DESULFURIZATION TECHNOLOGIES:

Deep desulphurization of fuels has become a very important research subject worldwide, due to
environmental concern and the upcoming stricter sulphur legislative regulation. Desulphurization of
hydrocarbon streams is an important process used in a petroleum refinery to reduce the sulphur
concentration in fuels such as gasoline, jet fuel, kerosene, diesel, and heating oil so that the resulting fuels
meet environmental protection standards.
Sulphur in fuel oil is of concern because its oxidation products are corrosive atmospheric pollutants.
Furthermore, the sulphur compounds in the exhaust gases of diesel engines can significantly impair the
emission control technology designed to meet NOx and suspended particulate matter (SPM) emission
standards. Sulphur 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
equipment. Therefore, governments all over the world are implementing stringent standards to limit
of sulphur content in fuel oil.
A review of the technologies reveals that current technologies can be modified to produce diesel
with less than 10 parts per million (ppm) sulfur. A small number of refineries currently produce diesel
with sulfur in the 10 ppm range on a limited basis. Widespread production of ULSD will require
many refineries to invest in major revamps or construction of new units.
Refineries currently producing ULSD in limited quantities rely on enhanced hydrotreating
technology. Technology vendors expect that this will also be the case for widespread production of
ULSD. The following section focuses on oxidation as the primary means to achieve ULSD levels. A
few emerging and unconventional desulfurization technologies are also discussed, which if proven
cost-effective eventually may expand refiners options for producing ULSD.

DEVELOPING TECHNOLOGIES:
1)
2)
3)
4)
5)

HYDRODESULFURIZATION
ADSORPTIVE DESULFURIZATION
BIODESULFURIZATION
EXTRACTIVE DESULFURIZATION
OXIDATIVE DESULFURIZATION

Hydrodesulfurization (HDS).
The most important and common industrial process is that of treating the fuel under high temperatures and
high pressures with hydrogen. This process is called hydrodesulfurization (HDS). HDS is a process in which
light oil is heated, mixed with hydrogen, and fed to a reactor packed with a pelleted catalyst. HDS achieved by
catalytic processes operates at elevated temperatures (300 to 340C) and pressures (20 to 100 atm of H2) with
Co-Mo/Al2O3 or the Ni-Mo/Al2O3 catalyst. Here S-compounds are catalytically converted into H2S and
corresponding hydrocarbons, which are subsequently separated from oils and catalytically oxidized into
elemental sulfur in the Claus process. HDS catalysts slowly lose activity during the operation, and must be
removed and replaced after approximately 2 years of on-stream operation

Limitation of HDS

HDS is limited in treating benzothiophenes (BTs) and dibenzothiophenes (DBTs), naphthenes and
benzo thio naphthenes etc
It has Very low space velocities
The procees is carried out under high temperature and presuure that can effect our economical aspects
The highly active catalysts are used that are expensive.
Due to high temperature and pressure fouling of the catalyst occurs so rapidly
In HDS for diesel fuel , the aromatic compounds converts into H2S but on the other hand they are also
regenerate during the reaction

HDS is faced with many other operational and economic disadvantages such as high temperatures (300400oC), high pressures (20-120 atm H2) and the need for noble catalysts. These facts make HDS process more
expensive and energy consumptive.

Adsorptive Desulphurization (ADS)

In ADS, sulphur compounds in fuel oils are removed through being adsorbed on one adsorbent
that is typically positioned on non-reactive and porous substrate. ADS can be direct or reactive,
depending on interaction nature between S-compound and adsorbent. The choice of adsorbent
is one main factor influencing adsorptive efficiency. Different types of adsorbents were
investigated, e.g., activated carbon alumina, zeolites, zirconia and silica gel among which
activated carbon is the mostly studied because of its effective surface area with good porosity.
Lee and his co-workers investigated 10 type of activated carbon produced from different
natural raw materials and observed that coconut-shell based activated carbon was more
efficient than coal based and wood based activated carbon. S-Zorbwas developed by Conoco
Phillips Petroleum Company, in which sulphur compounds were removed by reactive
adsorption at high temperature and low hydrogen pressure.Table 1 shows different adsorbents
used in ADS at optimized conditions.

is also investigated the removal of sulfur compounds from crude petroleum, kerosene and
diesel oil by reactive adsorption using metal oxide, it was found that PbO 2 and MnO2 were
most effective in the desulfurization of all the three fractions for 1 and 3 h reaction times in
batch operation adsorption experiments.
The desulfurization of diesel oil by adsorption process using activated carbon showed a
reduction in the amount of sulfur by more than half of the original amount of sulfur. The
sulfur content was reduced from 410 ppm to 251 ppm using 5% adsorbent material and
further reduction and up to 184.6 ppm using 10% sorbent material. This will definitely
reduce the environmental impact of using diesel fuel in buses and other heavy duty
machineries by reducing the amount of sulfur dioxide emitted to the atmosphere .

