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An evaluation of desulfurization technologies for sulfur removal from liquid
fuels
Vimal Chandra Srivastava*
Received 14th June 2011, Accepted 18th October 2011
DOI: 10.1039/c1ra00309g
Published on 05 December 2011. Downloaded on 6/27/2019 5:27:31 AM.

Sulfur compounds represent one of the most common impurities present in the crude oil. Sulfur in
liquid fuel oil leads directly to the emission of SO2 and sulfate particulate matter (SPM) that
endangers public health and community property; and reduces the life of the engine due to corrosion.
Furthermore, the sulfur compounds in the exhaust gases of diesel engines can significantly impair the
emission control technology designed to meet NOx and SPM emission standards. The research efforts
for developing conventional hydrodesulfurization and alternative desulfurization methods such as
selective adsorption, biodesulfurization, oxidation/extraction (oxidative desulfurization), etc. for
removing these refractory sulfur compounds from petroleum products are on the rise. Research
laboratories and refineries are spending huge amounts of money in finding a viable and feasible
solution to reduce sulfur to a concentration of less than 10 mg l21. This paper reviews the current
status in detail of various desulphurization techniques being studied worldwide. It presents an
overview of novel emerging technologies for ultra-deep desulfurization so as to produce ultra-low-
sulfur fuels.

1. Introduction of crude oil. Naturally occurring sulfur compounds left in fuels

Energy production is one of the most pressing issues of modern
times. Economic activity and energy usage are intimately linked.
The production of useful goods and services requires energy.
Fossil fuels are the most widely used sources of energy in the
world. Although the percentage of energy obtained from fossil
fuels declined over recent years, the share of world energy from
fossil fuels is still over 82%, half of which comes from
petroleum.1 Crude oil, a complex mixture of organic liquids, is
the largest source of energy. Major portions of the crude oil are
used as transportation fuels such as gasoline, diesel and jet fuel.
It occurs naturally in the ground and was formed millions of
years ago. The sulfur content and the American Petroleum
Institute (API) gravity are two properties which have a great
influence on the value of the crude oil. The sulfur content is
expressed as a percentage of sulfur by weight and varies from less
than 0.1% to greater than 5% depending on the type and source
of crude oils.2 Sulfur compounds exist in various forms and can
be classified into four main groups: mercaptans, sulfides,
disulfides and thiophenes (THs).
Sulfur compounds are undesirable in refining process as they
tend to deactivate some catalysts used in crude oil processing and
cause corrosion problems in pipeline, pumping, and refining
equipments. Table 1 shows the level of sulfur in global supplies
Department of Chemical Engineering, Indian Institute of Technology
Roorkee, Roorkee -247667, Uttarakhand, India.
E-mail: vimalcsr@yahoo.co.in; vimalfch@iitr.ernet.in;
Fax: +91-1332-276535, 273560; Tel: +91-1332-285889
lead to the emission of sulfur oxide gases. These gases react with
water in the atmosphere to form sulfates and acid rain which
damages buildings, destroys automotive paint finishes, acidifies
soil, and ultimately leads to loss of forests and various other
ecosystems.3 Sulfur emissions also cause respiratory illnesses,
aggravate heart disease, trigger asthma, and contribute to
formation of atmospheric particulates.4 Automobiles are also
adversely affected by presence of sulfur compounds in liquid
fuels. Sulfur levels in automotive fuels have a profound effect on
the efficacy of catalytic converters.
The current industrial method for removal of sulfur from fuels
is hydrodesulfurization (HDS), which is a high temperature, high
pressure catalytic process. This makes HDS a very costly option
for deep desulfurization. Moreover, HDS is not effective for
removing heterocyclic sulfur compounds such as dibenzothio-
phene (DBT) and its derivatives, especially 4,6-dimethyldiben-
zothiophene (4,6-DMDBT). Deep desulfurization of gasoline
(from 500 to ,10 ppm sulfur) is restricted largely by DMDBT,
which is the least reactive sulfur compounds. Oxidative
desulfurization (ODS), oxidation–extraction desulfurization
(OEDS), adsorptive desulfurization and bio-desulfurization
(BDS) are the other desulfurization techniques that have the
potential to produce ultra clean fuels. In ODS, the sulfur
containing compounds is oxidized to sulfone by chemical
reaction using an oxidant viz. H2O2, H2SO4, etc. The sulfone
compound is then easily extracted from the fuel due to its higher
polarity. In the adsorption process, the adsorbents used in the
process selectively grab the sulfur. The active adsorbent is placed

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Table 1 Sulfur levels in the global supplies of crude oil10

Crude Oil Sulfur weight Production Crude oil Sulfur weight Production
Region gravity (API) (%, 1990) (tpd) gravity (API) (%, 2010) (tpd)

Alaska 26.970 1.11 1954 28.340 0.99 1645

Canada 31.400 1.52 2000 32.000 1.62 2500
California 17.430 1.59 970 18.730 2.60 951
Rest of USA 35.110 0.86 4510 36.930 0.88 2470
Africa 31.280 0.17 7000 32.640 0.18 6100
Europe 33.200 1.09 16 330 33.700 1.10 15 530
Latin America 25.060 1.62 7770 27.100 1.82 9850
Middle East 33.730 1.69 29 100 34.350 1.71 35 760
Far East 33.800 1.09 16 330 37.300 1.10 15 530
World Average 31.300 1.13 70 800 32.810 1.27 83 450

on a porous, non-reactive substrate that allows the greatest decreased lung function. Therefore, desulfurization of fuels is
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surface area for adsorption. Adsorption occurs when the sulfur
molecules attach to the adsorbent on the substrate and remain
there separate from the fuel. BDS has drawn wide attention
recently because of its green processing of fossil fuel. However,
the slowness of the removal process is a major hindrance in the
use of BDS process.
Today, the strongest motivation for the reduction of sulfur in
fuels is due to environmental regulations which are imposing
stringent limits for sulfur levels in transportation fuels. New
techniques are required to remove the sulfur from lower quality
feed stocks to ensure that energy is available at a reasonable cost.
This paper reviews the current status and details of various
desulphurization techniques being studied worldwide to remove
sulfur compounds from liquid fuels and aims to identify the
research gaps in these techniques.
2. Effect of sulfur on the environment
The pollution emitted by vehicular engines greatly affects the air
quality. The sulfur compounds are converted to sulfur oxides by
combustion, and these ultimately lead to acid rain.5–7 Sulfur
dioxide and other combustion related pollutants from sulfur
compound containing fuels lead to environmental concerns such
as smog, global warming and water pollution.8 Even with more
stringent heavy-duty highway engine standards, these engines
will continue to emit large amounts of nitrogen oxides (NOx) and
particulate matter (PM) both of which contribute to serious
public health problems. The PM present in diesel exhaust is
likely to cause high levels of lung cancer in humans. Other health
effects include aggravation of respiratory and cardiovascular
diseases, aggravation of existing asthma, chronic bronchitis and
extremely important in the petroleum industry.
The removal of sulfur from petroleum is also necessary from
industrial point of view. The automobile manufacturers demand
removal of sulfur containing compounds out of petroleum in
order to reduce overall emissions from vehicles. This is because
sulfur compounds poison the catalytic converters that reduce
particulates and NOx emissions.9 Sulfur affects these emission
control devices by strongly adsorbing to the precious metal
catalysts, preventing the adsorption and reaction of hydrocar-
bons, NOx, and carbon monoxide.10
In addition, sulfur compounds in petroleum also cause
corrosion to parts of internal combustion engines and refineries
because of the formation of the oxyacids of sulfur from
combustion products.11 Also, sulfur compounds are undesirable
in refining processes because they tend to deactivate some
catalysts used downstream and upgrading of hydrocarbons.12
Moreover, sulfur compounds contribute to the formation of
gummy deposits in liquid petroleum products.
3. Standards
The United States Environmental Protection Agency (US EPA)
mandated reduction of the sulfur content of diesel fuel and gasoline.
In 2006, EPA mandated maximum sulfur content of 15 ppm in
diesel fuel.10 Table 2 shows the journey of emission standards the
worldwide.13 According to Euro V norms the fuel sulfur content will
have to be reduced to as low as 10 ppm in near future. Sulfur
regulations that took effect in Canada and the USA in June 1, 2006
reduced the sulfur content in on-road diesel fuel and gasoline from
500 mg kg21 and 350 mg kg21 to 15 mg kg21 and 30 mg kg21,
respectively.14,15 Currently, the maximum allowable sulfur content
in diesel in USA and Europe is 10 mg kg21.16,17

Table 2 Roadmap of emission standards worldwide. Modified from CAI-Asia13

Country 96 97 98 99 00 01 02 03 04 05 06 07 08 09 10

California (US) CARB (90 ppm) CARB (80 ppm) CARB (15 ppm)
USA EPA (500 ppm) 300 ppm 80 ppm 15 (ppm)
EU Euro II (500 ppm) E III (150 ppm) E IV 50 ppm E V 10 ppm
China (H) EI Euro II Euro III Euro IV
Thailand Euro I E II Euro III E IV
Singapore Euro I E II Euro III E IV
Malaysia Euro I Euro II E III
India (metros) EI Euro II Euro III E IV
India Euro I Euro II E III
Nepal Euro I
Philippines Euro I
Indonesia Euro II

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The latest regulation in India, which was regulated in 2010 for
major cities of India, reduced the gasoline sulfur content from
150 ppm to 50 ppm and the diesel sulfur content from 350 ppm
to 50 ppm. Refineries in India are facing major challenges to
meet the fuel sulfur specification along with the required
reduction of aromatics contents.18 In coming sections, details
of various sulfur removal technologies like HDS, ODS, OEDS,
adsorptive removal and BDS are discussed.
4. Hydrodesulfurization
4.1. Introduction
HDS is used traditionally in refineries to reduce the sulfur
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content in fuels. Interest in HDS was initially stimulated by the
availability of hydrogen from catalytic reformers.19 Typically,
the HDS process involves catalytic treatment with hydrogen to
convert the various sulfur compounds to H2S and sulfur-free
organic compounds at high temperature and partial pressure of
hydrogen.20–21 Conventional catalytic HDS method for reducing
sulfur content requires severe conditions of operation. In
refineries, the H2S resulting from the HDS reaction is eventually
converted to elemental sulfur by a modified version of the Claus
process.22
4.2. Reaction conditions for HDS reaction
The HDS reaction in refineries is carried out in trickle-bed
reactors. These reactors are commonly operated at temperatures
in the range 300–450 uC, and at H2 pressures of 3.0–5.0 MPa,
usually with CoMo/Al2O3 or NiMo/A12O3 catalysts.7,23 Under
these harsh conditions, olefins get hydrogenated, leading to a
loss of octane rating and excess hydrogen consumption. Under
mild HDS conditions, H2S can react with olefins in the reactor to
create recombinant mercaptans which are linear or branched
thiols of typically 5–12 carbons. The formation of recombinant
mercaptans causes sulfur to be retained in the product, limiting
the effectiveness of the HDS process. Further research in HDS
catalysis and process designs are being carried out so as to
increase the sulfur removal and still maintain the fuel quality at
some minimum specification.
In the fuel cell systems, HDS reactions are preferable to be
carried out at atmospheric pressure. Since hydrogen is valuable
reactant in the fuel cell, it is desirable to run the HDS reaction
with a low H2/fuel ratio. HDS has been adapted for phosphoric
acid fuel cell (PAFC) systems, which operate with natural gas.24
HDS has also been investigated for use in conjunction with a
direct carbonate fuel cell.25 The mechanism of HDS is discussed
in subsequent section. At atmospheric pressure, the HDS
reaction proceeds only via hydrogenolysis route and not via the
hydrogenation (HYD) route26 which is considered to be the
effective route in desulfurizing the refractory sulfur compounds
such as 4,6-DMDBT.
At atmospheric pressure and at temperatures >300 uC, the
hydrogenation of aromatic rings is thermodynamically limited.
This is advantageous in the fact that the catalysts active sites
don’t get occupied for the hydrogenation of aromatic com-
pounds. However, inhibition in the presence of aromatics has
been noticed even when they are not hydrogenated. Studies to
determine the optimum operational pressure for the HDS unit
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for fuel cell application are, therefore, scope of interest for
further research.
4.3. Mechanism of HDS
It is generally accepted that the HDS proceeds through the
reaction network proposed by Houalla et al.27–28 In general, the
reaction mechanism of DBT and 4,6-DMDBT through HDS
process is suggested to proceed via two main pathways. One is a
DDS or hydrogenolysis pathway where sulfur is removed without
abetting the aromatic rings. The other is via a hydrogenation
desulfurization (HYD) pathway, in which aromatic rings of DBT
compounds are preferentially hydrogenated to 4H-or 6H-DBT
intermediates and are subsequently desulfurized.20
The reaction mechanism for the HDS of DBT at 300 uC and
102 atm is illustrated in Fig. 1.28 The reaction of hydrogen with
DBT gives biphenyl (BiPh) as predominant organic product. In
the HYD pathway mechanism, the primary reaction products
formed directly from DBT are tetrahydrodibenzothiophene
(THDBT) and/or hexahydrodibenzothiophene (HHDBT). Both
THDBT and HHDBT are very reactive intermediates and are
difficult to isolate for detection. These compounds get further
desulfurized to form cyclohexylbenzene (CHB) as the secondary
product. This pathway is referred to as HYD pathway since the
sulfur compound is hydrogenated prior to desulfurization.
Direct C–S bond hydrogenolysis of DBT gives biphenyl via
DDS pathway. Sequential hydrogenation of biphenyl produces
CHB. Bicyclohexyl (BiCh) is the tertiary product formed in
traces via the slow hydrogenation of CHB formed by any of the
two pathways.
The DDS reaction is faster than the HYD. However, the HYD
pathway becomes relatively fast with an increase in H2S and/or
H2 concentration in the reaction mixture; with an increase in
methyl groups in the 4 or 4 and 6 positions; and with more active
catalyst for hydrogenation e. g. NiMo/Al2O3 vs. CoMo/Al2O3.27–29
Houalla et al.27–28 found that the activity of NiMo/Al2O3
catalyst (per unit surface area) was about twice as much as
that of the CoMo/Al2O3. The yield of CHB, at a given
Fig. 1 Pathways for the HDS of DBT at 300 uC and 102 atm in the
presence of CoMo/Al2O3.28
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conversion, was about three times higher with NiMo/Al2O3
catalysts than with CoMo/Al2O3. This indicates that HYD is a
better route for increasing the desulfurization extent of the
refractory compounds. The desulfurization rate of hindered
compounds is greatly increased through the HYD route.
Without one or both of the rings, the sulfur molecule becomes
much more flexible, and the sulfur atom approaches the
catalyst surface much easily and gets removed.
In general, when the unpaired electrons of the sulfur can
resonate with the pi electrons of the organic structure, the energy
of the carbon-sulfur bond (C–S) becomes practically identical
with that of the carbon-carbon (C–C) bond.30 This leads to a
reduction in the selectivity of the HDS process, and hydrogena-
tion of carbon-carbon bonds happens. Saturated hydrocarbons
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4,6-DMDBT were found to be similar under the industrial
conditions with sulfided CoMo/Al2O3,27 CoMo/Al2O3–zeolite,33
and NiMo/Al2O3.34 The presence of aromatic compounds in the
fuel further inhibited the activity towards HDS. Polar com-
pounds such as nitrogen- and oxygen-containing compounds are
also known to have strong inhibiting effects on HDS reac-
tions.35–36 Egorova and Prins35 reported that even trace amount
of naphthalene had an inhibitive effect on the HDS of DBT and
4,6-DMDBT at 340 uC and 5 MPa. It has been reported that
H2S, produced by the HDS reaction itself, inhibits the HDS
reaction in hydrocarbon fuels, especially in direct sulfur
extraction reaction.37–39 However, inhibitive effect of H2S on
the HDS reactions depends upon the sulfur content of the raw
fuel feed. The inhibition to the HDS process is related to the

