8

Sulfur removal from heavy and light petroleum

hydrocarbon by selective oxidation
M. RASHID KHAN, Saudi Aramco, Saudi Arabia
and E. SAYED, Imperial College, UK

Abstract: Environmental concerns have driven the need to reduce sulfur-

containing compounds to an extremely low level in transportation fuels.
Conventional hydrodesulfurization catalysts can be used to remove a significant
portion of the sulfur from petroleum distillates. Removing the last traces of
sulfur compounds where the sulfur atom is sterically hindered, as in multi-ring
aromatic sulfur compounds, is a significant challenge. One recent area of
innovation to remove sulfur from upgraded crude is oxidative desulfurization, a
process that can operate under mild conditions and without the need for
external H2. In this paper, the mechanism, process, and the new inventions of
selectively oxidative desulfurization are reviewed.

Key words: sulfur compounds, hydrodesulfurization, oxidative desulfurization,

reaction kinetics, patents, process development, process economics.

8.1 Introduction
Removing sulfur from compounds where the sulfur atom is sterically hindered, as in
multi-ring aromatic sulfur compounds, is a significant challenge and a number of
hydrotreating technologies were presented. In certain crudes, a significant portion of
sulfur heteroatom is bound within aromatic structure and doubly hindered (e.g.,
4,6-dimethyldibenzothiophene). Use of conventional hydrodesulfurization catalysts
at extreme high temperature can cause yield loss, faster catalyst coking and product
quality deterioration (e.g., color). Using high pressure may require a large capital
investment. To meet stricter specifications in the future, such hindered sulfur
compounds will also have to be removed from distillate feedstocks and products. As
a result there are numerous innovative initiatives for economical removal of sulfur
from distillates and other hydrocarbon products (Table 8.1).

8.2 Background
A vast variety of sulfur compounds are present in petroleum and hydrocarbon
fuels (Fig. 8.1). These sulfur compounds can be classified into four main groups:
mercaptans (thiols), sulfides, disulfides and thiophenes, which have different
reactivity as illustrated in Fig. 8.2.
Hydrodesulfurization (HDS) is a process in which hydrocarbon fuels are
heated, mixed with hydrogen and fed to a reactor packed with particulate catalyst.

243
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244 Advances in clean hydrocarbon fuel processing

Table 8.1 Processes to achieve ultra-low sulfur fuels

Technology Process Key features Commercial

type experience

Hydrotreating ExxonMobil’s • Meets <10 ppm Over 25 SCANfining

by selective SCANfining and reduced octane loss. units at various
hydrogenation 1 and 11 (for • Employs Akzo Nobel’s stages of licensing.
gasoline) RT-225 catalyst.
• SCANfining I: operated at
moderate-to-high severity
conditions
• SCANfining II: severe HDS
operation to process
high-S feed
Axen’s Prime • Minimizes olefins First unit installed at
G+ (for saturation, thereby BP/Veba Germany
gasoline) reducing H2 use refinery. A new unit
and octane loss of 57.5K b/d at
with < 10 ppm S. TOTAL’s Belgium
• Uses a proprietary refinery 70 licenses
dual-catalyst (with a total of
system to process 1.9mm b/d capacity)
FCC and pyrolysis have been awarded.
gasoline.
• Separates light
olefins from the
heavy S-laden compounds
which
are treated separately.
Nippon Oil’s • It is claimed to Built a $42mm,
Improved reduce FCC gasoline sulfur 31 Kb/d
ROK-Finer to >10 ppm demonstration unit
process with minimum olefin at its Sendai Oil
hydrogenation. Refinery
Thiophene BP’s OATS • No H2 required First unit (15 Kb/d) at
alkylation (for gasoline) 99.5% S removal Bayernoil refinery in
rate, loss of 0–2 Germany
octane number commissioned in
(versus 6–10 with 2001. Two additional
conventional units are installed
hydrotreating. including one
• Catalyze thiophene combined with
to form high boiling point Axen’s Prime G+
compounds at mild process
conditions to
be fractionated later.

