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Retraction for Catalysis Science & Technology

Towards near zero-sulfur liquid fuels: a perspective review

Barbara Pawelec, Rufino M. Navarro, José Miguel Campos-Martin and José L. G. Fierro

Catal. Sci. Technol, 2011 (DOI: 10.1039/C0CY00049C). Retraction published 3rd December 2012

We, the named authors, hereby wholly retract this Catalysis Science & Technology article, due to
significant similarity with previously published work.

Signed: B. Pawelec, R. M. Navarro, J. M. Campos-Martin and J. L. G. Fierro, October 2012.

Retraction endorsed by Jamie Humphrey, Editor, Catalysis Science & Technology.

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Cite this: Catal. Sci. Technol., 2011, 1, 23–42

www.rsc.org/catalysis PERSPECTIVE
Towards near zero-sulfur liquid fuels: a perspective review
Barbara Pawelec, Rufino M. Navarro, José Miguel Campos-Martin and
José L. G. Fierro*
Received 15th November 2010, Accepted 14th December 2010
DOI: 10.1039/c0cy00049c

This perspective review discuses the fundamentals and factors influencing the removal of the
least reactive sterically hindered S-containing compounds present in transportation fuels, and
more specifically in the diesel fraction. The challenge for deep desulfurisation of diesel fuels is
the difficulty of removing the refractory sulfur, particularly 4,6-dimethyldibenzothiophene, with
conventional hydrodesulfurisation (HDS) processes. The first part presents the principles and
problems associated with existing HDS processes, and the concepts, advantages and
disadvantages of various new approaches together with the latest developments in deep HDS
catalysts and the scientific basis for improvements in the performance of the new generation
of catalysts. Special attention is paid in the second part to the progress made in alternative
process concepts and technologies that are being developed for ultra low sulfur fuels.

Introduction The combustion of fossil fuels releases harmful emissions

into the atmosphere that impact on living organisms, as well as
With the growing awareness that oil is a finite resource, it is a cause the greenhouse effect. Major emissions of NOx, SOx,
very important task to try to utilize it as effectively as possible CO2 and particulate matter are the cause of most concern for
whilst limiting its environmental impact, for example, by pollution in our environment. Emissions of NOx, together
reducing the sulfur and aromatic levels in the various hydro- with hydrocarbons, increase the ozone levels in the troposphere
carbon fuels. The problem of the CO2 emissions intrinsically while SOx gases cause acid rain. The greenhouse gases (GHGs)
associated with hydrocarbon combustion and its climatic most closely identified with transportation are carbon dioxide
consequences must be taken seriously. In the overall context, (CO2), nitrous oxide (N2O), and methane (CH4). Other
fuel quality and fuel economy are important parameters that vehicle-related pollutants also contribute to global warming,
the refining and automotive industries will have to improve although their quantification is more difficult; these include
continuously, prompted by ever-stricter environmental legisla- CO, non-methane hydrocarbons (NMHCs), nitrogen dioxide
tion. In addition, last century’s hike in oil production now (NO2), and ozone (O3). Black carbon (soot) emitted from
manifests itself in a degeneration of the average crude quality, diesel vehicles is another emerging GHG concern.4 Sulfur-
as the remaining contents of the known reservoirs tend to be of containing compounds and polyaromatic hydrocarbons
heavier and sourer composition. New wells are constantly present in diesel fuel are responsible for the particulates or
being sought out; nowadays, prospectors often have to explore soot in diesel.5,6 Traces of sulfur present in diesel fuels
remote and hostile off-shore areas, yet major discoveries also poison the oxidation catalysts in the emission control
are encountered increasingly seldom. Although the necessity system and reduce their effectiveness for the oxidation of
of alternative energy solutions is widely recognized, oil and harmful carbon monoxide, hydrocarbons and volatile organic
hydrocarbon fuels are predicted to prevail for many years to matter.7
come.1,2 Environmental regulations have been introduced in many
Fossil fuels are used in the day-to-day production of electri- countries around the world to reduce the sulfur content of
city and the propulsion of vehicles. In particular, motorised diesel fuel to ultra low levels (10 ppm) with the aim of lowering
transport is over 95% dependent on oil and accounts for the diesel engine’s harmful exhaust emissions and improving
almost half its global use. This made road transport a signifi- air quality.8 Meanwhile, the demand for transportation fuels
cant source of air pollution in the last century, and car engines has been increasing in developed countries over the past two
are still a major producer of toxic emissions, with subsequent decades. Basically, all these motor fuels are derived from oil,
adverse effects on human health.3 with the sole exception of coal (and natural gas)-derived fuels
produced in South Africa by Fischer–Tropsch synthesis. The
global demand for energy and, in particular, transportation
Sustainable Energy and Chemistry Group, Institute of Catalysis and
Petrochemistry, CSIC, Marie Curie 2, Cantoblanco, 28049 Madrid, fuels keeps growing. Global energy consumption in 2007 was
Spain. E-mail: jlgfierro@icp.csic.es; Web: http://www.icp.csic.es/eqs/ about 12.0 billion toe (toe = tonnes of oil equivalent) and is