lead to a lower-grade fuel, and require additional processing competition between the inhibitors and the organosulfur
steps. compounds for adsorption on the catalyst active sites.
Thus it may be said that reactivity of high boiling point
4.4. Effect of refractory organosulfur compounds on HDS organosulfur compounds such as BTHs and DBTs that are
present in intermediate distillates like diesel, toward HDS
The effectiveness of the HDS process depends on the type of the
reaction is substantially lower than that of the low boiling point
sulfur compound. Nag et al.31 carried out HDS of various
compounds such as thiols, sulfides, and disulfides that are
organosulfur compounds using sulfided CoO–MoO3/c–Al2O3 as
present in natural gas and light feedstocks.7,23,40 Aromatic,
catalyst. They found that the following order of reactivity for
cyclic, and condensed multicyclic compounds are also considered
HDS: TH > BTH > benzonaphthothiophene > tetrahydroben-
to be more difficult to remove.41 The sterically hindered BTHs
zonaphthothiophene > DBT. The substitution of these com-
and DBTs are, therefore, the target compounds for HDS in most
pounds by ring alkylation further affected the reactivity.
of the present studies. DBT, 4-methyl-DBT (4-MDBT) and 4,6-
Kilanowski et al.32 carried out HDS of methyl-substituted
DMDBT etc., therefore, must be removed to reduce sulfur
DBTs (DBTs) at atmospheric pressure using sulfides CoMo/c–
content in fuel.42
A12O3. They showed that the reactivity of DBTs, with methyl
substitution in different positions, decreases in the following
4.5. Catalysts for HDS
order: 2,8-dimethylDBT (2, 8-DMDBT) > DBT (DBT) >
4-methyldibenthothiophene (4-MDBT) > 4,6-dimethylDBT Table 3 summarizes recent researches conducted for optimiza-
(4,6-DMDBT). The reactivity trends for DBT, 4-MDBT, and tion of HDS processes utilizing various catalysts and reactor

Table 3 Sulfur removal by HDS at optimized conditions

Optimum Conditions
Sulfur S Conc. Temp. Pressure %S
Process Compound Oil Catalyst System Co (ppm) (uC) (MPa) Removal Reference

Deep HDS Alkyl DBTs Light Oil Co-Mo/Al2O3 Packed Bed 4000 300 — 67% 43
Three stage HDS Alkyl DBTs Diesel CoMo + NiMo Packed Bed 7060 250 2.9 97% 44
HDS Alkyl DBTs Heavy gas oil Co-Mo-A1 Trickle bed 1800 360 5.5 20% 45
Deep HDS Alkyl DBTs Gas oil Co-Mo/c–A12O3 Fixed bed 13 200 350 3 96% 46
HDS Alkyl DBTs Heavy gas oil Co, Ni, Mo, W Trickle Bed 13 300 320 5.4 80% 47
supported on Al2O3/SiO
In situ H2 BT Water/Toluene Mo Batch autoclave 350 340 20 99.5% 48
generation emulsion
Staged HDS Alkyl DBTs Medium cycle oil NiMoS/Al2O3 Packed Bed 4900 340 5 97% 49
Deep HDS Alkyl DBTs Light cycle oil Co-Mo supported Packed Bed 21 900 350 4.5 57% 50
on MCM-41
Lab Scale HDS Alkyl DBTs Middle NiMo/c–Al2O3 Trickle bed 16 740 350 4 90% 51
distillates
Deep HDS Alkyl DBTs Gas oil CoMo/Al2O3 + Packed Bed 14 350 340 3 98% 52
NiMo/Al2O3
HDS Alkyl DBTs Gas oil NiMo sulfide on Packed Bed 11 780 340 4.9 94% 53
Al2O3–Si support
Deep HDS Alkyl DBTs Gas oil CoMoS and NiMoS Batch autoclave 340 — 4.9 97% 54
Oil presaturated Alkyl DBTs Diesel CoMo Two phase reactor 1200 400 7 99% 55
with H2
Lab Scale Alkyl DBTs Diesel P and Ni–Al2O3 520 340 4 50% 56
Deep HDS supported Mo
oxycarbides
HDS Thiophene n-Heptane FeS–MoS supported — 1000 280 0.1 30% 57
on Al2O3 and carbon