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 Sulfur removal from heavy and light petroleum hydrocarbon 245

Adsorption ConocoPhillips’s • Small amount of First unit was

S- Zorb Sulfur- H2 is used; no commissioned in
Removal recombination of 2001. Desulfurization
Technology H2S with olefins plant (35 Kb/d) at
(SRT for gasoline to make ConocoPhillips’s Lake
and diesel) mercaptans. Charles, (2005) > 40
• Selective units are licensed
adsorbent. worldwide.
Solvent UOP’s Sulfur-X • No hydrogen in involved, A 2.5 Kb/d demo unit
extraction (for gasoline) 100% operated in a
product yield, no European refinery for
recombination several weeks with
of H2S with olefins to 95% desulfurization
make mercaptans. and 90% of olefins
• Proprietary solvent to retention
absorb thiophenes,
mercaptans and
light substituted
thiophenes.
Improved UOP’s HyCycle • Reduced H2 use, higher
hydrocracking Unicracking heat efficiency (to save up
technology (for to 15% operating costs),
diesel)and UOP’s lower capital costs
Advanced Partial because of lower
Conversion equipment requirement.
Technology • The HyCycle process uses
(APCU), an a separator-finisher,
extension of the backstaged series-flow
HyCycle reactors and a special
fractionator.
• 25% lower H2
pressure
Chemical UniPure’s • Capable of reducing A 50 b/d demo unit is
oxidation Advanced Sulfur 300–3000 ppm S producing ULSD at
Removal (ASR) down to < 5 ppm. Valero Energy’s Krotz
process • Can be installed Springs, LA.
(for gasoline and as a stand-alone
diesel) unit at terminals
to take care of off-spec
products.
• Oxidation using an
aqueous solution of
recycled formic acid
and H2O2 to oxidize sulfur
compounds
to sulfones which
are extracted by
acid.

(Continued overleaf)

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246 Advances in clean hydrocarbon fuel processing

Table 8.1 (Continued)

Technology Process Key features Commercial

type experience

National Energy • Remove 500–5000 ppm N.A.

Technology S in diesel down
Laboratory and to undetectable levels,
Carnegie Mellon no H2 required and mild
University’s operating conditions.
Selective • Iron complex with a
Oxidation hydrogen-peroxide-
using a “green activating ligand called
catalyst” TAML (terta amido
macrocyclic ligand).
• The liquid phase
(containing an extracting
agent, the catalyst, H2O2)
in a two-phase system to
extract sulfur in the oil
phase.

8.1 Typical organosulfur compounds in transportation fuels.8

Temperatures in the reactor typically range from 316–427 °C. The reactor
pressure ranges from 34.5–172.5 bar depending on the difficulty of removing the
sulfur. In the manufacture of diesel or jet fuel, pressures higher than 62 bar are not
uncommon. The feed and hydrogen mixture typically flows through the reactor,
passing around and through the particulate catalysts. Upon leaving the reactor, the
mixture of treated fuel and hydrogen flows through a series of mechanical devices
to separate and recycle the hydrogen, remove hydrogen sulfide generated in the
reaction and recover the desulfurized product. As used in large integrated
refineries, HDS can be very effective and relatively inexpensive.
The HDS is limited in treating benzothiophenes (BTs) and dibenzothiophenes
(DBTs), especially DBTs having alkyl substituents on their 4 and/or 6 positions
(Fig. 8.2). The relative rates and kinetic information regarding various compounds

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 Sulfur removal from heavy and light petroleum hydrocarbon 247

8.2 Reactivity of various organic sulfur compounds in HDS versus their

ring sizes and positions of alkyl substitutions on the ring.25

are also shown in Fig. 8.2. The production of ultra low levels of sulfur-containing
compounds therefore requires the application of severe operating conditions and the
use of special active catalysts. An alternative process, able to be operated under
moderate conditions and without need for H2 and catalysts is desirable. Oxidative
desulfurization (ODS) provides a new option for deep desulfurization of hydrocarbon.
The main advantages of oxidative desulfurization are claimed to be as follows:

• Easier to remove less reactive sulfur species such as benzothiophene and its
derivatives, than the conventional hydrotreating.
• No increases in refinery hydrogen demand.
• Finishing process to reduce current sulfur levels in fuels to new ultra-low
sulfur levels.
• Good fit with small- or medium-sized refineries.

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248 Advances in clean hydrocarbon fuel processing

• Potential for field, on-board ship or terminal desulfurization.

• Ability to achieve near-zero sulfur fuels.