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The increasing attention being paid worldwide to the

chemistry of diesel fuel processing is related to both thermal
efficiency and environmental aspects, which include both
pollutants and greenhouse gas emissions. As a general trend,
diesel fuel demand is expected to increase significantly over the
next two decades.31 In addition, interest in ultra-clean fuels
also stems from the use of new emission control technologies
for internal combustion engines (especially diesel fuels), and
for using the on-board or on-site reforming of hydrocarbon
fuels to supply the H2 required to feed the future generation of
Fig. 1 Global energy demand by type in billion tonnes of oil electric cars. Since the general chemistry of diesel fuels is well
equivalent in 2007 (left) and estimates for 2015 (right). Adapted by known,32 the objective of this Perspective Article is to provide
British Petroleum from the World Energy Outlook 2009. a selective overview of new design approaches and the
associated catalysis and chemistry, as well as of processes for
expected to grow until 13.3 billion toe by 2015 (Fig. 1) Oil the deep desulfurisation and deep hydrogenation of hydro-
consumption rose from around 70 million barrels per day in carbon fuels, particularly diesel fuels. In a first instance,
1995 (1 barrel = 159 L) to over 80 in 2005, and it is projected the major drivers of the demand for new and better hydro-
to grow to over 90 million barrels per day in 2020.9 While a processing catalysts are examined, and then the challenges
significant part of the demand is located in North America, the faced in catalyst development are considered.
largest growth is observed in the Asia-Pacific region. The
future growth of energy demand in the Asia-Pacific area has
recently seen a series of calls for new grass-root refineries, 2. Drivers of ultra low sulfur fuel production
mainly to be located in the Middle East and Asia-Pacific.
2.1 Environmental legislation on diesel fuel specification
Current predictions suggest that only 60% of all the new
projects announced will actually materialize. This means The SOx oxides, particulates and other harmful pollutants
that new refineries imply new hydroprocessing units and present in exhaust engines are the main reasons for targeting
further growth of the overall market for hydroprocessing sulfur content in fuel, mainly in the diesel fraction, and
catalysts. This is just one reason for the industry now needing decreasing it to ever lower levels in many countries worldwide.
hydrocracking units and catalysts to process the ‘‘bottom of It has been shown that low S-levels in fuels and the use of
the barrel’’. appropriate particulate filters can reduce particulate matter by
In addition, the new environmental regulations that limit as much as 90%.33 In the USA, the acceptable level of sulfur in
the S-levels of transportation fuels, and specifically diesel highway diesel was first reduced from 2000 ppm to 500 ppm by
fraction, are beneficial from an environmental point of view, the Clean Air Act (CAA) amendments in the nineties, then to
and meeting their stringent requirements is a major challenge 350 ppm, 50 ppm and 15 ppm in the years 2000, 2005, and
for the petroleum refining industry.10–14 The very low S-levels 2006, respectively (Fig. 2).34 In the EU, Germany was the
to be achieved in motor fuels necessarily imply the ultra-deep first country to adopt the 10 ppm sulfur limit for diesel as
desulfurisation of the diesel feed stream. The shift from from January 2003. Other EU countries and Japan introduced
normal to ultra-deep desulfurisation is a very complicated diesel fuel with 10 ppm into the market from the year
issue. Factors such as feedstock source,15,16 catalysts,17–20 2008 (Fig. 3).35,36
reactivity of S-compounds,21,22 inhibition effects of H2S,23–25 Similar ultra low sulfur specifications are also targeted in
nitrogen compounds,26,27 aromatics,28,29 and process parameters,30 many other countries, and will be predominant worldwide
among others, have a significant bearing on the degree of during the next decade. The specifications proposed for clean
desulfurisation of feeds. diesel by the Worldwide Fuel Charter (WWFC), which reflects