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configurations.43–57 HDS with Mo, Ni or W-based catalysts are
widely used to reduce organosulfur compounds such as
mercaptans, thioethers, and disulfides. The most common
catalysts used in HDS are cobalt or nickel promoted molybde-
num sulfide. Recent research in HDS aims to develop catalyst
that can effectively remove the refractory organosulfur com-
pounds. Subsequent section aims to discuss about various
catalysts developed for HDS, their synthesis, characterization,
activation and operating conditions.
4.5.1. Catalyst preparation method. Generally, the catalyst
preparation method has immense effect on the catalyst activity
for any particular reaction/conversion. Only few studies have
been reported in the literature that explain the effect of the
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catalyst preparation method on HDS. However, the reasons for
better activity of a catalyst developed by one method over other
method are not well understood. Venezia et al.58 studied the
influence of the preparation method of CoMo/silica catalysts on
HDS of TH. The catalysts were prepared by either total sol–gel
route or incipient wetness impregnation/co-impregnation, and
the results were compared with catalysts supported on commer-
cial silica. The catalyst supported on sol–gel silica with the two
metals loaded by co-impregnation in the presence of nitrilo-
triacetic acid showed the highest activity. Papadopoulou et al.59
found that the CoMo/A12O3 catalyst prepared by depositing
first the Mo precursor through equilibrium deposition filtration
(EDF), and then, Co precursor via dry impregnation resulted in
catalysts that had higher activity than the catalysts prepared by
co-EDF or by a conventional impregnation technique.
4.5.2. Synthesis, characterization and activity of catalysts for
HDS. An extensive number of studies have been reported in the
literature on synthesis, characterization and activity of catalysts
for HDS. Almost all the transition metals in their sulfides form
have been tested for their activities toward HDS.60–61 When
tested individually, the activity towards HDS varied over three
orders of magnitude across the periodic table. The most active
catalysts are found to be from the second and the third rows. The
difference in activity has been related to the electronic and
structural properties.
The synergetic effects of the bimetallic catalysts like CoMo/
Al2O3, NiMo/Al2O3, NiW/Al2O3, CoW/Al2O3, and PtPd/A12O3
has been extensively studied.35,62–64 Isoda et al.33 performed a
study using a blend of CoMo/Al2O3 and Ru/Al2O3 catalysts, and
compared its activity towards the HDS of 4,6-DMDBT in the
presence of naphthalene to those of CoMo/Al2O3, NiMo/Al2O3,
and Ru/A12O3. The blend catalyst showed the highest rate of
HDS of 4,6-DMDBT through its selective hydrogenation with-
out excessive hydrogenation of naphthalene. Lecrenay et al.65
found that the commercial NiMo/Al2O3 exhibited three times
higher activity than that of the commercial CoMo/Al2O3 on the
HDS reaction pathways of 4,6-DMDBT in decalin. This was
ascribed to the higher hydrogenation activity of NiMo/A12O3
catalyst as compared to CoMo/A12O3. Steric hindrance is
considered to be the reason behind the low reactivity of 4,
6-DMDBT.66 Hydrogenation of the aromatic ring leads to
easing of steric hindrance, thus, catalysts with higher hydro-
genation capability show higher catalytic activity towards the
HDS of 4,6-DMDBT. Li et al.67 investigated the HDS of
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tetrahydro-, hexahydro-, and dodecahydro-dimethyl DBT
(DMDBT) over sulfided Mo and NiMo on c–Al2O3 catalysts
at 300 uC and 5 MPa. Tetrahydro-DMDBT reacted by
hydrogenation to hexahydro-DMDBT, which in turn reacted
to dodecahydro-DMDBT by hydrogenation and to 3,3-
dimethylcyclohexylbenzene by desulfurization. All four diaster-
eoisomers of hexahydro-DMDBT were observed, all of which
interconverted rapidly during HDS. Rodriguez-Castellon et al.68
prepared HDS catalysts by incipient wetness impregnation of
Ni–Mo(W) and Co–Mo(W) species over siliceous MCM-41
doped with zirconium. All the catalysts displayed a very good
performance in the temperature range of 300–340 uC, with
conversions between 49.0% and 92.6%. The Ni promoted
catalysts displayed better performances than those of Co
promoted catalysts in the HDS of DBT.
Yoosuk et al.69 carried out a comparative study of unsup-
ported MoS2 and Me/MoS2 (MeLCo, Ni) catalysts prepared by
hydrothermal synthesis. Sakanishi et al.70 studied the HDS of
4,6-DMDBT using Ru and NiMo catalysts supported on
carbon. The carbons examined in the study were carbon blacks,
granular active carbons with moderate and large surface areas,
and pitch-based activated carbon fibers (ACF) with large surface
areas. The NiMo/C catalysts exhibited higher activity for the
HDS of 4,6-DMDBT at relatively higher temperatures of 340–
380 uC than a commercial NiMo/A12O3 catalyst regardless of the
type of the carbon support. The main route was found to be the
DDS. Nav et al.71 prepared Co/Mo catalysts supported on a Ti–
loaded hexagonal mesoporous SBA-15 material. The Ti–loaded
SBA-15 catalysts were more active than the Ti–free counterpart
due to the enhancement of the DDS route in this reaction.
Supported platinum has also been studied as a catalyst for
HDS under standard industrial conditions. Qian et al.64
compared the activity of unsulfided Pt/A12O3 (3 wt%) with the
conventional CoMo/Al2O3 catalyst. Both the catalysts were
found to have similar activity towards HDS of DBT in decalin.
Navarro et al.72 compared Pt-based catalysts with the commer-
cial CoMo/A12O3 in HDS of commercial diesel fuel. It was
found that both Pt/HY zeolite and R/ASA (amorphous silica-
alumina) were more active than the CoMo/A12O3 catalyst.
Robinson et al.73 used catalysts with high hydrogenation activity
to desulfurize 4-ethyl, 6-methyl DBT (4-E, 6-MDBT). The HDS
activity was found to be in the following order: Pt/ASA & Pt/
Al2O3 > NiW/Al2O3 & CoMo/Al2O3 or NiMo/Al2O3. The
superiority of Pt/ASA catalyst in HDS of 4-E, 6-MDBT was
attributed to its superior hydrogenation activity. Both sulfides
and unsulfided Pt/ASA were found to have similar catalytic
activities. Reinhoudt et al.74 utilized unsulfided (reduced) Pt to
hydrodesulfurize 4-E, 6-MDBT at 360 uC and 60 atm. The
catalyst activity was found to reduce in the following order: Pt/
ASA > CoMo/Al2O3 > Pt/Al2O3. Baldovino-Medrano et al.75
tested a Pt/c–Al2O3 catalyst in simultaneous HDS of DBT and
hydrodearomatization (HDA) of naphthalene reactions.
Samples of it were subjected to different pretreatments:
reduction, reduction–sulfidation, sulfidation with pure H2S and
non-activation. The reduced catalyst presented the best perfor-
mance, even comparable to that of Co(Ni)Mo catalysts.
4.5.3. Supports for HDS catalysts. Many different supports
have been investigated in an attempt to enhance the HDS
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activity of the catalysts. Reinhoudt et al.74 compared Pt/ASA to
Pt/XVUXY (zeolite) for HDS of 4-E,6-MDBT in a batch reactor
and found that although the zeolite supported catalyst showed
higher activity initially, it deactivated with time. Okamoto
et al.76 studied the effect of different support on the activity of
Co–Mo sulfide model catalysts. The supports used were A12O3,
TiO2, ZrO2 and SiO2. The specific activity of the CoMoS phase
supported on SiO2 was found to be 1.7 times higher than those
on the other supports. Klimova et al.77 prepared a series of Al–
containing mesoporous molecular sieves SBA-15 with different
Si/Al molar ratios (50, 30, 20 and 10) by chemical grafting
method using aluminum(III) chloride as alumina source.
Catalytic activity of Mo and NiMo/SBA-15 catalysts increased
with Al incorporation in the support reaching a maximum at Si/
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Al molar ratio of 20. High activity of NiMo/Al-SBA-15 catalysts
in 4,6-DMDBT HDS was attributed to a good dispersion of Ni
and Mo active phases and to the bifunctional character of these
catalysts. Zepeda et al.78 showed that titanium incorporation
into hexagonal mesoporous silica (HMS) material had a positive
effect on the activity of supported CoMo catalysts in the HDS of
DBT and 4-ethyl, 6-methyl-DBT (4E6MDBT). The catalyst with
a Si/Ti = 40 (molar ratio) was the most active in the HDS of
DBT. A further increase in the Ti–content led to a decrease in
Brønsted acidity and the BET surface area of the catalysts, which
resulted in a decrease in the bifunctional character of the
catalysts. Raman spectroscopy demonstrated that Ti–incorpora-
tion into HMS material lead to a decrease in the degree of
polymerization of Mo species, and this implied a better
dispersion of MoS2.
In the past few decades there has been intense activity on
oxides and mixed oxides as supports to Mo, CoMo, NiMo, W
and NiW. These supports have been prepared using several
methods, and effects of preparation on physico-chemical proper-
ties have been studied. The support and catalysts were
characterized in few cases, however, most of the times only
activity data is available. There is insufficient data to arrive at a
consensus regarding the factors that are responsible for such
increase in activity. Effect of catalyst support is not well
researched and documented in the literature. This area is needed
to be well understood for developing better catalyst for HDS.
4.5.4. Coking and activation of HDS catalysts. HDS catalysts
regularly experience some degree of deactivation in commercial
operation depending on the feed source. The heavier the
feedstock, the faster the catalyst deactivates.79 Vogelaar et al.80
investigated the deactivation of Mo/Al2O3 and NiMo/Al2O3
catalysts when subjected to the HDS of TH at atmospheric
pressure. The catalysts were activated/sulfided using a H2S/H2/
Ar gas mixture. The major cause of deactivation of the Mo/
A12O3 catalyst was found to be coke deposition on the active
sites. In contrast, the main cause for deactivation for the NiMo/
A12O3 catalyst was the loss of sulfur atoms during the course of
the reaction. This process was fully reversible by H2S/H2
treatment. Sulfided catalysts (CoMo/A12O3 and NiMo/Al2O3)
maintain their activity as long as they are not reduced to their
metal or oxide forms. The presence of sulfur compounds (mainly
in the form of H2S) helps maintaining the catalyst activity.81–83
Deactivation caused by loss of sulfur could be avoided by
using catalysts that activate without sulfiding, while the
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deactivation caused by coking could be avoided if coke-tolerant
or coke-preventing catalysts are used. The catalyst is activated
before being used in the HDS process by sulfiding the metallic
phase. The activation/sulfiding step is done by treating the
catalyst with a mixture of HDS and H2 or a feed containing
sulfur compounds and H2.19 Qian et al.64 and Reinhoudt et al.74
demonstrated that Pt based catalysts are sufficiently active
without sulfiding the metal phase as compared to Mo, Ni, or Ru
based catalysts.
It is generally recognized that the carbon-supported HDS
catalysts have a potential advantage over alumina-based
catalysts, particularly with respect to the low coking properties
of the former which can result in prolonged catalyst life.
Additional benefits can also be gained by recovering the active
metals (cobalt, nickel, molybdenum or tungsten) from spent
catalysts by burning off the carbon and the coke.
4.6. Commercial HDS and future challenges in refineries
HDS is a commercially proven refining process that passes a
mixture of heated feadstock and hydrogen over catalysts to
remove sulfur. Refineries desulfurize both distillate streams
generated during direct distillation of crude oil and streams
coming out from conversion units such as fluid catalytic cracking
(FCC) and hydrocracker units. HDS can be performed either
before FCC or after, depending on the refinery design. However,
HDS must be performed before reforming, due to the poisoning
effect of sulfur on Pt. In the HDS reactor, sulfur is reduced
liberating H2S which is then removed from the flue gas by amine
scrubbing. HDS is the primary desulfurization technology used
today, although caustic washing to remove low molecular weight
thiols is also performed. Most HDS operations also remove
nitrogen compounds and some metal impurities.5
Refineries meet the ultra low sulfur specifications on fuels that
are produced from straight runs streams by controlling the
hydrogenating conditions and selecting the appropriate catalysts.
The difficulty however arises in the desulfurization of other
steams that come from the conversion units, which mostly
include the refracted sulfur compounds. Isoda et al.84 improved
the currently practised HDS processes to remove sulfur from
DBT derivatives by using a nickel-supported zeolite catalyst.
This technology also has two steps. The reaction is carried out at
270 uC for 1 h and at a hydrogen pressure of 250 Pa in the first
step, and then, the products are further desulfurized over a
CoMo/A12O3 catalyst at 300 uC for 2 h at a hydrogen pressure of
250 Pa to remove 4,6-DMDBT. The disadvantage of the process
is high temperature and pressure. Having more steps during the
desulfurization also brings extra cost for the refineries.
There are several constraints in the HDS process. Meeting the
sulfur requirement for gasoline is believed to be the greatest
challenge for the refining business requiring substantial revamps
to equipment or even construction of new units. This is due to
the fact that most of the gasoline production in the market today
is coming from cracked stocks that contain a larger concentra-
tion of compounds with aromatic rings and high olefin content,
thus, making sulfur removal more difficult. The need to
desulfurize the cracked stocks in addition to the straight-run
streams is forcing the refiners to choose the most cost-effective
technology.20–21,85–88 In India, refiners today decrease the sulfur
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content to about 50 ppm but as the sulfur limits are decreased,
there will be a need to increase the number of HDS units, which
will tremendously increase the demand for hydrogen. Higher
temperatures and pressures will also be needed to remove the
recalcitrant sulfur compounds which raise operating costs.89
HDS is limited in treating BTs and DBTs (especially DBTs
having alkyl substituents on 4 and/or 6 positions). The
production of light oil with very low levels of sulfur-containing
compounds requires the application of severe operating condi-
tions and the use of especially active catalysts.90–92 Moreover, the
HDS process has reached a stage where increasing temperature
and pressure are just not enough to remove last traces of sulfur
without affecting the octane number.90
Another problem is that the increased use of the HDS process
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to extract sulfur from petroleum adds to the volume of H2S. This
puts pressure on the Claus plant capacity, which produces
hydrogen for the refineries.91
In the case of diesel, a two stage deep desulfurization process
will most probably be sufficient to meet the 10 ppm sulfur target
in future. The first stage can reduce the sulfur level to below
50 ppm with a second stage that could produce diesel product
with 10 ppm sulfur or less. In some cases the first stage could be a
conventional hydrogenating unit with moderate adjustments to
the operating parameters. The second stage would require
substantial modification of the desulfurization process, primarily
through use of higher pressure, increasing hydrogen flow rate
and purity, reducing space velocity, and choice of catalyst.88,92
Several academic and industrial research groups are working to
improve the current HDS technology practised in refineries.
Although HDS processes have dominated desulfurization of
petroleum in the past their cost and the requirements of the
upcoming strict fuel specifications combine to motivate the
development of innovative process technologies.
5. Oxidative desulfurization (ODS)
5.1. Introduction
ODS is a promising technology for the reduction of sulfur at low
temperature (y50 uC) and atmospheric pressure.93 In ODS,
heavy sulfides are oxidized by adding one or two oxygen atoms
to the sulfur using appropriate oxidants without breaking any
carbon–sulfur bonds, yielding the sulfoxide and sulfone,
respectively. These oxidized compounds are then extracted or
adsorbed from the light oil due to their increased relative
polarity. Thus, the ODS is basically a two stage process;
oxidation, followed by liquid extraction.
Oxidation of DBT to the corresponding sulfone can be
represented as:40,42,94
Oxidation of the DBT derivatives to the corresponding
sulfones increases their polarity and molecular weight. This
facilitates their separation by extraction,12 distillation,90 or
adsorption.95 Any of these separation methods could be used
for separation of sulfur from the organic phase.
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Petroleum industries commonly employ solvent extraction
techniques to remove sulfur and nitrogen compounds from light
oil. The solvent is recovered and reused through a distillation
process.88,96 However, the difference in polarity between sulfur
and other aromatic hydrocarbons is very small. Therefore,
employing only solvent extraction is accompanied by associated
loss of useful hydrocarbons along with reduction of sulfur
compounds removal.88,92,97–98 The selective oxidation approach
of increasing the polarity of sulfur compounds followed by their
removal by selective extraction, therefore, has received much
great attention recently.
5.2. Oxidants in ODS
A significant research effort has been conducted on ODS over
the years. Many oxidants have been investigated that include
organic and inorganic peroxy acids, catalyzed hydro-peroxides,
peroxy salts, NO2, tert-butyl-hydroperoxide, O3, etc.88,93,99–105
ODS process were first employed using nitrogen dioxides as an
oxidant, followed by extraction with methanol to remove both
sulfur and nitrogen compounds from petroleum stocks. Few
investigators have used an oxidizing gas containing nitrogen
oxides for purifying hydrocarbon aqueous oils containing both
sulfur and nitrogen compound.88,92,96 Attar and Corcoran106
oxidised diesel fuel with nitrogen oxides. Overall 70% conversion
of sulfur compounds to sulfones was obtained at 140 uC.
However, this technology yields many undesirable byproducts
because of initiation of a very non-selective reaction by nitrogen
oxides in the presence of oxygen. Also, there is always a safety
problem due to the possibility of a rapid and explosive reaction.
Several peroxy organic acids (formic, acetic, propionic,
performic, pertrifluoro acetic acids etc.) and Caro’s acid
(peroxysulfuric acid) have been employed at 95–125uF near
atmospheric pressure for selective oxidation of organic-sulfur
compounds.90,96,107 Liu et al.108 investigated the oxidation of
model sulfur compound and diesel oil by K2FeO4 in water-
phase, in organic acid and in the presence of phase-transfer
catalysts. The results showed that the oxidation activity of BT
and DBT was low in water-phase, even after adding phase-
transfer catalyst to the system. This was because K2FeO4 reacted
rapidly with water to form brown Fe(OH)3, thus, losing the
oxidation ability. The oxidation activity of the BT and DBT
increased markedly in acetic acid. Moreover, the addition of the
solid catalyst to the acetic acid medium promoted oxidation of
organic sulfur compounds. Conversions of the BT and DBT
were 98.4% and 70.1%, respectively, under the condition of room
temperature, atmospheric pressure, acetic acid/oil (v/v) = 1.0,
K2FeO4/S (mol/mol) = 1.0 and catalyst/K2FeO4 (mol/mol) = 1.0.
Under the same condition, 96.7% sulfur removal (457 ppm to
15.1 ppm) was obtained from diesel oil which was subjected to
oxidation followed by furfural extraction. Nehlsen5 reported the
oxidation and extraction of organo-sulfur compounds, including
TH and alkyl sulfides with concentrated sulfuric acid. Sulfuric
acid is not typically regarded as an oxidizing acid due to the
stability of the sulfate ion. However, in the presence of sulfur
atoms with lower oxidation states, such as those in sulfides,
sulfate can be reduced. The reaction between H2S and
concentrated sulfuric acid is fast and yields elemental sulfur,
water, and SO2 as reaction products.
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Shiraishi et al.109–111 accomplished desulfurization of sulfur
compounds such as DBTs and BTs with alkylating agents, CH3I
and AgBF4 in the presence of dichloromethane. This process was
based on the formation and subsequent precipitation of
S-alkylsulfonium salts. Main drawback of this process was
methylation of other aromatic hydrocarbons. Shiraishi et al.112
reported desulfurization of light oils to less than 0.05 wt% based
on the formation and subsequent adsorption of N-tosylsulfimides,
produced by the reaction of the sulfur compounds in the light oils
with chloramine T. The desulfurization of high-aromatic-content
light oil was relatively more difficult due to the chlorination of the
aromatic hydrocarbons by chloramine T which becomes compe-
titive with chlorination of the sulfur compounds.
H2O2 is the most common oxidant because of its environ-
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mental friendliness. The oxidation of sulfur compounds with
H2O2 has been studied over various catalytic systems such as
HCOOH, CCl3COOH, polyoxomethalate CF3COOH, methyl-
trioxorhenium(VII), and phosphotungstic acid, titano silicates,
and solid base.92,94,99,112–118 Shiraishi et al.109 reported sulfur and
nitrogen removal from light oils using hydrogen peroxide and
acetic acid. Lanju et al.119 carried out ODS of simulated gasoline
consisting of model sulfur compounds of TH and 3-methythio-
phene (3-MC4H4S) dissolved in n-heptane in hydrogen peroxide
(H2O2) and formic acid oxidative system over metal oxide-
loaded molecular sieve. The results showed that the sulfur
removal rate of simulated gasoline was higher in H2O2/organic
acid systems than in H2O2/inorganic acid systems. The cerium
oxide-loaded molecular sieve was found very active catalyst for
oxidation of simulated gasoline in this system. The sulfur
removal rates of C4H4S and 3-MC4H4S were enhanced when
phase transfer catalyst (PTC) was added. The sulfur removal rate
of simulated gasoline reduced with the addition of cyclohexene
and xylene into the solvent n-heptane. Al-Shahrani et al.120
utilized a catalytic system composed of Na2WO4, 30% H2O2 and
CH3COOH for the deep removal of sulfur in diesel. Treatment of
model solutions of octane containing DBT and 4,6-dimethyl
DBT with the above ODS system showed 100% conversion of
the THs to sulfones at 70 uC in less than 1 h. At modest
temperatures and under atmospheric pressure, the catalytic
system was effective for removing most of the last few hundred
ppm of HDS-persistent organic sulfur containing compounds in
diesel.
Transition metal based catalysts namely methyl trioxorhenium
mixed molybdenum/tungsten oxides121 and tungsto phosphoric
acid (TPA)122 have been used in conjunction with a hydrogen
peroxide as oxidant. Herbstman and Patel123 also reported that
the use of same catalyst followed by a high temperature thermal
or KOH treatment at 250 uC accounted 43% desulfurization.
D’Alessandro et al.124 reported a catalytic system consisting of
metal-sulfophthalocyanines (MPcS) and monopersulfate or
hydrogen peroxide as oxidants for the DBT ODS. Among the
various MPcS catalysts examined (MLFe, Co and Ru), the
ruthenium derivative exhibited the best performance with
persulfate and iron derivative and hydrogen peroxide.
Gutierrez et al.125 developed and evaluated Mo/c–Al2O3
catalysts for the ODS of diesel fuel using H2O2 as the oxidizing
reagent. The results showed that the activity for sulfur
elimination depended mainly on the presence of hepta-and
octamolybdates species in the catalyst support and the use of a
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polar aprotic solvent. Likewise, the presence of phosphate
markedly increased the sulfur elimination. Using this catalyst,
it was possible to reduce sulfur levels in diesel fuel from about
320 to less than 10 parts per million by weight (ppmw) at 333 K
and atmospheric pressure. Caero et al.126 evaluated ODS
activities of DBTs in hexadecane for a series of V2O5 catalysts
supported on alumina, titania, ceria, niobia and silica. It was
observed that the sulfone yield was not proportional to textural
properties or V content. Total S-removal was close to 99% using
vanadia on titania as catalyst, and this decreased according to
the support used in the order: alumina > titania > niobia > Al–Ti
mixed oxide > SBA-15. The oxidation activity of DBTs for V
catalyst supported on niobia or alumina presented higher
catalytic activity than all the other catalysts (niobia > alumina
> SBA-15 > titania > ceria > Al–Ti mixed oxide). However, in
the presence of an N-compound such as indole the best catalytic
performance was obtained with titania-supported catalysts.
Collins121 used tetra-amido macrocyclic ligand (TAML)
activators to enhance the oxidizing ability of hydrogen peroxide
at low catalyst concentration and mild reaction conditions.
TAML activators are used in many different areas including the
pulp and paper, textile and laundry industries; mineralization of
organohalogens, and others.127,128 They are capable of rapidly
oxidizing the DBT derivatives that are of concern to the
petroleum industry. Fe–TAML activators were used under
different reaction conditions including variable pH, temperature
and solvent composition. Micromolar concentrations of the
FeF2B activator were reacted with H2O2 to convert greater than
99% of millimolar solutions (>7000 : 1 substrate: catalyst
concentrations) of DBT derivatives to the corresponding
sulfones under mild conditions. Yang et al.100 reported oxidation
of DBT into sulfone using polyoxometalates with a Keggin
structure such as H3PM12O40 [M, Mo(VI), W(VI)]. H3PW12O40
(HPWA) was supported on mesoporous molecular sieves SBA-
15 to obtain HPWA-SBA-15. HPWA-SBA-15 has both catalytic
oxidation ability and adsorption ability. The non-polar DBT
were converted into polar DBT sulfones that were easily
absorbed on HPWA-SBA-15.
5.3. ODS by other methods
5.3.1. Radiation assisted oxidation. Irradiation techniques can
be applied to reduce sulfur compounds using radiation induced
reactions of hydrogenation in which hydrogen results from the
radiation-induced hydrocarbon destruction. This was supple-
mented by radiation methods developed for H2S extraction from
gaseous mixes. Zaykina et al.129 showed that radiation proces-
sing can be efficiently used for conversion of mercaptans and
other light sulfuric species to sulfones, sulfuric oxides and acids.
Irradiation method of desulfurization includes two stages. The
first stage is radiation processing, and the second stage is the
extraction of highly oxidized sulfuric compounds. No desulfur-
ization of the overall product occurs in the first stage. However,
strong oxidation of sulfuric material in the first stage removes its
chemical aggressiveness and enhances its removal. It also causes
some sulfur redistribution in the overall product leading to the
partial desulfurization of light oil fractions. The high level of
sulfur oxidation is due to the double oxidation processes of
radiation and ozone-containing atmospheric air activation. The
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Scheme 1 Mercaptan oxidation and transformation via radiation
assisted oxidation.101
ozone-containing air excited by energetic electron bombardment
appears here in the role of an oxidizer. One of the routes
for mercaptan oxidation and transformation is shown in
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Scheme 1:101
Accumulation of hydrogen hampers mercaptan conversion,
but controlled access of ozone-containing air mixed into the
reactor allows one to regulate the degree of mercaptan
conversion. The application of ozone as an oxidizer for oil
mixtures was proposed earlier.130 One of the virtues of this
technology is the possibility of achieving any desired degree of
sulfur oxidation at minimum processing time and maximum
process simplicity. This approach is technically feasible; how-
ever, it requires the development of special equipment and use of
a multi-step process.
Nadirov et al.131 and Zaykin et al.132 studied the processing of
heavy fuel oil by two irradiation methods under two different
modes with the purpose of producing light oil fractions from the
feedstock and, simultaneously, transforming sulfur into harmless
and easily extractable forms. The feedstock was irradiated by 2
MeV electrons in the temperature range 300–400 uC using
different values of other operational parameters (dose rate, P;
dose, D). Mode 1 (P = 6 kGy/s, D = 30 kGy) used severe
irradiation conditions and resulted in high yields of motor fuels.
Mode 2 (P = 2 kGy/s, D = 70 kGy) was milder and caused lesser
changes in hydrocarbon contents and appeared to be more
favorable for conversion of sulfur compounds. 80% mercaptan
conversion was reached in this milder mode and more than 90%
of the total sulfur was concentrated in the heavy liquid fraction
with boiling temperature higher than 350 uC.
5.3.2. Ultrasound assisted ODS. It is well known that the use of
ultrasound can significantly improve the reaction efficiency
under phase transfer conditions.133–135 Ultrasound helps in
improving the liquid–liquid interfacial area for viscous films
containing gas-filled bubbles and cavitation bubbles through
emulsification. Very fine ultra emulsions formed with the help of
ultrasonic waves greatly improve the interfacial area available
for reaction thus increasing the effective local concentration of
reactive species, and enhancing the mass transfer in the
interfacial region. Therefore, ultrasound increases the reaction
rate under phase transfer conditions.136 Furthermore, cavitation
during sonication produces extreme local conditions and a
microenvironment with high temperature and high pressure,
which also creates active intermediates that permit the reaction
to proceed instantaneously.137
Catalytic ODS process under phase transfer conditions and
ultrasonication is termed as ultrasound assisted ODS (UAOD).
This photo-induced oxidation process uses the absorption of
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short wavelength UV light for the direct photo-excitation of
DBTs. This process relies on shock waves to agitate sulfur
molecules, and allows for their extraction from oil as sulfones.138
The conceptual model of the oxidation step in the UAOD
process may be depicted as a catalytic cycle, as depicted in
Fig. 2.139–141 It consists of four basic steps: First, the metal
precursor (simply represented as W(O)n), is peroxidized and
disaggregated to form anionic peroxometal complex as W(O2)n
in the presence of excess H2O2, phosphotungstic acid; second,
quaternary ammonium salts such as Oc4N+Br2with large
lipophilic cation function as PTA, and transfer the peroxometal
anion into organic phase; third, organic sulfur compounds such
as DBT get oxidized by the peroxometal complex with high
efficiency and high selectivity; lastly, the reduced oxo species,
which dissociate with PTA, returns to aqueous phase and
restores the catalytic cycle.102
5.3.3. Photo-oxidation. Desulfurization of model compounds
such as DBTs has also been studied by photo-decomposition
with UV light in the organic phase, and removal of resulting
sulfur compounds into water or acetonitrile phase.142–145 For
diesel fuels containing various levels of sulfur content, the use of
ultrasonication followed by solvent extraction showed removal
efficiency of sulfur-bearing compounds exceeding 99% in a short
contact time at ambient temperature and atmospheric pres-
sure.102
A high pressure mercury lamp (l > 280 nm) has been used for
desulfurization by direct photo-oxidation,143,144,146 gasoline147
and gas oil.148–149 Hirai et al.143 investigated photodecomposi-
tion of DBTs dissolved in tetradecane by the use of a high-
pressure mercury lamp (l > 280 nm). The decomposed products
were removed to the water phase as SO422 at conditions of room
temperature and atmospheric pressure. The order of reactivity
for the DBTs was DBT , 4-MDBT , 4,6-DMDBT which is just
opposite to that for the HDS method. The desulfurization yield
of commercial light oil, however, was only 22% following 30 h of
irradiation. This low yield was due to the depression of
photoreaction of the DBT by the presence of aromatic
compounds such as naphthalene and its derivatives in the light
oil.143 Hirai et al.144 used same method for photodecomposition
of benzothiophenes and alkyl sulfides.
Fig. 2 Conceptual model of catalytic oxidation in UAOD process.
W(O2)n2 represents the Keggin heteropolytungstate anion, Q+ represents
the quaternary ammonium cation of octyl from the PTA.139–141
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Photosensitized oxidation has been also investigated for light
oil to utilize light in the visible region (l > 400 nm) more
efficiently.145,150–151 Hirai et al.142 found that the addition of
benzophenone (BZP), a triplet photosensitizer, enhanced the
removal of DBT from tetradecane. However, this reaction didn’t
proceed in the presence of naphthalene (NP), because of triplet
energy transfer from photoexcited DBT or BZP to ground-state
NP. The addition of H2O2 enhanced the desulfurization of
commercial light oil as well as the removal of DBT from
tetradecane. This was due to the fact that H2O2 acted as a weak
oxidizing agent for photoexcited DBT and interrupted the
energy transfer from excited DBT to NP to some extent. The
desulfurization yield, with the use of 30% H2O2 solution, of
commercial light oil was 75% following 24 h of photo-irradiation
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and the sulfur content in the light oil was reduced from
0.2 wt% to less than 0.05 wt%.145 In these studies,143–145
desulfurization was basically done by photodecomposition of
sulfur-containing compounds in the light oil phase, followed by
the transfer of the resultant decomposed compounds into the
aqueous phase. Thus, deactivation of the photoexcited DBTs by
naphthalene was predictable. However, H2O2 is known to be
photodecomposed by the absorption of the short-wavelength UV
light (l , 280 nm), which is necessary for the direct
photoexcitation of DBT.
In earlier studies, photochemical reactions suffered from the
quenching effect caused by associated aromatic hydrocarbons in
fuels; and the desulfurization yield for real fuels was significantly
lower than those for model solvents such as hexane and
tetradecane.152 Extractive photo-oxidation, which combines the
extraction of organosulfur compounds in polar solvents and
subsequent photo-oxidation, was investigated to reduce the
quenching effect by aromatic hydrocarbons.8,146,150,153 Shiraishi
et al.8 found that DBT gets converted to DBT–O and then to
DBT–O2, DBT sultine, and aromatic sulfonate or sulfinate anion
in presence of acetonitrile by the UV irradiation. These products
are highly polarized and are therefore not distributed into the
nonpolar light oil phase. This process reduced the sulfur content
of commercial light oil (CLO) from 0.2 to 0.05 wt% after 2 h of
irradiation and that of straight-run light gas oil (LGO) from 1.4
to 0.05 wt% after 10 h of irradiation. The separation of the
coextracted aromatics from acetonitrile was carried out success-
fully by using light paraffinic hydrocarbon stripping agents.
Shiraishi et al.153 identified in detail the acidic products of BT
and DBT in acetonitrile. This was achieved by methylation of the
compounds with diazomethane and analysis using gas chroma-
tography with atomic emission detection (GC-AED) analysis
and Gas chromatography with mass spectra (GC-MS) analysis.
Studies on indirect photo-oxidation that generates oxidizing
agents in situ by UV irradiation (400 nm > l > 300 nm)154 and
photocatalytic oxidation using TiO2 (l > 290 nm)155–157 have
also been reported. Abdel-Wahab and Gaber158 used anatase-
type TiO2 and studied photocatalytic oxidation of DBT in
acetonitrile. Matsuzawa et al.159 reported photo-oxidation of
DBT and 4,6DMDBT in acetonitrile using titanium dioxide
(TiO2) including P25 as catalysts. DBT was found to be more
stable than 4,6DMDBT and that the rate of photo-oxidation
differs depending on the kind of TiO2.
UV light below 280 nm has been used for fundamental studies
on the mechanism of photo-oxidation of aliphatic disulfides,
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sulfides and thiols160–163 as well as the mechanism of photo-
dissociation of aliphatic disulfides.164 Robertson and Bandosz157
used a multilayer TiO2–hectorite nanofilm photocatalyst for the
photo-oxidation (l , 280 nm) of dibenzothiophene (DBT) in
nonpolar organic solution (tetradecane), as a model for diesel
fuel. Photo-oxidation of DBT was performed with and without
catalyst, at 254 and 300 nm and comparison was made with a
commercially available TiO2 catalyst, Degussa P25. At 300 nm in
the presence of catalyst, photo-oxidation preceded primarily
by indirect photolysis, according to a zero-order rate law. At
254 nm, the rate was determined primarily by first-order direct
photolysis, though the presence of the catalyst increased the
overall rate of removal. Further adsorption of oxidation
products by silica reduced the sulfur concentrations below
10 ppm. Tao et al.152 investigated selective photooxidation and
adsorptive desulfurization of kerosene using a 5W low-pressure
mercury lamp at 25 uC in the presence of O2. There is a group of
sulfur compounds that are easily photo-oxidized with UV light
below 280 nm in the presence of molecular oxygen without using
any catalysts. The reactivity of these sulfur compounds was at
least 100 times higher than those of DBTs and the photooxida-
tion of these highly reactive sulfur compounds was completed
within 30 min. The easily oxidized sulfur compounds can be
removed from kerosene with adsorbents, such as molecular sieve,
silica gel and activated alumina. On the other hand, non-reactive
sulfur compounds such as DBTs were removed by adsorbents
such as activated carbon by hydrophobic interaction. As a result,
total sulfur content can be reduced from 7 ppm to less than
0.1 ppm.
However, at the present stage, there are a number of problems
that need to be solved to make the extractive photo-oxidation
desulfurization process technically and economically feasible.
Better solvents need to chosen so as to increase sulfur
compounds solubility and aromatic rejection. Recovery of
solvent needs special attention. Combination of a solvent and
a photosensitizer has to be optimized to increase the rate of the
organosulfur compounds photo-transformation. Photosensitizer
may be stabilized on the surface of a solid carrier so without
losing its ability to accelerate photo-oxidation of the sulfur
compounds.88
5.3.4. Electrochemical catalytic oxidation. Wang et al.165–166
developed a process for gasoline desulfurization using electro-
chemical catalytic oxidation within an electrochemical fluidized-
bed reactor having particle group anode. The particle group
anode was activated carbon-supported cerium dioxide (CeO2/C),
the electrolyte was aqueous cerium nitrate solution, and copper
pillar was used as cathode in the electrochemical reactions. The
CeO2/C particle group anode accelerated the electrochemical
reaction rate and promoted the electrochemical catalysis
performance for the electrochemical desulfurization reaction.
The theoretical decomposition voltage ranged from 0.1–0.5 V in
pure acid electrolyte system, however, desulfurization reactions
could not be carried out spontaneously. The reactions became
spontaneous after the use of aqueous cerium nitrate solution as
electrolyte. Cell voltage, concentration of the Ce3+ ions, feed
volume flow rate and the CeO2 percentage by weight at the
optimal desulfurization conditions were 3.2 V, 0.08 mol l21,
300 ml min21 and 5.0 wt%, respectively. Under these conditions
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the concentration of sulfur in gasoline was reduced from 310 to
50 ppmw.
5.3.5. Plasma ODS. Plasma ODS of mixed organic sulfides in
the liquid phase was investigated by Liu et al.40 The organic
sulfides namely mercaptan, thioether and TH were oxidized at a
temperature of 285 uC and a pressure of 120 Pa. The
desulfurization was not complete, and the process was not
economical.
Table 4 summarizes recent researches conducted for optimiza-
tion of ODS processes with and without use of any oxidants.
5.4. Extraction in ODS
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of solvent and oxidized compounds by a simple distillation for
recycling and re-use.
Some common water-soluble polar solvents used are dimethyl
sulfoxide (DMSO), dimethylformamide (DMF), acetonitrile,
etc.88,99,114,168–169 The former two solvents have a high extrac-
tability for sulfones but also have a high boiling point (573 K).
This is close to the boiling point of the sulfones, thus creates
difficult in separation and reuse for further extraction.
5.4.1. Ionic Liquids. Ionic liquids (ILs) are organic salts having
melting point below 100 uC that are composed of organic cations
and organic/inorganic anions.170 Attractive properties of ILs
such as nonvolatility, solubility for organic/inorganic com-