8.3 Oxidative desulfurization chemistry

8.3.1 First step of oxidation
An effective oxidant can convert sulfur-containing compounds to much more polar
oxidized species. Such oxidants include peroxy organic acids, catalyzed hydro-
peroxides, inorganic oxidants such as inorganic peroxy acids, peroxy salts and O3,
etc. Such oxidants can donate oxygen atoms to the sulfur in mercaptans (thiols),
sulfides, disulfides and thiophenes to form sulfoxides or sulfones (Fig. 8.3). All of
these oxidized sulfur-containing compounds are orders of magnitude more soluble
in non-miscible solvents than their unoxidized counterparts. The selectivity of the
oxidation of the organosulfur compounds to the oxygenated products and the
sulfur-deficient hydrocarbons has its origin in the preferential attack of oxygen at
the C–S bonds of the organosulfur compounds, in the vicinity of the catalytic
surface sites, because of the weakness of C–S bonds relative to strong C–O bonds.

8.3.2 Removal of oxidized sulfur

The second step of this method of sulfur removal generally involves the removal
of the oxidized compounds by contacting the distillate with a selective extraction

8.3 The ideal reaction for DBTs and BTs.

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 Sulfur removal from heavy and light petroleum hydrocarbon 249

solvent. Extraction technique using water-soluble polar solvents (DMSO, DMF,

and acetonitrile) were used.12–16 The former two solvents have a high extractability
for sulfones but have a boiling point (573 K) which is close to the boiling point of
the sulfones, and thus they may not be reused. Acetonitrile was used as the
extraction solvent, since it has a relatively low boiling point (355 K) and is
separated easily from the sulfones by distillation. When acetonitrile is contacted
with hydrocarbon fuels, a large quantity of aromatics is extracted simultaneously
with the sulfones. The addition of water suppresses the extractability of the
sulfones.24

8.3.3 Solvent
The suitable solvents should be sufficiently polar to be selective for polar
compounds for the process of extraction. Examples of polar solvents include
those with high values of the Hildebrand solubility parameter; higher than about
22 have been successfully used to extract these compounds. Examples of polar
liquids, with their Hildebrand values, are shown in Table 8.2.
Polarity considerations are insufficient to define successful extraction solvents.
Methanol, for instance, has sufficient polarity, but its density, 0.79 g/cc, is about the
same as that of typical hydrocarbon fuels, making separations very difficult. Other
properties to consider include boiling point, freezing point, and surface tension.
The properties exhibited by DMSO make it an excellent solvent for extracting
oxidized sulfur and nitrogen compounds from liquid hydrocarbon fuels.4,24,41

Table 8.2 Some examples of polar liquids,

with their Hildebrand values41

Liquid Hildebrand values

(MPa)1/2

Acetone 19.7
Butyl cellosolve 20.2
Carbon disulfide 20.5
Pyridine 21.7
Cellosolve 21.9
DMF 24.7
n-Propanol 24.9
Ethanol 26.2
DMSO 26.4
n-Butyl alcohol 28.7
Methanol 29.7
Propylene glycol 30.7
Ethylene glycol 34.9
Glycerol 36.2
Water 48.0

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250 Advances in clean hydrocarbon fuel processing

8.3.4 Reaction kinetics

Otsuki et al. reported the following trend for sulfur compound oxidation reactivity in
a formic acid/H2O2 system:20 methyl phenylsulfide > thiophenol > diphenyl sulfide
> 4,6-dimethyldibenzothiophene > 4-methydibenzothiophene > dibenzothiophene >
benzothiophene > thiophenes. This trend confirms that the refractory sulfur
compounds in HDS are the most reactive in the oxidation. The reactivity of the
compounds seems to correlate well with their electron density except for the
dibenzothiophenes with methyl substitutes at 4 and 6 positions.3,6,11,13,21,22,48
Two main catalysts used for selective desulfurization are organic acids and
polyoxometalates. Organic acids include formic acid, acetic acid, etc. Polyoxometalates
have long been studied for oxidation reactions, particularly the polyoxometalate/
hydrogen peroxide system for organic substrate oxidations.3,6,11,21,22,48 The
tungsten and molybdenum polyoxoperoxo species in the presence of hydrogen
peroxide were also studied.
Mure Te et al. have carried out a comparative study of the dibenzothiophenes
oxidations using a series of polyoxometalates as catalyst precursors to better
understand the oxidation reactivity of the typical refractory sulfur compounds in
diesel fuels18. Using model compounds of diesel, experiments were carried out to
compare the reactivity of the different dibenzothiophenes in oxidation reactions
using polyoxometalate/H2O2 systems. Oxidation reactivity decreased in the order
of dibenzothiophene > 4-methyldibenzothiophene > 4,6-dimethyldibenzothiophene,
and the same reactivity trend that exists in HDS (Fig. 8.4). Oxidation of the

8.4 4,6 DMBT conversions as function of reaction time at various

reaction temperatures. Data points represent experimental results.
Lines are predictions from a kinetics model.