Fig. 2 Trends in diesel sulfur fuel specifications for high way transportation vehicles.

24 Catal. Sci. Technol., 2011, 1, 23–42 This journal is c The Royal Society of Chemistry 2011
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This journal is © The Royal Society of Chemistry 2011

Fig. 3 Trends in sulfur specifications for non-road diesel (NR: non-road, and LM: locomotive and marine diesel).

Table 1 Worldwide fuel charter diesel fuel category 4 specifications of contaminant compounds, such as arsenic compounds, for
example, compared to traditional North Sea and Middle
Source fuel specification Worldwide fuel charter category 4
East crudes. The effects from heavier crude supply are thus
Density, max/g cm 3 0.840 twofold. Since the demand for light products is increasing at
S/ppm 5–10 the expense of heavier fuels (e.g. heavy fuel oil), more crude
Cetane index 452
Cetane number 455 conversion will be needed to upgrade the heavy crudes to
Aromatics/vol% o15 provide the desired product mix. Secondly, the higher level of
Polynuclear aromatics/vol% o2 metal-containing micelles in the feed will require more effective
T90 (max 1C) 320
T95 (max 1C) 340
guard bed catalysts and systems.
A very exciting and emerging field is the production of
syncrudes (synthetic oils) in Canada and Venezuela. Canadian
the view of car/engine manufacturers concerning the fuel syncrudes are produced from tar sands by a process of
qualities required for engines in use and for those yet to be extraction and bitumen upgrading.40 The upgrading of
developed, require a higher cetane index, significant reduc- these tar sands, via bitumen, to synthetic crude oil is most
tion of polyaromatic hydrocarbons (PAH), and a lower T95 challenging with respect to hydrotreating, since the bitumen
distillation temperature in addition to ultra low sulfur levels contains two to four times as much sulfur, nitrogen and
(Table 1). Car manufacturers have concluded that substantial aromatic compounds as standard crudes. The levels of arsenic-
reductions in both gasoline and diesel fuel sulfur levels to quasi and silicon-containing compounds can be quite high, which
S-free levels are essential to enable future vehicle technologies creates its own problems in such processing schemes. The
to meet stringent vehicle emission control requirements and operating conditions for the hydroprocessing of these types
reduce fuel consumption. Similar tighter sulfur specifications of crude are much more severe compared to the processing of
have also been introduced for non-road diesel37 (Fig. 3). In conventional crude fractions. Consequently, the experience
2004, the US Environmental Agency (USEPA) issued the with conventional hydrotreating catalysts operating under
clean air-non-road-Tier 4 final rule which mandates that these sorts of conditions is limited, and it can be assumed that
starting from 2007, the fuel sulfur level in non-road diesel fuel opportunities will open up with the development of bespoke
should be reduced to 500 ppm from its current 3000 ppm level. catalysts for this area.
This includes fuels used in locomotive and marine applications
(except marine residual fuel used by very large engines in
ocean-going tankers). In 2010, fuel sulfur levels in most non-road 3. Deep HDS
diesel fuel have been reduced to 15 ppm, making it possible
for engine manufacturers to use advanced emission control 3.1 Reactivities of sulfur compounds
systems that significantly reduce harmful fumes. The sulfur compounds can be classified into four groups
according to their HDS reactivities that are described by the
2.2 Heavier crudes
pseudo-first-order rate constants: (i) sulfur compounds dominated
Oil refiners are increasingly processing heavier and worse by alkyl benzothiophenes (BTs); (ii) dibenzothiophenes (DBT)
quality feedstocks, while the specifications for middle distillates and alkyl dibenzothiophenes (DBTs) without alkyl substituents
and gasoline/diesel engines are becoming more stringent.38 at the 4- and 6-positions; (iii) alkyl DBTs with only one alkyl
There is a continuous trend within the refining industry substituent at either the 4- or 6-position; and (iv) alkyl substi-
whereby crudes are becoming heavier (higher density and tuents at the 4- and 6-positions (as shown in Fig. 4).12,41,42 The
viscosity) and sourer, which means a larger amount of sulfur. latter species are termed refractory sulfur compounds and
A prediction by Hart is that over the next 15 years an extra both steric hindrance and electronic factors are claimed to
0.15 wt% of sulfur will be recorded in crude, giving an average be responsible for their low reactivity.42–46 The relative rate
level of 1.28 wt%.39 In addition, the shift in crude diversity constants of HDS, assuming pseudo first-order kinetics,
and source will continue. For example, more Russian and for some alkyl-substituted dimethyl DBTs are displayed in
Caspian crude import is expected in Western Europe, and Fig. 5.44 According to these values, the relative reactor volume
these crudes are heavier and contain high heteroatom amounts requirements for various degrees of sulfur removal by