The sulfoxides and sulfones produced after ODS have increased
relative polarity, and are preferentially extracted from light oil
using a non-miscible solvent.88,92,96,167 The extraction efficiency
depends on the solvent’s polarity. Polarity, however, is not the
only criteria for the selection of suitable solvents. Methanol, for
example has sufficient polarity, but its density, 0.79 kg m23, is
about the same as that of typical light diesel oil and is therefore
not preferred extraction solvent. Other properties such as boiling
point, freezing point, and surface tension need to be considered
carefully to evaluate the potential for separation and recovery of
the solvent for recycling and reuse.92,96
Depending on the solvents used for extraction, the oxidized
compounds and solvent are separated from the light oil by
gravity separation or centrifugation. Any unused oxidant that
remains in the light oil is removed by water washing and
extracting. The light oil is water washed to recover any traces of
dissolved extraction solvent and unused oxidant. It is then
polished using other methods such as absorption using silica gel
and aluminum oxide. The solvent is separated from the mixture
pounds, good thermal/chemical stability, nonflammability,
recyclability, and environmental friendliness make ILs as
suitable extractants for sulfur compounds.170–172 ILs have been
used either for direct extraction of S-compounds (extractive
desulfurization, EDS)173–194 or for extraction of oxidized
S-compounds obtained for ODS.170,195–205 EDS studies have
been performed using ILs that are composed of anions such as
BF42, PF62, AlCl42, and EtSO42 and cations such as
imidazolium and pyridinium.173–194 ILs can be tailored by
sensible selection of cation, anion and substituents so they can
be designed to perform selective liquid–liquid separations.206–209
The earliest application for desulfurization by IL was reported
in 2001.176 They found that multi-step extraction using AlCl3 ILs
reduced the sulfur concentration from 500 mg l21 down to
235 mg l21. Phillips210 also used AlCl3 and AlCl4 based ILs for
the removal of S-containing compounds. Eber et al.211 proposed
design of industrial equipment for deep desulfurization of oil
refinery streams by extraction with ILs. Imidazolium-based ILs
with PF62 and BF42 anions;192–193,212 and N-alkyl-3-methylimi-