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 Sulfur removal from heavy and light petroleum hydrocarbon 251

dibenzothiophenes was achieved under low reaction conditions but the

reaction rate increased with temperature or reaction time even for the least
reactive 4,6-dimethyldibenzothiophene. There is a decrease in reactivity of
dibenzothiophenes as methyl substitutes increased at the 4 and 6 positions on
dibenzothiophene rings. Interestingly, in a formic acid/H2O2 system, the oxidation
reactivity of the dibenzothiophenes showed the reverse trend, suggesting that
stereoscopic hindrance might play a role when bulky polyoxoperoxo species,
which likely form in a hydrogen peroxide solution, act as catalysts.18
The polarity of the hydrocarbon fuels increases with increasing aromatic
concentration, such that the solubility of the sulfones in the oil also increases with
increasing aromatic concentration. As a result, the extractability of the sulfones
from high-aromatic-content oil is relatively low. The results show that the highly
substituted sulfones of DBTs and BTs are removed more easily compared to those
sulfones having alkyl substituents of low carbon number. The extractability of
sulfones depends on the dipole moment values for the compounds. Highly
alkyl-substituted DBT-O2 and BT-O2, of high dipole moment values, is therefore
extracted easily from hydrocarbon fuels into acetonitrile solution. The aromatics
in hydrocarbon fuels are oxidized to their corresponding carbonyl compounds,
which impacts fuel quality.50

8.3.5 Review of inventions and recent innovations

Some of the granted patents in oxidative desulfurization technology are reviewed
in Table 8.3. Guth and Diaz (1974) and Guth et al. (1975) used nitrogen dioxides
followed by extraction with methanol to remove both sulfur and nitrogen
compounds from petroleum. Tam and Kittrell (1984) removed sulfur and
heteroatom nitrogen compounds from shale oils, by reacting the oil with an
oxidizing gas containing nitrogen oxides and then extracting the oxidized oil with
solvents. Patrick et al. (1990) used nitric acid or nitrogen oxides as oxidants. The
oxidized products are composed of a liquid phase and a byproduct that is
a semisolid-like residue with high sulfur content. US Patent No. 3,847,800,
Guth and Diaz proposed a process for treating diesel fuel that used oxides of
nitrogen as the oxidant. Nitrogen oxides have several disadvantages. In the
presence of oxygen, nitrogen oxides initiate a very non-selective form of oxidation,
termed auto-oxidation. Several side reactions also take place including the
creation of nitro-aromatic compounds, oxides of alkanes and arylalkanes, and
auto-oxidation products. Nitrogen oxide based oxidants do not yield the
appropriately oxidized sulfur compounds in distillate hydrocarbon fuels without
creating many undesirable byproducts. The Guth and Diaz patent proposes the use
of methanol, ethanol, a combination of the two and mixtures of these and water as
an extraction solvent for polar molecules. Although these have been proved to be
acceptable extraction solvents for this system, they do not perform as well
as others.32

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Table 8.3 Some of the granted patents in oxidative desulfurization

technology31–46

Technology type Patent no. Main features

Oxidation + solvent 6,406,616 (Unipure) • Hydrocarbons are contacted at

extraction. and report from elevated temperatures with an
BP, PetroStar oxidizing/extracting solution of
and others formic acid, a small amount of
hydrogen peroxide, and nearly
25 wt % water.
• H2O2 used as oxidizing agent
followed by silica adsorption of
oxidized sulfur compounds.
• Pyroxyacetic acid is used also to
oxidize sulfur compounds
followed by extraction process
using methanol, dimethyl
formamide and methyl
pyrrolidone or acetone.
• Disadvantage: in some cases,
much of the usable oil (30 %) is
removed along with the sulfur
compounds. Large volume of
solvent is required.
Peroxometal 5,958,224 (Exxon) • Oxidizing sulfur compounds to
sulfoxides and sulfones using
peroxometal complex as oxidizing
agent.
• Producing diesel oil < 50 ppm
sulfur.
Different types of acid 5,087,350 • Removing S and Fe from coal or
(Laboratorios oil and their derivatives or from
Paris) minerals by oxidative extraction
performed with hypochlorous acid
(HClO).
• Phosphotungstic acid + H2O2
system can be as oxidizing
agent.
HDS catalyst 6,277,271 • Hydrocarbonaceous oil + recycle
(UOP LLC) stream containing sulfur-oxidized
compounds contacted with a HDS
catalyst.
• Resulting hydrocarbonaceous
stream + oxidizing agent give
sulfur-oxidated compounds.
• Hydrocarbonaceous oil with less
sulfur-oxidated compounds.
• Portion of the sulfur-oxidated
compounds is recycled to the HDS
reaction.