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Fig. 4 Structures of refractory sulfur compounds. (1) thiophene; (2) benzothiophene; (3) dibenzothiophene; (4) benzo(b)naphtha 2,3-thiophene;
(5) 4-methyl dibenzothiophene; (6) 4,6-dimethyl dibenzothiophene; (7) 2,8-dimethyl dibenzothiophene; and (8) 3,7-dimethyl dibenzothiophene.

Based on conventional approaches to the standard HDS

processing of diesel fuels when reducing the sulfur level from
the current 500 to 15 ppmw (the regulation in 2006), the
volume of catalyst bed will have to be increased to 3.2 times
that of the current HDS catalyst bed. When reducing the
sulfur level to 0.1 ppm by conventional HDS processing for
fuel cell application, the volume of catalyst bed will have to be
increased by about sevenfold. There is no doubt that the use
of high temperature and high pressure renders the process
prohibitive. In other words, using current commercial HDS
processes without changing the reactor volume means catalyst
activity will have to be increased by a factor of 3.2 and 7 to
meet the new regulation and fuel cell applications, respectively.
It might be difficult to meet this requirement by making small
incremental improvements to existing hydrotreating catalysts
that have been developed over the past 50 years.
The petroleum refining industry is therefore facing a major
Fig. 5 Relative values of the rate constants (kthiophene/kDMDBTs) for the challenge to meet the new stricter sulfur specifications in the
desulfurization of different dimethyl substituted dibenzothiophenes. early 21st century, when the quality of crude oils continues
to decline in terms of increased sulfur content and decreased
conventional single-stage HDS of diesel fuels have been API gravity.
calculated. The estimation of volume requirements is based
3.2 Reaction pathways
on the results from HDS kinetics studies using a commercial
CoMo/Al2O3 catalyst,44 assuming 1.0 wt% S in feed. Important progress has been made in the fundamental under-
Sulfur removal in gasoline is relatively straightforward by standing and practical application of hydrotreating catalysis
current catalytic HDS processes. The challenge in the deep and metal sulfide-based catalysts for HDS, as discussed in
desulfurisation of FCC naphtha involves the selective conver- several excellent reviews.47–50 The following discussion focuses
sion of sulfur compounds without saturating olefinic com- on the deep desulfurisation of polycyclic sulfur compounds.
pounds, which contribute to octane number enhancement. For The hydrodesulfurisation of DBT and alkyl DBTs proceeds
the straight-run kerosene used for making jet fuels, sulfur mainly via two parallel routes, as shown in Fig. 6. The first
removal by HDS is more difficult than that from naphtha, but route involves direct desulfurisation (DDS) leading to the
less difficult compared to that from gas oil. Recent papers have formation of biphenyl, while the second route involves the
reported that the sulfur compounds remaining in diesel fuels at hydrogenation (HYD) of one of the benzene rings of the DBT,
a sulfur level below 500 ppm are the DBTs with alkyl producing tetrahydrodibenzothiophene in the first step, which
substituents at the 4- and/or 6-position, because of their lower is further desulfurised to cyclohexylbenzene.51,52 It has been
HDS reactivity.10,41–44 When the total S-content is reduced to shown that the HDS of unsubstituted DBT occurs preferen-
30 ppmw, the sulfur compounds remaining in the hydrotreated tially via the direct sulfur extraction (DDS) route. The alkyl
oil belong solely to the fourth group, indicating that the lower substituents affect the HDS of DBT in two ways: (i) they reduce
the sulfur content, the lower the HDS reactivity, which has their HDS reactivity; and (ii) they change the ratio between the
been discussed by Whitehurst et al. in their review paper.45 rates of the two routes. The HYD route becomes dominant with
More recent studies using various straight-run gas oils from the introduction of alkyl substituents in the 4- and/or 6-positions
different crude oils have confirmed the differences in reactivity of the DBT molecules.48,50 It has been documented that partial
between different sulfur compounds.46 saturation changes the spatial configuration of the molecule,50