Table 4 Sulfur removal by ODS at optimized conditions

Optimum Conditions
S Conc. Temp. Pressure %S
Process Sample Model Oil Reagent System Co (ppm) (uC) (atm) Removal Reference

Oxidation- DBT n-Octane H2O2 + Batch 800 60 1 99% 103

Adsorption Activated C
Oxidation- DBT n-Octane H2O2 Batch 800 60 1 60% 103
Adsorption
Oxidation- DBT Toluene (40%) H2O2 Batch 5000 50 1 92% 93
Extraction Hexane (60%)
Oxidation BTs Decalin H2O2 + Batch 500 40 1 98% 104
Amphiphilic Catalyst
Oxidation Tetrahydrothiophene cyclohexane H2SO4 Batch 2000 22 1 99% 5
Oxidation Thiophene + n-Heptane H2O2 + Formic Acid Batch 500 50 1 80% 119
3-methylthiophene
Oxidation DBT + 4,6-DMDBT Octane Na2WO4 + 30% H2O2 Batch 500 70 1 100% 120
+ CH3CO2H
Oxidation- DBT Iso-Octane t-BuOOH + Batch 174 70 1 97.43% 105
Adsorption HPWA-SBA-15
Oxidation Alkylated DBTs Diesel H2O2 + Mo/c–Al2O3 Batch 320 60 1 97% 125
Oxidation DBTs Hexadecane H2O2 + V2O5 Batch 500 60 1 99% 126
based catalysts
Oxidation BT + DBT Petroleum ether K2FeO4 Batch 457 35 1 98% 108
Radiation — Crude Oil — — 3000 350 — 90% 129
Oxidation
Ultrasound DBT Toluene H2O2 Batch 3000 75 1 98% 102
Oxidation
Electrochemical — Gasoline CeO2/C based anode Electrolysis 310 25 — 83% 165
Oxidation Cell