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H2O2 6,881,325 (BP) • Mixing the feed with ammonium

salt + acid
• Producing less sulfur and/or less
nitrogen fuel.
• Immiscible acid phase is recycled
to oxidation zone.
NOx and methanol 3,847,800 and • NOx used as oxidant agent to
4,746,420 oxidize sulfur compounds. (Mainly
(REI Tech.) producing sulfones).
• Then, methanol or/and ethanol or/
and mixture of both with water
are used as solvent for polar
molecules.
• Disadvantage: several side
chain reactions including the
creation of nitro-aromatic
compounds, oxides of alkanes
and arylalkanes.
Thermal oxidation 3,847,798 and • Oxidation of high boiling
5,288,390 petroleum fractions above
(Sun Company) 550 °F.
• Treating the oxidized compounds
at about 1300 °F to produce H2S.
• Disadvantage: only small degree
of desulfurization and loss of
valuable products due to cracking
and coke formation.
Biodesulfurization 6,130,081 • Decomposing heterocyclic sulfur
(PEC, Tokyo) compounds by cleaving C–S
and 5,968,812 (EBC, bonds under high-temperature
Woodlands) conditions in isolated
microorganisms.
• Improving the removal of sulfinate
group from an organosulfinate
compound using an effective
amount of Lewis acid.
Ultrasound 6,827,844 • Fossil fuel mixed with aqueous
(SulphCo) and liquid + dialkyl ether all subjected
6,402,939 to ultrasound.
(SulphCo) • Producing an organic phase as
desulfurized fuel.
Also
• Fossil fuel mixed with H2O2 in
aqueous organic subjected to
ultrasound.
• Oxidizing sulfur compounds to
sulfones.
• Removing sulfones by polar
extraction.

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254 Advances in clean hydrocarbon fuel processing

One oxidative desulfurization method involves the oxidation of high boiling

petroleum fractions (above about 288 °C) followed by treating the oxidized
compounds at elevated temperatures (to about 700 °C) to form hydrogen sulfide
and/or hydro-processing to reduce the sulfur content of the hydrocarbon material.
See, for example, US Pat. No. 3,847,798 (Sun Yoo)31 and US Pat. No. 5,288,390
(Vincent A Durante).37 Such methods have proven to be of only limited utility
since only a small degree of desulfurization is achieved and there is substantial
loss of valuable products that may result due to cracking and/or coke formation.
Therefore, there was a need to develop a process which gives an increased degree
of desulfurization while decreasing cracking or coke formation.31,37
Several different oxygenation methods for improving fuels have been described
in the past. For example, US Pat. No. 2,521,69829 describes a partial oxidation of
hydrocarbon fuels as improving cetane number. This patent suggests that the fuel
should have relatively low aromatic ring content and high paraffin content. US
Pat. No. 2,912,31330 states that an increase in cetane number is obtained by adding
both a peroxide and a dihalo compound to middle distillate fuels. US Pat. No.
2,472,15228 describes a method for improving the cetane number of middle
distillate fractions by the oxidation of saturated cyclic hydrocarbon or naphthenic
hydrocarbons in such fractions to form naphthenic peroxides. This patent suggests
that the oxidation may be accelerated in the presence of an oil-soluble metal salt
as an initiator, but carried out in the presence of an inorganic base. The naphthenic
peroxides formed are undesirable initiators for gum formation. Consequently,
gum inhibitors such as phenols, cresols and cresyic acids must be added to the
oxidized material to minimize or prevent gum formation. These latter compounds
can be toxic and carcinogenic.28–30
US Pat. No. 4,494,961 (Chaya Venkat and Dennis E. Walsh)33 relates to
improving the cetane number of raw, untreated, highly aromatic, middle distillate
fractions having a low hydrogen content by contacting the fraction at a temperature
of from 50–350 °C and under mild oxidizing conditions in the presence of a
catalyst which is either (1) an alkaline earth metal permanganate, (2) an oxide of
a metal of Groups IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIIIB of the periodic
table, or a mixture of (1) and (2). European Patent Application 0,252,606 A2 also
relates to improving cetane number of a middle distillate fuel fraction which may
be hydro-refined by contacting the fraction with oxygen or oxidant, in the presence
of catalytic metals such as tin, antimony, lead, bismuth and transition metals of
Groups IB, IIB, VB, VIB, VIIB and VIIIB of the periodic table, preferably as an
oil-soluble metal salt. The application states that the catalyst selectively oxidizes
benzylic carbon atoms in the fuel to ketones.33
US Pat. No. 4,723,963 to William F. Taylor34 suggests that cetane number is
improved by including at least 3 wt% oxygenated aromatic compounds in middle
distillate hydrocarbon fuel boiling in the range of 160–400 °C. This patent states
that the oxygenated alkyl aromatics and/or oxygenated hydroaromatics are
preferably oxygenated at the benzylic carbon proton.34