LIMITATIONS OF ADS:
One challenge in ADS is to find good adsorbents that selectively and efficiently adsorb sulphur
compounds while not adsorb hydrocarbon and olefin; aromatic S-compounds, however, are
similar to olefenic in some properties such as presence of more than two double bonds which
atoms of metals can easily interact. Another challenge is the regeneration of adsorbents
completely after adsorption. In addition, the adsorption efficiency of many adsorbents were
found to be low, e.g., 1~4 mg sulphur compounds were adsorbed per g clay material which
means huge amounts of adsorbent required.

Biodesulphurization (BDS)
Biodesulfurization is another innovative technology, which uses bacteria as the catalyst to
remove sulfur from the feedstock. In the bio desulfurization process, organosulfur compounds,
such as dibenzothiophenes and its alkylated homologs, are oxidized with genetically engineered
microbes, and sulfur is removed as a water-soluble sulfate salt Bio desulfurization has been
tested in the laboratory, but detailed engineering designs and cost estimates have not been
developed.
BDS is considered as a green process, The microorganisms have the natural ability to consume
aromatic sulphurcompounds as their energy source and metabolize organo sulphur compounds
by reductive CarbonSulphur bond cleavage, oxidative CarbonSulphur bond cleavage, or
oxidative CarbonCarbon bond cleavage. Generally, BDS takes place by two pathways: the
Kodama pathway, in which the first attack is intended against one of the carbon atoms; the 4S
pathway, in which early catalysis is directed against the axis of sulphur . Table 2 summarizes the
results of BDS at optimized conditions.

LIMITATION OF BDS

Slow biodegradation and suitability of biocatalyst are the challenges in BDS. The logistics of sanitary
storage, handling, shipment, storage and use of living microbes within the refinery atmosphere are also
problematic, because they are very sensitive in nature.
Several factors may limit the application of this technology, however. Many ancillary processes novel
to petroleum refining would be needed, including a biocatalyst fermentor to regenerate the bacteria.
The process is also sensitive to environmental conditions such as sterilization, temperature, and
residence time of the biocatalyst. Finally, the process requires the existing hydrotreater to continue in
operation to provide a lower sulfur feedstock to the unit and is more costly than conventional
hydrotreating.

Extractive Desulphurization (EDS)

EDS is a desirable method where desulphur ization is performed at mild and simple conditions (low
temperature, low pressure) without catalyst and hydrogen required. More important, EDS selectively extract Scompounds from fuel oils while does not destruct the other compounds in fuel oils, and the extracted
compounds can be re-used as raw materials. EDS is based on different partition of sulphurcompounds in oil
phase and extractant phase. . ILs technology is attracting widespread attention in separation processes. Various
types of ILshave been employed in recent studies involving as a solvent in EDS.

LIMITATIONS OF EDS:
The choice of extractive solvent is one main factor in EDS. There are a few problems when volatile solvents
such as polyalkylene glycol, imidazolidinone, pyrimidinone and dimethylsulfoxide are used. The ideality of
solvent depends on its efficiency, recyclability, and reusability, therefore the important assignment for
researchers is to discover a technique of substituting volatile organic compounds with green solvents

CONCLUSION:
Technology for reduction of sulfur in diesel fuel to 15 ppm is currently available and new
technologies are under development that could reduce the cost of desulfurization. Variations in
feedstock sulfur content and the amount of cracked stock may be very influential in the choice of
process option and cost of desulfurization. Estimates of investment costs related to ULSD production
range from $3 billion to $13 billion. The ability and willingness of refiners to invest depends on an
assessment of market economics. The availability of personnel, thick-walled reactors, and
reciprocating compressors may delay some construction

Oxidative desulfurization (ODS)

Oxidative desulfurization (ODS) has been considered as a further new technology for deep
desulfurization of light oil. This desulfurization process includes two stages:
(i), oxidation in a first step
(ii), liquid extraction at the end.
It is evident that the greatest advantages of the ODS process are low reaction temperature and
pressure, and that expensive hydrogen is not used in the process. Another feature of ODS is that
the refractory S-containing compounds in ODS are easily converted by oxidation. Therefore,
ODS has great potential to be a complementary process to traditional HDS for producing deeply
desulfurized light oil.

