packed column experiment and saturation of the media, both
alumina samples were calcined in a furnace through a temperature program up to 550 C for 24 h. Air was allowed in the
furnace to help the oxidation of adsorbates. Figure 7 represents
the results of particle size effect and also the effect of calcining
on the adsorbent structure and adsorption capacity.
The initial adsorbance capacity of nanopowder alumina is
56% higher than the acidic alumina with 104 m particle size.
This is due to higher surface area provided by the nanoparticles
(350-720 m2/g) comparing to the 155 m2/g for acidic alumina.
More studies on characterizing these two adsorbents prove that
the agglomeration of nanoparticles is one reason for the lower
than expected adsorption capacity of the alumina nanopowder.12
Recovering the media from the adsorbate is achieved by
calcining the alumina at 550 C through a temperature program.
The amorphous acidic alumina at 104 m is recovered 91.2%
whereas boehmite (R-monohydrate) with the 2-4 nm particle
size recovers 84.3%. Table 4 shows the properties of the two
alumina phases and the percentage of reduction in capacity of
the adsorbents after calcining.
Amorphous phase alumina has more stability compared to
the R-phase alumina to maintain its capacity after calcining for
regeneration. The dynamic adsorbing capacity of activated
alumina depends on the concentration and polarity of the target
compound, presence of other compounds (competitive adsorption), regeneration conditions, flow rate, and contact time.
3.3. Selectivity among Sulfide and Sulfone. Figure 8 shows
the C/C0 ratio changes of DBT and DBTO versus the volume
of the mixture passed through the column. This breakthrough
(12) Etemadi, O.; Yen, T. F. Surface Characterization of Adsorbents in
Ultrasound Assisted Oxidative Desulfurization Process of Fossil Fuels. J.
Colloid Interface Sci., in press.

curve shows that 92% of the DBT passes through the column
retaining 8% of the original concentration in the media. No
DBTO peak was observed in the GC injections, confirming the
adsorbance of the total concentration of DBTO to the packed
alumina.
The first peak of DBT appeared in the GC after passing 70
mL of DBT and DBTO mixture in toluene. Since the amount
of soaked toluene in the media was 66 mL, this shows that the
affinity of DBT to adsorb to acidic alumina was very low. The
alumina media from the adsorbate was recovered by DMF polar
solvent that is able to leach out the remaining DBT and the
adsorbed DBTO from the packed acidic alumina to a certain
extent that is not leachable anymore. The mass balance of DBT
and DBTO shows 88% recovery of the alumina media from
the adsorbed DBT and DBTO. The polar adsorption phenomenon was the reason for attracting most of the DBTO from the
toluene mixture with DBT to the media. Acidic alumina was
able to separate DBT from DBTO and pass up to 92% of the
DBT, leaving all the DBTO inside the column. This system
can be used after the UAOD process to adsorb the oxidized
sulfur compounds.
3.4. Competitive Adsorption among Sulfones. There is
different affinity among refractory sulfur compounds toward
adsorption to alumina. A mixture of BTO + DBTO with equal
concentrations of each compound is passed through an alumina
packed column. Figure 9 identifies the peaks for BTO and
DBTO after injection of the BTO + DBTO solution into the
GC-SCD. Figure 10 shows the different affinities in adsorption
between BTO and DBTO molecules to acidic alumina. Sulfur
density, molecule size, and the pore size of the adsorbent are
critical parameters for the different affinities of sulfur compounds toward adsorption.
3.5. Regeneration of Adsorbent and Sulfone Removal. The
original concentration of DBTO solution in toluene was 460
ppm. After heating, the exhausted alumina samples were

Aspects of SelectiVe Adsorption

Energy & Fuels, Vol. 21, No. 3, 2007 1627

400 C, the minimum amount of DBTO is extracted and the

main bulk of DBTO has been oxidized to SO2. Samples in this
experiment were heated in a furnace for 2 h, whereas a longer
calcining time was applied to alumina as described in section
2.6 in order to remove DBTO molecules from alumina for better
recovery. Therefore, 4 h of calcining is chosen to regenerate
alumina up to 98%. The consistency of regenerated alumina
characteristics will be studied for several reuses.
4. Conclusions

Figure 10. Breakthrough curve of acidic alumina for the BTO +

DBTO solution.

Figure 11. Variation of DBTO concentration in regeneration of

sulfone-loaded alumina by temperature.

extracted with toluene and DMF, consecutively. Table 5 shows

the extraction results of DBTO-loaded alumina by toluene and
DMF.
The concentration of DBTO after toluene and DMF washing
after 400 C heating of alumina is 10 and 25 ppm, consecutively.
Therefore, more than 92% of the adsorbent is regenerated after
heating up to 400 C. Figure 11 clarifies that the optimum
temperature for acidic alumina regeneration is 400 C. Above

Alumina was identified as an adsorbent for oxidized sulfur

compounds in BTO and DBTO solutions. The stability of
alumina after regeneration through calcining was confirmed by
maintaining 98% of the adsorption capacity after heat treatment
at 550 C, whereas activated carbon lost 43% of its original
capacity after calcining. The acidobasicity of alumina is an
important factor for providing adsorption sites for oxidized sulfur
compounds. Among the different phases of alumina, the
amorphous phase appears to show higher capacity than the
crystalline R phase relative to their surface area. Hidden grooves
and irregularities provide more topological traps for adsorption.
The selectivity of alumina was tested by adsorbing a sulfone
compound (DBTO) over its sulfide form (DBT) in a mixed
solution. After reaching the breakthrough curve for DBT, no
sign of DBTO appears from GC injections. The high affinity
of alumina toward polar compounds will be an advantage to
leave behind the nonpolar hydrocarbons in fossil fuels. The pore
size of the alumina adsorbent must be considered in the
competitive adsorption phenomenon of various sulfur compounds in fossil fuels. Amorphous acidic alumina is a selective
and stable adsorbent that can be used in an oxidative desulfurization process that provides a high yield of conversion of
sulfides to sulfones.
Acknowledgment. The authors are deeply grateful for the
financial support of U.S. Navy through Northrop Grumman and
CalNova Tech and that of the U.S. Army through the Army
Research Laboratory (ARL).
EF070016B