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Table 8.4 shows some of the latest filed patent applications in oxidative
desulfurization47 Oxidative desulfurization of middle distillates by reaction with
aqueous hydrogen peroxide catalyzed by phosphotungstic acid and tri-n-
octylmethylammonium chloride as phase transfer reagent followed by silica
adsorption of oxidized sulfur compounds has been described by Collins et al.7 This
described the oxidative desulfurization of winter-grade diesel oil which had not
undergone hydrotreating. While Collins et al. suggest that the sulfur species resistant
to hydrodesulfurization should be susceptible to oxidative desulfurization, the
concentrations of such resistant sulfur components in hydrodesulfurized diesel may
already be relatively low compared with the diesel oils treated by Collins et al.7

Table 8.4 Some of the latest filed patent applications in oxidative desulfurization47

Technology type Patent application no. Main features

O2 gas 20060021913 (BP) • Contacting the feedstock with an O2

gas in an oxidation zone in the
presence of an oxidation catalyst
comprising a zeolitic material.
• Reducing the sulfur and/or nitrogen
content of a distillate feedstock.
Acetic acid 20040118750 (BP) • Contacting a hydrocarbon feedstock
with an immiscible phase containing
hydrogen peroxide and acetic acid
in an oxidation zone to selectively
oxidize the sulfur and nitrogen
species.
• Then the hydrocarbon phase is
passed to an extraction zone
wherein aqueous acetic acid is used
to extract a portion of any remaining
oxidized impurities.
• The acetic acid phase effluent from
the oxidation and the extraction
zone is recovered for optional
recycle back to the oxidation and
extraction zones.
HDS catalyst 20050040078 (UOP) • Hydrocarbonaceous oil + recycle
stream containing sulfur-oxidized
compounds contacted with a HDS
catalyst.
• Resulting hydrocarbonaceous
stream + oxidizing agent give
sulfur-oxidated compounds.
• Hydrocarbonaceous oil with less
sulfur-oxidated compounds.
• Portion of the sulfur-oxidated
compounds is recycled to the HDS
reaction.
(Continued overleaf)

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Table 8.4 (Continued)

Technology type Patent application no. Main features

H2SO4 20050218038 • Contacting polyene compounds

with sulfuric acid at ambient
temperature to form two phases:
• Hydrocarbon phase with no loss in
octane number and a
• Spent acid phase.
• Hydrocarbon phase then can be sent
to desulfurization process
O2 gas + metal oxide 20050150819 • Converting the heterocyclic sulfur
catalyst compounds in the gas phase
oxygenated products as well as
sulfur-deficient hydrocarbons by
contacting it with metal oxide
catalyst in the presence of O2 gas.
• Recovering the oxygenated products
separately from a hydrocarbon
stream with substantially reduced
sulfur.
Sonic Energy 20050182285 • Exposing the crude or organic liquid
to a sonic energy at different
frequency help to reduce the sulfur
and nitrogen level.
• Advantages:
• Can be performed with or without
oxidizing agent.
• With or without elevated
temperature or pressure.
• Can be performed as either
continuous process or batch
process.
Ultrasound 20040222131 • The sulfur species present in the
crude oil or other refinery streams is
oxidized to sulfoxides and/or
sulfones by ultrasound with or
without oxidizing agent.
• The oxidized sulfur species are
converted to hydrogen sulfide gas
by hydrodesulfurization processes.