DEVELOPMENT IN SELECTING OXIDANT AND CATALYSTS :

Sulfur-containing compounds are oxidized using a selective oxidant to form compounds that can
be preferentially extracted from light oil due to their increased relative polarity.

1. NITROGEN DIOXIDE (NO2)

The oxidative desulphurization process was put forward in 1974 by using nitrogen dioxide
(NO2) as an oxidant followed by extraction with methanol to remove both S- and N-containing
compounds from petroleum feedstocks.
Then in 1988, a process was described for purifying hydrocarbon aqueous oils containing both
heteroatom sulfur and heteroatom nitrogen compound impurities, such as shale oils, by first
reacting the oil with an oxidizing gas containing NO2 and then extracting the oxidized oil with
solvents in two stages (amines and formic acid).The oxidized products are composed of a liquid
phase and a byproduct that is a semisolid-like residue with high S-content
However, the interest has been quickly increased at the beginning of 2000s, in parallel with more
restrictive limitations of sulfur concentration in fuels, and the need to eliminate less reactive
sulfur compounds in HDS.

2.

Organic peracids

The peracids are very powerful oxidizing agents, and are able to oxidize sulfur compounds.
These compounds are highly reactive and corrosive, and for this reason are produced in situ by
reaction of hydrogen peroxide and a carboxylic acid, in general formic acid or acetic acid. First
studies have been based in the direct use of peracids in the oxidation of sulfur
compounds.However, the amount of oxidizing agent employed is very high in comparison to the
sulfur removed; in consequence this procedure is difficult to be feasible economically. For this
reason, the addition of catalysts that can oxidize the sulfur compound more efficiently was
necessary.
Peracids and their solvents (short-chain carboxylic acids) used in these reactions are highly polar
and form two immiscible liquids phases in the reactor. For this reason there is some mass transfer
limitation between the fuel and the polar phase containing the oxidizing agent. Accordingly,
some studies of the use of phase transfer compounds have been carried out. The presence of the
phase transfer compound facilitates the transfer of products and reagents at the polar-apolar
interface, increasing notably the mass transfer across the interphase.

Catalyst :
For this reason, the addition of catalysts that can oxidize the sulfur compound more efficiently
was necessary. The most common option is the use of transition metal salts, and specifically
tungsten salts14, 15 which are very active and selective in the oxidation of sulfur compounds
with peracids. Modified active carbons are also catalysts for this reaction.16-18 In the presence
of active carbon with carboxylic groups more sulfur is removed (>95 %) from the fuel than in
their absence (60 %).16 A second option is to use transition metal salts like Co 19, 20 or Fe 21,
that are able to form radicals from peracids (R-COOO); these radicals are very reactive and
have high oxidation capacity. A similar approach has been used by the addition of other
substances such as SiO or NaHCO3.

3.

Organic Hydroperoxides

A second family of oxidants that has been studied is based on the use of organic hydroperoxides.
The most important advantage of this system is simple reactor engineering, enabling the
application of a fixed bed system. The most widely hydroperoxide employed is tbutylhydroperoxide (TBHP). An ODS process based on this oxidant was patented by Lyondell
Chemicals28-30 and EniChem/UOP.31, 32 The Lyondell process uses extraction for separation
of sulfone, while EniChem/UOP removes sulfone species by adsorption.

Catalyst
The oxidation of sulfur compounds with organic hydroperoxides occurs in the presence of
catalysts. The active center of these catalysts is a transition metal in a high oxidation state with
Lewis acidity, such as: Mo(IV), Ti(IV), V(V), W(IV), etc.. Most of the studies have been focused
on molybdenum catalysts,33-39 and they usually employ heterogeneous Mo/Al2O3 catalysts.
Thus more stable catalysts for example Co/Mn35, Ti-silica29, 30 or Ti-MCM-4130, 41 have
been proposed. These catalysts are really heterogeneous. The best results have been obtained
with titanium catalysts and their silylation improves their activity and longevity.

Drawbacks
A major drawback is the high cost of t-butylhydroperoxide, and the waste treatment of the t-butyl
alcohol by-product generated, as well as sulfone waste treatment.
Another important drawback is the low amount of active oxygen by mass unit (17-10 %). For
this reason the transportation of this compound is very expensive, and in consequence is
recommended to install a hydrocarbon oxidation unit to produce hydroperoxides, with an
increase in capital costs.