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dazolium bis(trifluoromethylsulfonyl)imide ILs213–216 have also
been used by several investigators. However with these ILs, a
change in the content of aromatics was observed and suitability
for real industrial fuels was not well established. Imidazolium-
based phosphoric ILs were also tested184–186,217–218 which
showed encouraging results. Gao et al.179–180 and Domanska
et al.219 performed several extraction experiments with alkyl-and
alkylmethyl-pyridinium-based ILs with ethanoate and thiocya-
nate anions as alternative to the perfluorinated and tetrafluobo-
rate ones giving the good extraction performance. Instability and
regeneration of the Ils, corrosion problem, negative effects on
fuel quality and high total costs of deep fuel desulfurization
make the use of Ils in still a challenging task for research-
ers.172,212 A number of excellent reviews have already been
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published which critically evaluate desulfurization of liquid fuels
by Ils and these are referred for further study.170,209,212,220–223
5.5. Future challenges to ODS
There are two major problems associated with ODS. First, the
oxidants chosen do not always perform selectively. Some
oxidants cause unwanted side reactions that reduce the quantity
and quality of the light oil. The second problem is the selection
of a suitable solvent for the extraction of the sulfur compounds.
Using the wrong solvent may result in removing desirable
aromatic/olefinic compounds from the fuel or extracting less
than desired amount of the sulfur compounds from the fuel.93
Reaction selectivity, safety and cost are important concerns for
the selection of oxidant, catalyst and operating conditions for
ODS processing.
The catalytic systems reported are mostly toxic and expensive.
There are issues relating to ultimate fuel quality and economy of
the process. Thus, there is a need for a new technology that can
perform the oxidation reaction under mild conditions, and one
that can selectively oxidize the sulfur compounds. However,
despite all the disadvantages, greatest advantage of the ODS
process is low reaction temperature and pressure. It removes the
need for expensive hydrogen that is used in the conventional HDS
process. Another feature of ODS is that the refracted sulfur
compounds in ODS are easily converted by oxidation.115 ODS
avoids the aromatic and olefin saturation, and thus low octane
number. Therefore, ODS has great potential to be complementary
process to traditional HDS for achieving deep desulfurization.
The development and application of oxidation/extraction method
are considered among the most desired options because they can
lower the sulfur without negative impact on capital investment.
6. Adsorptive desulfurization
6.1. Introduction
Adsorption has been applied variously for removal of sulfur
compounds from liquid hydrocarbon fuels. Removal of DBT
and other sulfur compounds has been studied over zeolites,
aluminosilicates, activated carbon (AC), alumina, zinc oxide,
etc.224–239 However, only few adsorbents have shown high
selectivity for difficult to hydrotreat sulfur compounds such as
4,6-dimethylDBT. In the following sections, recent studies which
utilized various adsorbants have been discussed and research
gaps have been identified.
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6.2. Adsorbents
6.2.1. Activated carbon and its modifications. Activated
carbons are widely used as adsorbents for the treatment of
polluted water or wastewater. Commonly, most commercially
available activated carbons have good porosity and are of high
surface area, and consequently they have high efficiency for the
adsorption of various types of compounds.240 Lee et al.224
studied sulfur removal from diesel fuel. Ten different ACs
obtained from different sources were screened. It was concluded
that coconut shell-based carbons activated by high temperature
steam were more effective at sulfur removal than coal-based or
wood-based carbons.
Sano et al.226 proposed an integrated process for deep
desulfurization where conventionally hydrodesulfurized straight
run gas oil (HDS-SRGO) was desulfurized to less than 10 ppm S
over an ACF. The adsorption bed used in the desulfurization of
HDS-SRGO was used again to denitrogenate and desulfurised
SRGO as a pre-treatment step of conventional HDS process. As
shown in Fig. 3, twice use of ACF in sequence as an adsorbent
for HDS-SRGO and SRGO reduced the frequency of regenera-
tion and oil loss in the adsorption bed. Fully saturated
adsorption bed was regenerated by conventional solvent, such
as toluene. ACF showed low pressure drop and high perfor-
mance among the AC materials examined.
Modifications of carbon surfaces by incorporation of metals
and oxidation of carbon surface can have a positive effect on the
adsorption of DBTs.241–264 This happens due to p-electron
interactions of sulfur-containing aromatic compounds with
metals on the activated carbon257 and due to oxidation of
carbon surface.246,248,256
Incorporation of metals such as copper and iron increases the
capacity and selectivity for adsorption and the catalytic
transformations on the surface.249,256 The selectivity increase is
due to acid–base interactions of slightly basic thiophenes with
acidic oxygen containing groups246,248,254 or due to increased
polarity and redox reactions.249,258 Ania and coworkers,248–249
Zhou and co-workers250 and Yang and co-workers253 have
reported on the positive role of acidic groups for desulfurization.
It has been reported that both microporosity and the surface
chemistry are important for efficient desulfurization.254 The
increase in the adsorption capacity has been linked to the
development of pores with diameters less than 10 Å as a result of
various modifications of carbon materials.248,259–261 Pores
similar in size to DBT or DMDBT molecules, are important at
low surface coverage where dispersive forces are the stron-
gest.249,254,258–262 The amount adsorbed is also governed by the
volume in pores smaller than 10 Å. The small pores, which are
too small to accommodate functional groups, govern the
physical nonspecific adsorption process that is based on
dispersive interactions.
With the progress of adsorption, oxygen containing functional
groups248,254,262–263 and/or the introduced catalytic inorganic
phase258 start to affect/enhance the amount adsorbed via specific
interactions. Oxidation is an important factor since on the
surface of unmodified activated carbons other aromatic compo-
nents of liquid fuels are also adsorbed in significant quantities.
Oxidation of carbon surface leads to the formation of oxidized
species of DBT and 4,6-DMDBT, which are strongly adsorbed
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Fig. 3 Schematic diagram of consecutive adsorption process.226
via interactions with polar groups of the carbon surface. Thus,
oxidation increases the selectivity of DBT adsorption via an
increase in the number of specific adsorption centers, whereas
the adsorption of aromatic hydrocarbons decreases with an
increase in the extent of oxidation.246,248,254,258,262–263
6.2.2. Other adsorbents. Silica gel is the most widely used
adsorbent as its surface can be readily modified by reacting (or
grafting) with a monomolecular layer of organic ligand. Park
et al.237 studied selective desulfurization of commercial diesel by
adsorption of sulfur compounds onto metallic nanosize Ni
nanoparticles supported on mesoporous silica SBA-15 and KIT-
6. The maximum Ni concentration achieved was 30 wt% for both
the substrates. Under these conditions, the best dynamic
adsorption capacity observed was 1.7 mg g21 at 10 ppmw S
breakthrough level with a high sulfur diesel (240 ppmw) on
30 wt% Ni/SBA-15. For a low sulfur diesel (11.7 ppmw), the
corresponding result was 0.47 mg g21 for the same adsorbent at
0.1 ppmw S breakthrough level, which is considered to be
suitable for fuel cell applications.
Activated alumina has good adsorptive properties and has
been used for the removal of organic compound from aqueous
solutions. Unlike silica gel, which is amorphous, activated
alumina is crystalline. Oxygen vacancies (defects) are easily
formed on its surfaces, thus alumina has both Lewis and
Brønsted acid sites.265 The surface chemistry, as well as the pore
structure of activated alumina, can be modified, for example, by
treatment with acid (HCl or HF) or alkaline (to alter the acidity)
and controlled thermal treatment (to tailor the pore structure).
As a result, activated alumina is more versatile than silica gel and
has been applied more often as a sorbent.266 Larrubia et al.227
studied the adsorption of BT, DBT and 4,6-DMDBT on
alumina, zirconia and magnesia. It was found that adsorption
on alumina was the strongest, forever, 4,6-DMDBT adsorption
was limited due to steric effect. Etemadi and Yen228 studied the
surface properties of two different phases of alumina (amor-
phous acidic alumina and nanopowder alumina) through SEM
images. The effect of calcining on alumina particles was also
investigated through SEM images. Adsorption capacity of
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amorphous acidic alumina was found to be 1.6 times lower than
the nanopowder sample, though the surface area was 2.3 to 4.6
times smaller. Crystallinity of the adsorbent decreased its
adsorption capacity. Higher disorder provided more topological
traps, irregularities, and hidden grooves for higher adsorption
capacity. Therefore, the amorphous phase provided more sites
for adsorption. Srivastav and Srivastava267 recently reported the
usage of commercial grade activated alumina (aluminum oxide)
as adsorbent for the removal of DBT dissolved in n-hexane.
Optimum adsorbent dose was found to be 20 g l21. The
adsorption of DBT on alumina was found to be gradual process,
and quasi-equilibrium reached in 24 h. Baeza et al.239 used
copper supported on zirconia to separate low TH concentration
from a mixture of 2000 ppmw of TH in n-octane at room
temperature and atmospheric pressure. The results showed that
the capacity of copper supported zirconia to adsorb TH
increased as the copper content increased, reaching a maximum
at a concentration of 3% of copper. Kumar et al.268 also studied
various laboratory prepared zirconia based adsorbents for
removal of DBT from iso-octane.
Zeolites are crystalline aluminosilicates of alkali or alkali earth
elements, such as sodium, potassium, and calcium. The primary
structural units of zeolites are the tetrahedra of silicon and
aluminum, SiO4 and A1O4. These units are assembled into
secondary polyhedral building units such as cubes, hexagonal
prisms, octahedra, and truncated octahedra. The silicon and
aluminum atoms, located at the corners of the polyhedra, are
joined by shared oxygen. The final zeolite structure consists of
assemblages of the secondary units in a regular three-dimen-
sional crystalline framework.266 Weitkamp et al.229 found that
TH is adsorbed more selectively than benzene when passed (in
vapor phase) over a fixed-bed adsorber packed with ZSM-5
zeolite as a sorbent. Yang et al.230 and Takahishi et al.231
compared the vapor phase adsorption isotherm for the different
sorbents, it was found that CuY and AgY zeolites had the best
TH adsorption capacity. The adsorption capacities followed the
order Cu–Y and AgY & NanZSM–S > AC > Na–Y > modified
alumina. Hernandez and Yang232 used the combination of CuY
zeolite with AC as sorbent. This sorbent’s total sulfur uptake
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(saturation loading) was 18.9 mg S g21 sorbent for commercial
diesel fuel (430 ppmw S) fed to the column at room temperature.
The breakthrough loading was calculated to be 10.9 mg S g21
sorbent.
Several works have developed new adsorbents to remove the
thiophenic compounds from commercial fuels via p-complexa-
tion. Gongshin233 prepared sorbents using ion-exchange techni-
ques to introduce d-block metals like Ag+, Cu+, Ni2+ and Zn2+
into zeolites. These ion exchanged materials were capable of
producing fuels with a total sulfur concentration of less than
1 ppm. Ngamcharussrivichai et al.234 synthesized zeolites using
coal fly ash. The zeolites were used for adsorption of TH and
BTH in n-hexane solution. It was shown that the introduction of
different heteroatoms into the framework of zeolites leads to
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different catalytic and adsorption properties. Tang et al.236
introduced gallium atoms into the framework of Y zeolite by
treating the zeolite with an aqueous solution of ammonium
hexafluoro gallate. Desulfurization of various model fuels
containing about 500 mg sulfur/g were studied over the
synthesized Y zeolite ([Ga]AlY) with a liquid hourly space
velocity of 7.2 h21 at ambient conditions. At ambient conditions,
the breakthrough capacity for the adsorption of TH, THT and
4,6-DMDBT were found to be 7.0, 17.4 and 14.5 mg of sulfur/g
of adsorbent, respectively. Ma et al.269 explored various
transition metal-based adsorbents to find an adsorbent in which
the metal interacts with the sulfur atom and not the CLC double
bond of the thiophenic compounds. The proprietary metal
compound was supported on porous silica gel with 5% loading.
The adsorbent was tested for removal of DBT and 4,6-DMDBT
from gasoline, diesel and jet fuel. It was found that the adsorbent
had significant selectivity toward the sulfur compounds over
naphthalene and 2-methylnaphthalene. Wang et al.270 achieved
desulfurization of a JP-5 light fraction (841 ppmw S) for fuel cell
applications by Pi-complexation adsorption with CuCl and
PdCl2 supported on the MCM-41 and SBA-15 mesoporous
materials. PdCl2/SBA-15 exhibited the highest sulfur selectivity
and capacity for the desulfurization of jet fuel among all known
sorbents. The total sulfur content of JP-5 light fraction was
reduced from 841 ppmw S to below 50.0 ppmw S. The spent
PdCl2/SBA-15, regenerated by purging with benzene at 70 uC,
could recover about 44% and 48% of the adsorption capacity at
breakthrough and saturation, respectively, compared with the
fresh adsorbent. Lu271 developed and used intermetallic crystal-
line powder made of tin and antimony for the destructive
adsorption of sulfur compounds from heavy oil. This bimetallic
powder had a highly porous structure with discrete crystals. This
adsorbent was prepared by melting an equi-atomic mixture of tin
and antimony in a graphite crucible. The melt was held at 500 uC
with a hydrogen gas cover to avoid oxidation. It was then pored
into an atomization nozzle that was operated at high nitrogen
pressure. The adiabatic expansion of gas rapidly cools the
droplets and freezes into a uniform size of about 10–15 mm. A
specific organic chemical was added during the sputtering
process at 375 uC to produce the proper size of cavities and
pits on the surface of powders. Lu271 showed in his studies that
intermetallic powder had the ability to lower the contents of
sulfur both in organic and inorganic form.
Metal–organic frameworks (MOF) consist of metal cations
linked by polyfunctional organic linkers. Organic linkers act as
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bridging ligands between the metal ions to form highly ordered
porous three-dimensional networks with large pore volumes and
high inner surface areas.272–275 MOF have been used to adsorb
selectively organo-sulfur compounds.273–276 Gaseous sulfur
compounds have also been removed using MOFs.277 A few
important factors, such as open metal sites compounds and pore
functionality, have been suggested for the efficient removal of
S-compounds.273–276
Cychosz et al.273 also studied different MOF materials and
their adsorption characteristics for organosulfur compounds in
model oil. Blanco-Brieva et al.275 demonstrated that the
adsorption of DBT at ambient temperature (304 K) is much
higher on MOF systems than on the benchmarked Y-type zeolite
and activated carbons. It was also found that the extent of
adsorption on the Cu–(C300) and Al-containing (A100) MOF
systems than on the Fe-containing (F300) MOF. The higher
adsorption capacity of DBT observed on C300 was due to the
stronger interaction of S–atom of DBT with surface Cu2+ ions.
Achmann et al.276 observed that a special copper-containing
MOF (copper benzene-1,3,5-tricarboxylate, Cu–BTC-MOF)
was able to remove 78 wt% and 86 wt% of the sulfur content
from thiophene containing model oils (initial sulfur content =
30 mg kg21) and tetrahydrothiophene (THT)-based model oils
(initial sulfur content = 9 mg kg21). The sulfur content of low-
sulfur gasoline was reduced by more than 22% to 6.5 mg kg21.
The sulfur level in diesel fuel was reduced by an extent of 13 wt%.
It was also demonstrated that sulfur adsorption occurred in the
first hour after addition of the sorption-material. Khan et al.278
studied the adsorption kinetics and thermodynamics in the
adsorption of BT over MOFs. The study has focused on the
adsorption over isotypic MOFs12 such as MIL-53(Cr, Al)279–280
and MIL-47(V)281 to understand the effect of central metal ions
on the adsorption of S-compounds. MIL-47 showed the highest
BT adsorption capacity among the isotypic Me–BDCs because
of high acidity. The driving force of BT adsorption over the
adsorbents was due to entropy effect. It was concluded that for
efficient S–compounds removal, a MOF-type material should
have a specific adsorption site like an acidic site. Shi et al.282
functionalized MOF-5 by decomposing Mo(CO)6 onto its
surface and evaluated it for the selective adsorption of
dibenzothiophene from solutions containing i-octane, naphtha-
lene and/or benzene. The resulting materials had Mo loadings up
to 20 wt%, surface areas in excess of 1800 m2 g21. Sulfur uptakes
at breakthrough approached 0.5 mmol S g21. The presence of
relatively low concentrations of aromatics like naphthalene and
benzene did not interfere with the adsorption of DBT, however,
at the high aromatics concentrations the sulfur adsorption
capacities decreased. The results indicate that this new type of
sorbent could be used for removing organosulfur compounds
typically left in gasoline, diesel and JP-8.282
Table 5 summarizes some of the researches conducted for the
sulfur removal with various types of adsorbents at optimized
conditions.269–274
6.3. Reactive adsorption
Reactive adsorption desulfurization (RADS) combines the
advantages of both the catalytic HDS and adsorption desulfur-
ization.286–291 In the RADS, sulfur-containing molecules react
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Table 5 Sulfur removal by adsorption at optimized conditions

Optimum Conditions
S Conc. Temp. Pressure %S
Process Sample Model Oil Adsorbent System Co (ppm) (uC) (atm) Removal Reference