US Pat. No. 4,746,420, issued to Darian and Sayed-Hamid, also proposes the
use of nitrogen oxides to oxidize sulfur- and nitrogen-containing compounds
followed by extraction using two solvents – a primary solvent followed by a
cosolvent that is different from the primary.19 The sulfur and nitrogen results
published in this patent are consistent with those expected from incomplete
oxidation of these compounds followed by extraction.35

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Tetsuo claims many oxidants as being essentially equal in their ability to

oxidize sulfur- and nitrogen-containing compounds.10 Many of these oxidants are
not selective as found later. Oxidizers that proceed by an auto-oxidation
mechanism involving a free radical tend not to be selective for the sulfur- and
nitrogen-containing compounds of interest, producing numerous side reactions
and, hence, various undesirable byproducts. The author does not provide the level
of sulfur removal that his method achieves.
Zannikos et al. describe an oxidation and solvent extraction technique for the
removal of sulfur-containing compounds.51 Peroxyacetic acid was used in an
inefficient manner to oxidize the sulfur compounds in a diesel fuel. Methanol,
dimethyl formamide and N-methyl pyrrolidone were used as simple one-stage
extraction solvents at different ratios. The results of their work show these solvents
removed much of the usable oil along with the oxidized sulfur compounds. To get
sulfur levels of approximately 500 ppm with these solvents, the researchers
reported a loss of 30% or more of the overall fuel. Such a loss is completely
unacceptable on a commercial basis.
In a 1993 European Patent, Funakoshi and Aida claim a method of recovering
organic sulfur compounds from liquid oil using oxidizing agents, followed
by distillation and solvent extraction or adsorption.9 The organic sulfur is
recovered as sulfones or sulfoxides. Organic sulfur compounds in fuels could be
effectively recovered by a simple solvent extraction process.35 Using acetone,
dimethylformamide or other solvents, more than 90% sulfur removal from various
hydrocarbon fuels (ranging from gasoline to straight-run bottoms) could be achieved
through six to eight stages of extractions with a solvent to oil ratio of 1:1. When an
oxidation step is applied before the extraction, an even higher degree of sulfur removal
is obtained. Earlier work at Alberta Research Council by McFarlane and Hawkins
has shown that organic sulfur in bitumen and synthetic crude oil could be converted
to sulfones by hydrogen peroxide or performic acid although these researchers
found that the extraction of sulfur compounds from bitumen was ineffective.
Researchers from BP Chemical reported that dibenzothiophene could be 100%
converted to sulfones by using a phosphotungstic acid/hydrogen peroxide system
under mild conditions.16 Treatment of gas oils with the phosphotungstic acid/
hydrogen peroxide system shows that all the sulfur compounds present are oxidized.
The results also suggest that highly substituted dibenzothiophenes are the most
readily oxidized species containing a thiophenic nucleus. Zannikos et al. report that
a combination of oxidation with solvent extraction is capable of removing up to
90% of the sulfur compounds in petroleum fractions at acceptable liquid yield.51
The oxidation process itself leads to substantial sulfur removal without affecting the
boiling point distribution. Dolbear and co-worker report that the more refractory
sulfur compounds could be removed effectively using appropriate oxidants and
catalysts at near-ambient temperature and pressure.4,5,12 PetroStar Inc. is one of the
companies that are seriously pursuing this approach.20,27,49 Because of their leading
work in this direction, PetroStar was selected by the US Department of Energy as

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258 Advances in clean hydrocarbon fuel processing

one of the three teams to lead the development of ultra-clean fuels by developing
new refining processes that remove sulfur pollutants from crude oil.27
The desulfurization reactivity of actual hydrocarbon fuels, such as straight-run
light gas oil (LGO), commercial hydrocarbon fuels (CLO) and light cycle oil
(LCO), of differing sulfur and aromatic concentrations, was studied using oxidant
system H2O2 and AcOH, by Yasuhiro Shiraishi et al.51 The desulfurization
efficiency for hydrocarbon fuels fell in the order LGO > CLO > LCO. This order
is the same as that of the aromatic concentration in hydrocarbon fuels, and
demonstrates that high-aromatic-content hydrocarbon fuels are difficult to
desulfurize. The sulfones formed by oxidization are not only removed into the
aqueous phase but also form an insoluble precipitate and remain in the hydrocarbon
fuels. The low desulfurization efficiency for hydrocarbon fuels is caused by the
accumulation of sulfones in the resulting oil.
UniPure ASR-2 is a two-step process. The sulfur species are oxidized into sulfones
using an oxidant carried in the aqueous phase with a liquid catalyst. This reaction
consumes ’small’ amounts of oxidant; conversion of sulfur compounds into sulfones
occurs quickly with a 5 min reactor residence time. After separation from the oil, the
aqueous phase – containing spent catalyst and some sulfones – is sent to a recovery
section. At recovery, the sulfones are removed and the catalyst is regenerated. The oil
phase, which also carries some sulfones, is forwarded to an extraction step that uses
a solid adsorbent. Methanol is used to regenerate this Adsorbent. The final product is
diesel with 5 ppm of sulfur. Recovered sulfones can be disposed off in the refinery
coker. One ton per day of sulfone is extracted for each 1000 b/d of diesel (500 ppm
sulfur) processed with present equipment configurations for low sulfur specifications.