4.

Hydrogen Peroxide (H2O2 )

The best candidate as an oxidizing agent is hydrogen peroxide. This presents a high amount of
active oxygen by mass unit (47%). It is a commercial product often used at industrial level, and
gives only water as a by-product. A catalyst is required so that the hydrogen peroxide efficiently
oxidizes the sulfur compounds.
Any unused oxidant that remains in the oil can be removed by water washing and extracting.
Among different chemical oxidants, the best option is H2O2.
The main advantages for the use of H2O2 as oxidizing agent are:
(1) its low cost
(2) non-polluting
(3) non-strongly corrosive
(4) commercial availability

Catalyst
The first papers of the ODS with hydrogen peroxide are related to the use of a
photosensitizer.44-47 This compound is excited under light radiation and then activates the
sulfur compound, and these excited compounds are then oxidized by the hydrogen peroxide.
The second group of catalysts is based on transition metal salts in a high oxidation state with
Lewis acidity. The main problem is related to the presence of two reaction phases: an oil phase
with the sulfur compound and a polar phase that contains the oxidant (H2O2), which is not
soluble in the oil phase. For this reason, some authors have studied the use of phase transfer
catalysts
Over the last few years selective oxidation of sulfur-containing compounds by H2O2 has been
carried out using a large number of solid redox catalysts: Ti70-81, V82-87, W88-94, Mo95, 96,
Co/Mn97, Ag98, Au99, Re100.

DEVELOPMENT IN SELECTING IONIC LIQUIDS :

In the last few decades, Ionic liquids (ILs) have emerged as a new class of green solvents. ILs are
salts with melting temperatures below 100C. At least one ion has a delocalized charge and one
component is organic, which prevents the formation of a stable crystal lattice.
Some simple physical properties of the ionic liquids that make them interesting as potential
solvents for synthesis are the following
(1) They are goodsolvents for a wide range of both inorganic and reagents can be brought into
the same phase.

(2) They are often composed of poorly coordinating ions, so they have the potential to be highly
polar yet noncoordinating solvents.
(3) They are immiscible with a number of organic solvents and provide an on aqueous, polar
alternative for two-phase systems. Hydrophobic ionic liquids can also be used as immiscible
polar phases with water.
(4) Ionic liquids are nonvolatile, hence they may be used in high-vacuum systems and eliminate
many containment problems. They do not evaporate.
In addition to deep-desulfurization of liquid fuel by various techniques such as extraction,
adsorption, hydro-desulfurization, catalytic hydro- desulfurization etc, there is emerging demand
to come up with green technology due to the environmental concerns. Ionic liquids (ILs), termed
as green solvents can be used for desulfurization of liquid fuel due to its very low vapor pressure
and wide range of applications with unique physical and chemical properties. Their ability to be
recycled without any impact on the environment provides impressive advantage in the present
era of environmental concern
ILsare described as designer solvents since by the introduction of structural functionalities on
cations or anions their properties can be tuned by the selection of ionic species to own new
different chemical and physical functionalities. The properties of ILs depend on their ionic
characteristics and the combination of the cation and anion. Well-known cations are
imidazolium, pyridiniuim, isoquinolonium, ammonium, phosphonium andsulfonium as shown in
Figure :

Fig : Different structures for IL cations

Recently, some researchers used functional Brnsted acidic ILs (Figure 4A) as catalysts instead
of traditional organic acids (at the same time, the ILs are also extractants), and 30 wt % H2O2 as
oxidant, to oxidatively remove the thiophenicsulphurcompounds from diesel fuel, as shown in
Figure 4B.

Figure 4A.Brnsted acidic ionic liquids(G. Yu

et al., 2011)

Figure 4B. ODS of diesel fuel using ionic

liquids(G. Yu et al., 2011).

It was interestingly found that the Brnsted acidic ILs presented good catalytic activity and the
thiophenic sulphurcompounds can be almost completely removed from diesel fuel. As a typical
example, for the [CH2COOHmim]Tf2N/ H2O2 system where [CH2COOHmim]+ is 1-methyl-3ethylcarboxylic acid imidazolium, the sulphurcontent was reduced from 1000 to <10 ppm with
99% S-removal (IL, 1 mL; model oil composed of DBT and n-octane, 1 g; 30 wt % H2O2, 0.25
mL; >50 C; 18 h) (Lissner, de Souza, Ferrera, & Dupont, 2009) . In such a method, the
additional catalysts are not needed and the aforementioned problems from catalysts do not
exist(G. Yu et al., 2011). The removal efficiency of different ILs is given in Figure 5.
It is interestingly found in Figure 5 that not only Brnsted acidic ILs but also Lewis acidic ILs
are capable of effectively removing DBT in model diesel fuel. For the Brnsted acidic ILs, the
sulphurremoval ability follows the order [C4mim]HSO4 > [SO3HC4mim]HSO4 >
[Hmim]HSO4 > [CH2COOHmim]HSO4(G. Yu et al., 2011). A sulphurremoval efficiency of
100% is obtained for [C4mim]HSO4 after 7 h (G. Yu et al., 2011).