Adsorption DBT — Activated Carbon Batch 178 25 1 95% 225

2 step Thiophenes Gas Oil Activated Carbon Packed Bed 300 70 1.5 88% 226
Adsorption
Adsorption DBT sulfone — Alumina Packed Column 700 200 — 30% 227
Adsorption Thiophenes Diesel CuCl/c–Al2O3 Fixed Bed 140 25 1 99% 233
Adsorption Thiophene + BT n-Hexane Zeolites from Batch 500 30 1 63% 234
coal fly ash
Adsorption 4,6-DMDBT cyclohexane NiMoP/Al2O3 Fixed Batch 450 340 40 56% 235
catalyst + NaY zeolites
Adsroption 4,6-DMDBT n-Nonane Gallium + Y zeolite Fixed bed 500 60 — 97% 236
flow reactor
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Selective — Commercial Ni nanoparticles Fixed bed 11.7 200 — 99% 237

Adsorption diesel supported on silica
Reactive Thiophene Ni/SiO2 and Ni/ZnO Fixed Bed 300 0.02 238
Adsorption
Adsorption Thiophene n-Octane Cu–zirconia Fixed bed 2000 180 — 99% 239
Pi-complexation — JP-5 light CuCl and PdCl2 Fixed bed 841 350 — 94% 270
adsorption fraction supported on the
MCM-41 and SBA-15
Adsorption DBT Crude Oil Intermetallic Powder Packed Bed 250 25 1 55% 271
Adsorption DBT Toluene (45%) Ruthenium Complexes Batch 40 25 1 50% 283
Hexane (55%)
Adsorption 4,6Me2DBT Toluene (45%) Ruthenium Complexes Batch 40 25 1 40% 283
Hexane (55%)
Bond cleavage Thiophenes n-Hexane (C5Me5)Rh(PMe3)(Ph)H Batch — 64 1 — 284
Alkylation 3-methylthiophene n-Heptane Silica-supported Slurry tank reactor 340 85 1 60% 285
12-phosphotungstic zeolite

with a solid adsorbent in the presence of hydrogen.286 Conoco
Phillips Petroleum Co. developed a new S–Zorb process for the
production of low-sulfur gasoline by reactive adsorption of
sulfur compounds over a solid sorbent at elevated temperatures
under a low hydrogen pressure.243,292 Transition metals sup-
ported on base oxides are usually used as the adsorbents for the
RADS. Ni/ZnO is an ideal adsorbent, in which the ZnO acts not
only as an acceptor of sulfur released during the regeneration of
sulfided Ni species, but also acts as a co-catalyst for the
hydrogenation of sulfur-containing compounds over the surface
of Ni species.88,238,243,286–296
Tawara et al.288 used Ni/ZnO for bringing down sulfur in
kerosene to ,0.1 mg g21 in the temperature range 270–300 uC
under H2 atmosphere at a pressure of 0.60 Mpa. The sulfur-
containing compounds were first decomposed through the
catalytic hydrogenation. The H2S–like species formed were then
adsorbed in the adsorbent. It was supposed that ZnO acts as an
acceptor for sulfur produced from sulfur-containing molecules
on Ni particles which were suggested to be ‘‘continuously
regenerated’’ during reaction.286
During the reaction, the active phase of the adsorbent
consisting of metallic particles supported on ZnO, is transformed
into a mixture of sulfides. After complete transformation
(saturation), the adsorbent is regenerated in a two-stage process:
sulfides are firstly calcined to obtain oxides which are than
treated in H2 in order to reduce the supported metal. RADS with
Ni/ZnO requires less hydrogen as compared to HDS and also
due to absence of side hydrogenation reactions, decrease in
octane number is not observed.297
Many efforts have been made to reveal the mechanism of
RADS. Babich and Moulijn proposed a reaction scheme in
which thiophene is decomposed on nickel surface that was then
sulfidized followed by hydrogenation of NiS site and transfer of
H2S to ZnO.88 Bezverkhyy et al.238 studied the kinetics of
thiophene RADS on Ni/SiO2 and Ni/ZnO by thermal gravi-
metric analysis at 280–360 uC under 5–40 mbar of thiophene in
H2. In the case of Ni/SiO2, the interaction proceeded in two
steps: a rapid surface reaction followed by a slower bulk
transformation into Ni3S2. Maximum Ni conversion depended
on reaction conditions and observed conversion profiles were
described by an exponential equation corresponding to a
reaction of first order relatively to both sulfidable Ni amount
and thiophene. In case of the interaction between Ni/ZnO and
thiophene, a rapid increase of weight, similar to the first stage
observed on Ni/SiO2, was not followed by bulk Ni sulfidation,
but instead by a nucleation-controlled ZnO surface transforma-
tion. After formation of the surface ZnS layer, a complete
particles sulfidation had with kinetics being strongly dependent
on the reaction conditions. Zhang et al.298 also reported that the
decomposition of thiophene on Ni/ZnO may occur, while S is
trapped by ZnO and converted into ZnS in the reactive
adsorption process. ZnO with favorable textural structures has
good activity of taking up the S, which may be the main reason
that the Ni/ZnO adsorbents with ZnO calcined at different
temperatures display different desulfurization activities.
Huang et al.287 carried out sulfur K-edge X-ray absorption
near-edge structure (XANES) to investigate the transfer of sulfur
species during the RADS process with Ni/ZnO under nitrogen
and hydrogen. The results indicated that the desulfurization
processes under nitrogen and hydrogen are different in the
reaction mechanism (Fig. 4). In nitrogen, the desulfurization
over Ni/ZnO is achieved through physical and chemical

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Fig. 4 RADS process with Ni/ZnO under nitrogen and hydrogen
atmosphere.287
adsorption; a severe decrease in the desulfurization activity of
Ni/ZnO is observed with the time on stream and the
desulfurization capacity is very low. Hydrogen facilitates the
decomposition of DBT on active Ni species, the formation of
Ni3S2, and thereafter the transfer of sulfur to ZnO. Metallic Ni
as the active nickel species is preserved until most of ZnO is
converted to ZnS. On the basis of these observations, a possible
sulfur transfer mechanism for the RADS is then proposed. Thus
in hydrogen, the desulfurization turns to be a reactive adsorption
process and Ni/ZnO exhibits a high desulfurization activity and
capacity.287
6.4. Future challenges for desulfurization by adsorption
One of the advantages of desulfurization of fuels by adsorption
over HDS is operation at low temperature. Another advantage is
that while H2 is abundant in refineries for use in the HDS
process, it is a precious reactant for generating power for fuel cell
applications. In addition, recycling the H2 exiting the reformer
back to the pre-reformer HDS unit adds complexity to the fuel
processing system. On another note, HDS cannot be easily
applied to internal reforming fuel cell systems, such as molten
carbonate and solid oxide fuel cells, since there is no H2 rich
stream to feed to the HDS reactor. Furthermore, the sulfur
content of the fuel can theoretically be reduced to a very low
level due to removal of the refractory sulfur compounds that
cannot be removed easily by HDS.
Desulfurization by adsorption faces two major challenges. The
first is to develop easy remunerable adsorbents with a high
adsorption capacity for sulfur compounds. The second challenge
is to find adsorbents that selectively adsorb the sulfur
compounds, which are mainly aromatic sulfur compounds that
have not been removed in the HDS process in refinery, over the
other aromatic and olefinic compounds present in tests hydro-
carbon fuel. While the adsorption process is highly effective,
the adsorbents are difficult to regenerate, often requiring
774 | RSC Adv., 2012, 2, 759–783
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calcinations or solvent washing.232 The adsorption capacity of
many adsorbents has been on low. Economical clay materials
displayed capacities of 1–4 mg S compound per g clay, thus
requiring huge amounts of adsorbent. Pressure swing adsorption
is not effective due to the strong interaction of sulfur with the
adsorbent. Large adsorbent beds are, therefore, required to
minimize the number of turnovers, and multiple beds are needed
to keep a refinery on-stream. Repeated calcinations can also lead
to a loss of surface area due to sintering; reducing the amount of
sulfur a bed can remove. Most research efforts, therefore, focus
on creating less expensive and higher surface area materials. In
developing the selective adsorbent, the key consideration is to
design the adsorbent materials which selectively interact with
sulfur in the presence of large excess of aromatic compounds,
which exist in concentrations of >20% in comparison with less
than 1 wt% sulfur compounds.
Investigations into the structure–activity relations of adsor-
bents as well as the active sites in these systems are needed. It
may also be informative to establish the relationship between
desulfurization activity and the chemisorption of model hydro-
carbon compounds which are commonly found in fossil-based
fuels. The mechanisms and kinetics of desulfurization reactions
over various adsorbents also deserve research attention.
7. Biodesulfurization
7.1. Introduction
Biodesulfurization (BDS) has drawn wide attention recently
because of its green processing of fossil fuels for removal of
sulphur compounds. During initial research, many bacterial
species that had the ability to consume DBTs as their energy
source were isolated from their natural habitats. However, these
isolated microbial species could not specifically remove sulfur
from DBTs. Some of the isolated microorganisms used
thiophenic compounds as carbon and sulfur sources. Some other
used metabolized DBTs as carbon source and, in a series of
oxidizing steps, converted them into several water-soluble
compounds. The accumulation of these water-soluble end
products significantly inhibited microbial growth and DBT
oxidation.288 Several bacterial species which are capable of either
bio-transforming DBT or growing on it as a sole sulfur source
have now been identified. These include Arthrobacter,
Brevibacterium, Pseudomonas, Gordona, and Rhodococcus spp.
7.2. Mechanism of BDS
Most of the work over the last decade has focused on the
metabolism of sulfur heterocycles like DBT by rhodococcus
strains, pseudomonas bacteria and other related species.168,300
Rhodococcus seems particularly well suited for hydrocarbon
metabolism. Sulfur-metabolizing bacteria have been shown to
reduce the sulfur content of diesel fuel from 535 ppm to 75 ppm
in 24 h. Several species of bacteria metabolize organosulfur
compounds in one of three ways: reductive C–S bond cleavage,
oxidative C–S bond cleavage, and oxidative C–C bond cleavage.
Generally, there are two primary pathways for BDS of alkyl-
DBTs. One pathway is that in which the initial attack is directed
against one of the carbon atoms (the Kodama pathway) (Fig. 5)
This journal is ß The Royal Society of Chemistry 2012