26 Catal. Sci. Technol., 2011, 1, 23–42 This journal is c The Royal Society of Chemistry 2011
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intermediate. The DDS pathway is considerably slower than

the sulfur removal via the HYD pathway due to the presence
of the methyl groups. This may be due to the lower flexibility
in DBT and 4,6-DMDBT than in their partly hydro-
genated intermediates, making adsorption easier for the latter
molecule.

3.3 Inhibition effects

In the production of ultra low sulfur diesel fuel (o10 ppm S),
more than 99% of the S-containing compounds, including the
traces of least reactive alkyl DBTs present in the feedstock,
have to be removed during catalytic hydrotreating. The main
problem in the HDS of the sterically hindered alkyl DBTs is
the inhibiting effects of different poisons, such as N-containing
compounds, H2S and aromatic molecules, on their reactivity
under reaction conditions imposed for deep desulfurisation.
Fig. 6 Direct and hydrogenation reaction pathways for hydro-
As shown in the previous section, sulfur removal from DBT
desulfurization of 4,6-dimethyl dibenzothiophene. and alkyl substituted DBTs can take place along DDS and
HYD routes. The former involves direct sulfur extraction,
while the latter involves two steps: hydrogenation of one of the
making the sterically hindered sulfur more accessible for adsorp- aromatic rings in the first step, followed by S-removal as H2S
tion on the active site prior to reaction. in the second step. The poisoning effects of the inhibitors
The DDS pathway is severely inhibited, while the HYD (H2S, nitrogen compounds and aromatics) are different
pathway is hardly affected by the presence of alkyl groups in for the two routes and are discussed in some detail in
the 4- and 6-positions of DBT. It has been suggested that the several papers.13,54–56 In general, the inhibition order is as
alkyl groups in the 4,6-DMDBT do not play a significant role follows: nitrogen compounds 4 organic sulfur compounds 4
in the reactivity of 4,6-DMDBT along the HYD pathway, and polyaromatics E oxygen compounds E H2S 4 monoaromatics.
the difference in reactivity between DBT and 4,6-DMDBT lies The inhibition is not only for HDS but also between inter- and
essentially in the selective promoting effect on the DDS intra-molecular reactions, as well as its intermediate reaction
pathway.53 products.57–59
A common dihydro-dibenzothiophene intermediate was
suggested for the DDS and HYD reaction routes. The orienta-
4. Catalyst development for deep HDS
tion of the reaction toward one or the other of the two possible
pathways is due to the difference in reactivity of the common Catalysts consisting of molybdenum supported on alumina
dihydro intermediate in further hydrogenation or in the C–S and promoted with cobalt or nickel are traditionally used in
bond cleavage through elimination. The hindrance of the C–S hydrotreating processes. The role of the catalyst is to enhance
bond cleavage in the partially hydrogenated intermediate the removal of S, N and aromatics present in the refinery
could thus be the most likely reason for the low reactivity of streams by promoting HDS, hydrodenitrogenation (HDN)
alkyl DBTs with the alkyl substituent in the 4 and 6 positions. and hydrogenation (HYD) reactions. Conventional CoMo- and