8.3.6 Process development

A typical oxidative desulfurization process looks relatively simple. The process is
simply composed of a hydrodesulfurization process to reach about 500 ppm of sulfur
and followed by oxidative desulfurization process to reduce the sulfur level to about
10 ppm. Several major problems are impediments for commercial development.
First, the oxidants chosen do not always perform selectively. Many oxidants engage
in unwanted side reactions that reduce the quantity and quality of the hydrocarbon
fuels. The second problem is the selection of a suitable solvent for the extraction of
the sulfur compounds. Using improper solvent may result in removing desirable
compounds from the fuel or extracting less than a desired amount of the sulfur
compounds from the fuel. Finally, further work is needed to identify the most
effective catalyst and economical means to use or dispose of the byproducts.

8.3.7 Process economics

Lyondell Chemical developed a semi-commercial process at a 1 b/d in-house pilot
unit using t-butyl hydroperoxide oxidant which has the advantage of being fuel

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 Sulfur removal from heavy and light petroleum hydrocarbon 259

Table 8.5 A comparison between conventional hydrotreating and oxidative

desulfurization process14

Parameter Base operation Conventional Oxidative

hydrotreating desulfurization

Diesel sulfur, (wt ppm) 400 <10 <10

Diesel yield, Iv-% 98.5 97.0 97.0
Capital cost ($MM) 16.0
Hydrogen cost ($MM/yr) 6.7 9.5 6.7
Utilities cost ($MM/yr) 0.7 0.8 2.4
Catalyst cost ($MM/yr) 0.6 5.0 1.8
Total operating cost ($MM/yr) 8.0 15.3 10.9
Delta product value ($MM/yr) 1.7 2.0 1.7
Total operating cost ($bbl) 0.64 1.38 0.95
∆ NPV, (10%, 10 year) ($MM) <39> <31>

soluble and co-oxidant organic acid is not needed (NPRA, 2003). This oxidant has
multiple suppliers and was claimed to be the most cost effective source of active
oxygen. Semi-commercial operation showed that 10 ppm S diesel fuel was readily
achievable. The cost of the process was $600–750/b/d capacity installed cost with
an operating cost of < 2.5 cents per gallon for a unit taking today’s low-sulfur
diesel fuel to ultra-low sulfur diesel with less than 10 ppm of sulfur to be less than
2.5 cents per gallon including the cost of oxidant, all utilities, labor, taxes and
insurance. Table 8.5 illustrates the process economics of oxidative desulfurization
compared with conventional hydrodesulfurization technology. The study was
conducted by UOP and Eni.
The US Department of Energy (US DOE, 2001) estimated marginal
hydrotreating costs for 500 ppm sulfur diesel being converted to 7 ppm product to
be in the range of 4.7–9.2 cents per gallon. Another study by Charles River
Associates (Moncrieff et al., 2000) showed the incremental refining cost (based
on hydrotreating) for diesel fuel in the US to range from very low, for refineries
already having high pressure hydrotreaters, to as high as 15 cents per gallon for
refineries having no hydrotreating or hydrogen generation capabilities. Most of
the refiners studied have incremental costs in the range 5–8 cents per gallon.

8.4 Conclusions
Oxidative desulfurization technology was aimed as an alternative to revamping
HDS units to make ULS diesel or as an alternative to a new high pressure HDS
unit, although the refineries have already accepted the hydrotreating route to ULS
fuels. The approach can possibly serve as a stand-alone unit at terminals to take
care of off-specification products, if the related technical issues are addressed.
Oxidative desulfurization technology still needs additional research and

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260 Advances in clean hydrocarbon fuel processing

development, especially on the catalysts to make the oxidization more selective.

The oxidization–extraction method and use of byproducts could be further
improved. Although better understanding and processing hopefully will improve
economics, several companies have developed demonstration units on the
technology. Commercial process may evolve, if the underlying technical and
economical issues are addressed.

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 Sulfur removal from heavy and light petroleum hydrocarbon 261

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The review was conducted during Dr Khan’s personal time and reflects the opinion of the
author and not of that of his employer.

© Woodhead Publishing Limited, 2011