and one in which initial catalysis is directed against the sulfur
center (the 4S pathway) (Fig. 6).
In the destructive BDS (oxidative C–C bond cleavage)
mechanism, the initial attack is directed against one of the
carbon atoms, preferentialy one of the DBT phenyl rings. This
results in the breakage of one bond or a fragment from the
phenyl ring. The oxidative and carbon-destructive series of
enzymatic actions that attack carbon atoms in DBT phenyl
ring is known as Kodama pathway.301 This pathway for DBT
is shown in Fig. 5. It consists of three main steps including
hydroxylation, ring cleavage, and hydrolysis.302 The oxidation
in most cases produces 3-hydroxy-2-formyl-benzothiophene
(HFBT) and pyruvic acid (PA) are produced. The steps after
production of HFBT are not fully known. HFBT is chemically
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unstable and it is probably mineralized in nature. In cases
where methyl-DBT was subjected to Kodama desulfurization,
it was found that the carbon–carbon cleavage occurred on the
Fig. 5 Kodama enzymatic pathway on dibenzothiophene.299
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benzene ring that had no substituting group to form
corresponding methyl-HFBT.299 Several different genera,
majority of which are pseudomonas cultures have been
reported to carry out desulfurization through DBT carbon-
destructive pathway.303–307
Enzymatic attack at a carbon atom, typical of many aromatic
hydrocarbon degradative pathways, is undesirable for a process
designed to selectively remove organic sulfur compounds with-
out oxidation of other aromatics found in petroleum products.
Due to the undesired breakage of carbon-carbon bonds in
benzene rings, this type of desulfurization is considered to be a
destructive process.
Several anaerobic strains have demonstrated the ability to
remove organic sulfur from petroleum feedstocks by reductive
C–S bond cleavage (anaerobic BDS). For example, desulfovibrio
desulfuricans metabolizes DBT, releasing sulfur as H2S in the
presence of a reducing agent.299
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Fig. 6 The ‘4s’ pathway for the biological desulfurization of DBT and its derivatives.102,307
Kim et al.308 investigated the specific desulfurization by
Desulfovibrio desulfuricans M6. This anaerobic strain could
degrade 96% and 42% of BT and DBT, respectively. Metabolite
analyses proved that this strain could convert DBT to biphenyl
and H2S.
Some anaerobic microorganisms, such as Desulfomicrobium
scambium and Desulfovibrio longreachii, have been reported to
have the ability to desulfurize only about 10% of DBT dissolved
in kerosene. Under anaerobic conditions, oxidation of hydro-
carbons to undesired compounds such as colored and gum
forming products is minimal.301 This advantage can be counted
as an incentive to continue research on reductive BDS. However,
maintaining an anaerobic process is extremely difficult and the
specific activity of most of the isolated strains have been reported
to be insignificant for DBTs.309
The specific oxidative BDS (oxidative C–S bond cleavage)
pathway is often referred to as the ‘4s pathway’ because of the
four sulfur-containing intermediates (sulfoxide–sulfone–sulfi-
nate–sulfate). It involves consecutive biocatalytic oxidation of
DBT sulfur to sulfoxide (DBTO), sulfone (DBTO2), sulfinate
(HPBS) and hydroxybiphenyl (HBP). An example is shown in
Fig. 6 for converting DBT to sulfoxides, sulfones and finally to
hydroxyl biphenyl.226,310–315
This mechanism involves four enzymes that converts DBT-like
molecule into a phenolic product and SO322. Flavin-dependent
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DBT mono-oxygenase (DszC or DBT-MO (a tetramer encoded
by the desulfurizationc gene)) and DBT-sulfone mono-oxygenase
(DszA or DBTO2-MO (a dimer encoded by the desulfurizationa
gene)) are first two of these enzymes that require a third enzyme
(the flavin reductase DszD) for their activity. The fourth enzyme,
HPBS desulfinase (DszB), completes the reaction sequence.307
There are a number of potentially rate limiting steps including
enzyme kinetics involved in the desulfurization of CX-DBTs, and
other molecules dissolved in diesel. The first, and sometimes rate-
limiting, step in CX-DBT metabolism is the transfer of the
polyaromatic sulfur heterocycles from the oil phase into the cell.
In rhodococcus, the desulfurization enzymes are soluble and
presumably found in the cytoplasm.307 Once the molecules reach
the cell, the CX-DBT molecules are subjected to a series of
oxidations. The first two are catalyzed by the same enzyme,
DBT-MO. This enzyme requires flavin mononucleotide for
activity, which is provided by flavin mononucleotide oxidor-
eductase. The oxidation of dibenzothiophene sulfone (DBTO2)
to hydroxyl-phenyl benzene sulfonate is catalyzed by the next
monooxygenase (DBTO2–MO). This reaction also requires
reduced flavin mononucleotide (FMNH2) and molecular oxygen.
Hydroxy-phenyl benzene sulfonate is readily soluble in water. In
the final step, the inorganic sulfur is released by a HPBS
desulfinase. This reaction yields a hydrophobic aromatic
molecule, hydroxy biphenyl and sulfite. The hydroxy biphenyl
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is very soluble in oil, and finds its way back to the petroleum
fraction, thus, conserving the fuel value of the oil. It is also
unclear how Cx-hydroxy biphenyl or Cx-hydroxyphenyl benzene
sulfonate exit the cells. Hydroxy biphenyl (also known as
orthophenyl phenol or ‘dowicide number 1’) is a potent
industrial biocide.307 Experimental results suggest that mass
transfer is not limited by intermediate oil-to-water, water-to-cell
steps.
The throughput of substrates in this pathway is hindered at
several steps, including substrate acquisition, the supply of
reducing equivalents and enzyme turnover rates for specific
substrates.316 These slow the overall rate at which whole
bacterial cells can remove sulfur. In general, DBT and C1-DBT
are attacked preferentially followed by the more highly alkylated
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molecules. The position of the methyl group also influences the
reaction rate. Alkylation near the sulfur leads to slower rate of
desulfurization. Although, sphingomonas strain shows the
opposite trend.307
The genes responsible for the ‘‘4S’’ metabolic pathway
(oxidative C–S cleavage) have been cloned, sequenced and
engineered from a variety of microorganisms, and have been
transferred to several bacterial species after its initial discovery in
Rhodococcus erythropolis strain IGTS8. In the past few years
several new flavin reductases, including thermo-tolerant
enzymes, have been discovered. In addition, the least well
understood enzyme in the pathway, HPBS desulfinase, is
becoming better characterized.316
7.3. Recent studies in BDS
BDS using microorganisms and/or enzymes has been studied
since last few decades. Soleimani et al.299 recently published a
review paper on BDS of refractory organic sulfur compounds in
fossil fuels. This section presents the results of very recent studies
on BDS.
Conventional refining processes have been performed at much
higher temperature; therefore thermophilic biodesulfurizaiton is
desirable and could be easily integrated into the refining process
without cooling the stock to 30 uC.317 Moreover, thermophilic
biodesulfurization also reduces the viscosity of crude oil, which
makes the development of crude oil biodesulfurization more
practicable.318 Li et al.319 investigated the desulfurization for
DBT in tetradecane by a facultative thermophilic bacterium
Mycobacterium goodii X7B. The total sulfur level of DBT in
tetradecane was reduced by 99%, from 200 to 2 ppm within 24 h
at 40 uC. After 72 h treatment, 59% of the total sulfur content
(from 3600 to 1478 ppm) in Liaoning crude oil was removed.
Mohebali et al.320 investigated the ability of a newly isolated
bacterium, Gordonia lkanivorans RIPI90A (GenBank accession
number DQ321498) to desulfurize both DBT and DBT-contain-
ing hexadecane during both the growth and resting stages. The
highest specific activity, in terms of DBT-utilization occurred in
cells harvested from the late exponential growth phase. TH or
BTH was completely degraded by a DBT desulfurizing
bacterium Mycobacterium sp. ZD-19 within 10 h or 42 h, and
100% DBT or 4,6-DMDBT was removed within 50 h or 56 h,
respectively.321 Diphenylsulfide (DPS) possessed the lowest
desulfurization efficiencies with 60% being transformed within
50 h and 80% at 90 h. The desulfurization activities of five
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substrates were found to be in order of TH > BTH > DPS >
DBT > 4,6-DMDBT. The desulfurization rate of DBT or 4,6-
DMDBT in mixture was found to be lower than they are
desulfurized separately, indicating that the substrate competitive
inhibition existent when DBT and 4,6-DMDBT are mixed.
Caro et al.322 reported the BDS of DBT in oil–water emulsions
by aerobic Rhodococcus erythropolis IGTS8 strain. Addition of
b-cyclodextrins increased the diffusion of DBT into the aqueous
phase and avoided the accumulation of HBP, thus improving the
BDS yield. Higher biocatalyst cell concentrations decreased the
HBP production rates indicating combination of both inhibition
effects and mass transfer limitations. Alves et al.323 tested
enzymatic hydrolyzates of recycled paper sludge as suitable
feedstock for BDS by Gordonia alkanivorans strain 1B. Only the
hydrolyzate obtained after enzymatic mixture dialysis (dialyzed
hydrolyzate) allowed DBT desulfurization, in spite of faster
bacterial growth occurring on non-dialyzed hydrolyzate. For
dialyzed hydrolyzate, 250 M DBT was consumed after 96 h
displaying a maximum specific productivity of 2-hydroxybiphe-
nyl of 1.1 mol g21(dry cell weight) h. Complete consumption of
DBT was observed upon the addition of only phosphates and
ammonia. Addition of zinc further increased the 2-hydroxybi-
phenyl production by 14%. Madeira et al.324 performed a
stepwise evaluation of the enzymatic oxidation of DBT by
horseradish peroxidase (HRP). Reactions were carried out in
monophasic organic media containing 25% (v/v) acetonitrile.
Best results were observed in a reaction medium at pH 8.0
presenting HRP 0.06 IU/ml, DBT 0.267 mM, DBT:H2O2 molar
ratio of 1 : 20 (stepwise hydrogen peroxide addition) and
incubated at 45 uC for 60 min. Under these conditions 60% of
DBT was converted into DBT sulfoxide (12%) and DBT sulfone
(46%).
A summary of various researches conducted for the sulfur
removal using BDS at optimized conditions is given in
Table 6.319–335
7.4. Future challenges of BDS
Lower capital and operating costs, ability to produce substan-
tially less greenhouse gases and high valuable byproducts are the
potential benefits of BDS. Moreover, BDS takes advantage of
the specificity of enzymes, especially for DBT and substituted
DBTs. Therefore, BDS offers an alternative way to obtain ‘zero
sulfur’ products and has more promising prospects.
Development of biocatalytic desulfurization for the selective
removal of polyaromatic sulfur heterocycles from petroleum
products has focused on the 4S pathway which can remove sulfur
from substituted and un-substituted DBTs by attacking the
sulfur site and converting it to sulfone. Biological removal of
sulfur has several limitations that prevent it from being applied
today. The metabolism of sulfur compounds is typically slow
compared to chemical reactions.
Although, there is a lot of research going on in this area, the
application of BDS approach is limited by the slow biodegrada-
tion process.302 The rate of metabolism is rate limiting in the
process, though mass transfer resistance from the oil/water
interface to the microbe is also slow compared to the rate of
transfer of the sulfur compound to the oil–water interface. Large
amounts of biomass are needed (typically 2.5 g biomass per g
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Table 6 Sulfur removal by BDS at optimized conditions

Optimum Conditions
S Conc. Temp. Pressure %S
Process Sample Model Oil Microorganism System Co (ppm) (uC) (atm) Removal Reference

4S DBT hexadecane Gordonia alkanivorans RIPI90A Batch 100[320] 30 — 90%

4S DBT + 4, — Mycobacterium sp. ZD-19 Batch 92 30 — 100% 321
6-DMDBT
4S DBT Tetradecane Mycobacterium goodii X7B Fed Batch 200 40 — 99% 319
4S DBT Hexadecane Rhodococcus erythropolis IGTS8 Batch 100 30 — 80% 322
4S DBTs n-heptane Gordonia alkanivorans strain 1B Batch 100 35 — 63% 323
Biocatalytic Organosulfides Straight-run Caldariomyces fumago Batch 1600 25 1 99% 325
oxidation and thiophenes, diesel fuel
4S DBTs n-tridecane Bacillus subtilis WU-S2B Batch 100 50 — 50% 326
BDS DBTs n-tridecane Mycobacterium phlei WU-F1 Batch 150 50 — 99% 327
BDS DBT n-Hexadecane Rhodococcus sp. strain P32C1 Batch 1000 30 — 75% 328
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BDS DBT Decane Rhodococcus erythropolis Interface 184 30 — 90% 329

ATCC 53968 Bioreactor
4S DBT Hydrodesulfurized Mycobacterium sp. X7B Batch 535 45 — 86% 330
diesel
BDS DBT Ethanol Microbacterium strain ZD-M2 Batch 36 30 — 94% 331
BDS DBT n-Hexadecane Pseudomonas stutzeri UP-1 Batch 500 31 — 74% 332
BDS DBT + 4, Light gas oil Sphingomonas subarctica T7b Fermentor 280 27 — 94% 333
6DMDBT
4S DBT n-Hexadecane Bacterium, strain RIPI-22 Batch 100 30 — 77% 334
BDS — Hydrodesulfurized Pseudomonas delafieldii R-8 Fermenter 591 30 — 47% 335
diesel oil

sulfur), and biological systems must be kept alive to function
under variable input conditions found in refineries. This is
difficult since the rate of desulfurization strongly depends on pH,
temperature, and dissolved oxygen concentration. Separation of
the cells from the oil can also be difficult, and immobilized cells
often have lower activity and limited lifetimes. Despite consider-
able progress in BDS, there are still some difficulties in commercial
application in the industry. Critical aspects of the process include
cost of biocatalyst, reactor design and oil–water separation. Mass
production of biocatalyst with high desulfurization activity is an
important technique to decrease the cost of biocatalysts, which is
carried out by high cell density cultivation.335
Despite considerable progress in understanding of BDS, there
are several bottlenecks limiting commercialization of this
process, such as biocatalyst’s desulfurization rate and ability of
organic sulfur compounds.336 There have been few reports on the
microbial treatment mechanism of different sulfur compounds
when they are coexisting. Additionally, little is known about
which compound would be degraded preferentially or whether
the desulfurization rate is different between single and their
mixture. An understanding of the metabolic mechanism is still
expected and this will be the focus of the majority of research.337
8. Conclusions
Most researchers in the field of desulfurization have focused
their research into three categories: ODS, metabolism of sulfur
compounds using microbes, and selective adsorption. Despite
these research areas, the primary method for sulfur removal is
still HDS, which is a conventional, heterogeneous hydrogenation
reaction. Studies regarding reaction mechanisms and catalytic
centers involved in the hydrogenation of olefins and HDS of
thiophene and related compounds are still important. This issue
has gained a renewal of interest in recent years with the need of
deep desulfurization coupled to the necessity of saving a
maximum of octane rating in the fractions composing commer-
cial gasoline.
The extensive use of catalytic hydrogenation for sulfur
removal suggests that better techniques for desulfurization may
be found in a typical hydrogenation reactor. Before they can be
applied to desulfurization, however, the operation of different
types of hydrogenation reactors must be understood. The
oxidation-extraction technique can be used as an additional
process to the HDS to enable the refiners to meet the future
environmental sulfur regulations. The conventional HDS can
be used to lower the sulfur content to few hundreds ppm. Then,
the oxidation/extraction approach is applied to go for ultra-
deep desulfurization as it provides better mean and cost
effective way in order to meet the future sulfur environmental
requirements. Given the economic limitations of peroxide-
based ODS and the need for an alternate technology for
refineries where a supply of hydrogen peroxide is not readily
available, oxidation methods besides H2O2 are needed. There is
also not many detailed works to define the appropriate
conditions in terms of the optimum temperature, oxidants,
catalysts, solvents/fuel ratio for extraction, and the impact of
such solvents extraction on fuel quality. So these approaches
still need further research, especially in the area of designing
the appropriate selective catalysts. Much work still remains to
be done to address the suitability of future approaches to meet
the sulfur limit requirements.
Abbreviations
4E6MDBT 4-ethyl,6-methyl-DBT
AC Activated Carbon
ACF Activated Carbon Fiber
BT Benzothiophene
BDS Biodesulfurization
BiCh Bicyclohexyl

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