The proposal of a common dihydrodibenzothiophene inter- NiMo-based catalysts, however, do not have sufficient activity
mediate for both DDS and HYD reaction pathways poses to desulfurise diesel feed streams to ultra low sulfur levels
certain doubts. It has been proposed that the two HDS path- under normal operating conditions. They require severe
ways do not have a common intermediate and are determined operating conditions, such as high temperature, low space
by the conformation of the adsorbed DBT molecule. DDS velocity and high hydrogen partial pressure. Such severe
reaction starts with the p adsorption of the DBT molecule processing conditions generally lead to rapid catalyst deactiva-
via the S-atom, whereas the HYD reaction starts with s tion, shorter cycle times and reduced throughput. The develop-
adsorption of the reactant via the aromatic system. This would ment and application of more active and stable catalysts are
require different sites and different adsorption constants for among the most promising options for reducing the S-content
the DDS and HYD pathways. The main reason for this of diesel to ultra low levels by deep desulfurisation.60,61
difference is the aromaticity of the DBT structure, making p Studies have shown that around 4 times more active
adsorption more likely than s adsorption. It has been shown catalysts are required to reduce the S-content of diesel fuel
that methyl groups hinder the perpendicular s adsorption of from 500 to 50 ppm. Further improvement in catalyst activity
DBT, but hardly affect flat adsorption via the aromatic p system. is necessary when the sulfur content is to be reduced to ultra
It is suggested that in the HYD route, 1,2,3,4-tetrahydro- low levels (o15 ppm). Intensive efforts have been devoted
thiophene is formed as a partially hydrogenated intermediate, worldwide to the development of highly active hydrotreating
and the final removal of the S-atom from tetrahydrothiophene catalysts for the deep desulfurisation of diesel to ultra low
could occur by hydrogenolysis (through s adsorption). There- sulfur levels,62–65 and new generation catalysts with very
fore, the methyl groups suppress not only the s adsorption high HDS activity are being continuously developed and
of the reactant, but also of the partially hydrogenated introduced to the market. The development of improved

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hydrotreating catalysts has been possible through a clear Co–Mo–S phases is less disperse, consisting of multiple slabs
understanding of the key properties, namely, the nature of not linked to the support. Further studies have shown that the
the active sites and their structure, support effects and the degree of stacking in MoS2 layers and Co–Mo–S structures
textural characteristics of supports, which have significant can be controlled by tailoring support properties and prepara-
influence on catalyst performance.66–68 The scientific basis tion parameters. These will have a high MoS2 edge dispersion
for the high activity of the new generation hydrotreating that can accommodate more Co-atoms to form higher active
catalysts is presented and discussed in detail in the following single slab type II Co–Mo–S structures.
sections.