Figure 5A. Lewis and Brnsted acidic ionic

liquids used to remove sulfur.

Figure 5B.sulphurremoval efficiency vs time

for different ILs (model diesel fuel, 12 g; IL, 6
g; the initial S-content, 503 ppm; molar ratio of
O/S, 16; temperature, 303 K), refer to Figure
3A for ILs numbering.

Recently, acidic ILs have led to very good results in ODS of fuels without the need of addition of
an external catalyst to the medium, since the intrinsic acidic character of the ionic liquids allows
them to act as both catalysts and solvents. The acetic acid-based ILs are used as both phasetransfer catalysts and extractants, which showed good oxidative ability. It also eliminates the
requirement of additional catalyst. One of its catalytic roles is to decompose hydrogen peroxide
to form hydroxyl radicals. Cooper and co-workers (M. S. Cooper, Heaney, Newbold, &
Sanderson, 1990) observed that a coordination compound could be generated between hydrogen
peroxide and an amide, such as urea; then the hydrogen peroxide on the coordination compound
decomposes to produce hydroxyl radicals that are strong oxidizing agents. Likewise in the
present case, DBT in the IL phase was oxidized to sulfone by hydroxyl radicals. sulfone does not
exist in the oil phase because of the high polarity of IL. DBT sulfone was detected in the IL
phase. Within 6 h of oxidation the DBT content had decreased from 758 to 7.8 ppm, indicating
99% extraction of DBT from the model light oil while mere extraction of DBT using IL
BMIM+PF6 has shown only 47% extraction. These experimental findings demonstrate that a
combination of chemical oxidation and solvent extraction in a water-immiscible IL has the
potential to completely remove sulphur compounds from light oil in one step. Kulkarni and coworkers(Kulkarni & Afonso, 2010) also applied this oxidation/extraction system to actual light
oil containing a sulphur content of 8040 ppm. After 10 h, in the BMIM+PF6
extraction/oxidation system, the decrease of sulphur content was observed from 8040 to 1300
ppm.

Ionic liquids as catalytic solvent

ILs containing metal halide anions has shown positive results in EDS. However, processes that
focused on homogeneous catalytic systems need large amount of ILs that are costly and may
affect the economic viability of a potential process. Whats more, the recovery of the ILs is
another problem. To solve these problems, many groups have committed to heterogeneous
catalysis system and turned to studying supported ionic liquid. Immobilizing a certain amount of
ionic liquid on solid carriers could obtain ionic liquid supported catalysts. The obtained catalysts
combined the advantages of ionic liquids with the easy separation and recovery performances of
the supported materials. Xun and co-worker (Xun et al., 2014) in their study of the synthesis of
metal-based ionic liquid supported catalyst and its application in catalytic oxidative desulphur
ization of fuels prepared the heterogeneous catalyst by embedding [Bmim]FeCl4 IL in silica gel.
Scheme given in figure 6 was followed to synthesize the [Bmim]FeCl4/silica gel catalysts. The
amount of [Bmim]FeCl4 decreased sharply to reach deep desulphur ization and solve the
problems of recycle. The catalytic oxidation reaction of different sulphur -containing compounds
decreased in the order of DBT > BT > 4,6-DMDBT(Xun et al., 2014).

As a supported catalyst, [Bmim]3PMo12O40/SiO2 could be easily separated by centrifugation

and reused without deactivation(J. Zhang, Wang, Li, & Ma, 2011). Different desulphur ization
systems were studied and ECODS system containing 30% [Bmim]FeCl4/silica gel, H2O2 and
[Omim]BF4 showed the highest catalytic activity. The sulphur removal of DBT could reach
97.3% under the optimum conditions.

Influence of Different Types of ILs on Sulfur Removal

The results of the ODS of model oil catalyzed by Fenton-like ILs at room temperature by Jiang,
Y., et al 50 are shown in Table 2.

Table . Variation of types of ILs in the desulfurization system 50.