4.1 Conventional catalysts 4.1.1 Origin of synergy between Co(Ni) and Mo. A model
correlating stacking degree and selectivity properties for non-
The nature of the active phase in unpromoted and promoted
promoted and on-supported MoS2 catalysts was proposed by
MoS2 catalysts has been widely studied and reported in several
Daage and Chianelli.47 Two types of sites were distinguished
reviews.69,70 For unpromoted molybdenum sulfide catalysts, it
based on their location on the layers: the ‘‘rim’’ sites on the top
has been proposed that coordinatively unsaturated (CUS) sites
and bottom layers capable of hydrogenating and cleaving C–S
or exposed Mo ions with S-vacancies at the edges and corners
bonds, and the ‘‘edge’’ sites located at the outer edges of the
of MoS2 structures are active in hydrogenation and hydro-
interior layers that can only cleave C–S bonds. The specific
genolysis reactions. Basal planes are inactive in the adsorption
location of ‘‘rim’’ sites on exterior layers is responsible for
of molecules and are probably unimportant in hydrotreating
their hydrogenating character by facilitating the flat adsorp-
reactions. For Co- or Ni-promoted catalysts, several different
tion of DBT—a requirement for the hydrogenation step.71
structural models, such as monolayer model, intercalation
Regarding the HYD and DDS pathways of the HDS of DBT,
model, contact synergy model, Co(Ni)–Mo–S phase model,
it was shown that cobalt promotion sharply enhances the
and catalytic Co site model, have been proposed to explain the
quality of the sites involved in C–S bond cleavage steps.
role of the promoter and its location in the catalyst. Among
Following the identification of Co–Mo–S phase structures as
these, the Co(Ni)–Mo–S model proposed by Topsøe69 is now
the catalytically active phase, many theories were proposed to
widely accepted. The Co(Ni)–Mo–S structures are small MoS2
explain the electronic origin of the synergy between Co and
nano-crystals with the Co- (or Ni)-atoms located at the edges
Mo in the Co–Mo–S phase in enhancing the HDS reaction.
of the MoS2 layers on the same plane of MoS2 layers (Fig. 7).
Nørskov et al. approached the problem using ab initio calcula-
The relative amount of Co-atoms present as the Co–Mo–S
tions.71 Their basic idea was that the binding energy of a sulfur
phase was found to correlate linearly with HDS activity.
atom was the important variable in explaining the periodic
Further studies on the structure–activity correlation of these
trends and promoted systems. They found a monotonic
catalyst systems allowed the identification of two types of
relationship between sulfur bond strength per sulfur atom
Co–Mo–S structures, one type having substantially higher
and the catalytic specific activity of the sulfides using literature
activity than the other. The high and low activity forms of
data. The weaker the metal sulfur bond strength, the higher
Co–Mo–S were termed types II and I Co–Mo–S, respectively.
the HDS activity. Consequently, the HDS rate would
The type I Co–Mo–S structures were deemed to be incomple-
be proportional to the number of active sites (i.e. sulfur
tely sulfided and have some remaining Mo–O–Al linkages to
vacancies) at the catalyst surface, which in turn will be
the support. The presence of such linkages was related to the
inversely proportional to the metal–sulfur bond strength.
interaction that occurs in the calcined state between Mo and
Harris and Chianelli72 posited that the specific and unique
surface alumina OH groups leading to oxygen bridged mono-
activity of the cobalt (or nickel) promoted MoS2 phase is
layer-type structures that are difficult to sulfide completely. In
related to an electron donation from Co to Mo decreasing the
type II Co(Ni)–Mo–S phase, the support interactions are
Mo–S bond strength to an optimum range for HDS activity.
weaker and fully sulfided. The underlying MoS2 in type II
These electron donations will increase the electron density in
the highest occupied molecular orbital (HOMO) of Mo,
occupying anti-bonding orbitals and then somewhat weaken-
ing the Mo–S bond energy. This electron transfer will also
decrease the occupancy of anti-bonding orbitals for Co,
strengthening the Co–S bond. The S-atom shared between
Co and Mo will then present intermediate metal–S bond
strength. It was then assumed that this intermediate strength
would be in an optimum range for HDS activity. This weak-
ening effect of Co(Ni) promotion on the metal–S bond
strength is now well accepted and was confirmed using theo-
retical calculations as well as experimental techniques.73,74
Fig. 7 Schematic representation of the CoMoS model under reaction Based on S-bond energy calculation and experimental work,
conditions. Co is present in three different phases. (1) The active Thomazeau et al.75 used DFT calculations to predict that Ni
CoMoS nanoparticles; (2) a thermodynamically stable cobalt sulfide promoted trimetallic NiMoW sulfide catalysts are better than
(Co9S8); (3) Co dissolved in the Al2O3 support. Only the CoMoS bimetallic NiWS and NiMoS (or CoMoS and CoWS) cata-
particles are catalytically active. Taken from ref. 69. lysts, as shown in Fig. 8.

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over the past decade to improve the HDS activity of alumina-

supported CoMo and NiMo catalysts by maximizing the
concentration of the type II sites by a variety of methods.
To achieve this, approaches such as modified supports,
the development of new carriers, improvements in catalyst
impregnation and preparation techniques, and the use of
certain additives, have been considered and discussed in
excellent reviews.11,78,79 As mentioned above, the deep HDS
of sterically hindered sulfur compounds in diesel fuel will
require the enhancement of hydrogenation activity to hydrogenate
the aromatic rings of the S-containing compounds. The use of
supports with high acidity can also improve the HDS of
refractory sulfur compounds by promoting isomerization
and dealkylation reactions.53,80,81
Fig. 8 Schematic representation of the relative positions of the The active components in hydrotreating catalysts are mixed
Co(Ni)Mo(W)S systems on the volcano curve and explanation of sulfides of Mo and Co(Ni) as Co(Ni)–Mo–S phases deposited
the new synergy effects for NiMoWS systems (DEMS, energy variation on a carrier. The carrier or support material usually provides a
associated to a catalytic system). Adapted from ref. 75. high surface area to maximize active phase dispersion. The
support also gives the catalyst mechanical strength. Alumina is
Further insight into atomic structure, morphology of the most widely used support material in hydrotreating
MoS2 and Co(Ni)–Mo–S phases was forthcoming using a catalysts because it combines almost all the above charac-
combination of advanced experimental and theoretical techniques, teristics. It is highly stable, contains acidic and basic sites, has
such as scanning tunnelling microscopy (STM), high-angle a reasonably high surface area and porosity, can be easily
annular dark-field scanning transmission electron microscopy formed into desired shapes, and is relatively inexpensive.
(HAADF-STEM) and density functional theory (DFT). STEM Despite these advantages, great interest has still been shown
showed atom-resolved images of the catalytically active edges in new supports for HDS catalysts due to the need to develop
of MoS2 and Co(Ni)–Mo–S nano-clusters.76,77 The Mo-edge better ones.82,83 A large number of new materials with high
was found to have a special electronic edge state identified as surface area and other properties suitable for support applica-
brim sites76 (Fig. 9). DFT calculations revealed the metallic tions have been developed and tested. These include TiO2,
nature of the brim sites. The metallic nature of these brim sites ZrO2, MgO, carbon, SiO2, zeolites, etc.84–87 Attempts have
means they may bind S-containing molecules, and when hydrogen also been made to modify the alumina by mixing it with
is available at the neighbouring edge sites in the form of SH zeolites and other metal oxides such as SiO2, TiO2, ZrO2,
groups, hydrogen transfer and hydrogenation reactions can etc. to exploit the favourable properties of both carriers. As
take place. Therefore, these brim sites are catalytically active these mixed oxides have acid–base properties, they promote
for hydrogenation reactions, whereas direct sulfur removal can the desulfurisation of alkyl DBTs.88 Differences in catalytic
take place at both edges. performance may arise as a result of variations in metal–
support interactions that may influence the dispersion and
4.2 Preparation of ultra deep HDS catalysts
morphology of active phases. The process involving the
It has been well established that in CoMo- and NiMo-based formation of the Co(Ni) –Mo–S active phases of the catalyst
hydrotreating, type II Co(Ni)–Mo–S catalyst sites are highly and their dispersion on the support surface is strongly influenced
active for HDS. Therefore, intensive efforts have been made by the interaction with the support.

Fig. 9 (a) Atomically resolved STM image (Vt = 5.2 mV, It = 1.28 nA) of a triangular single-layer MoS2 nanocluster on Au(111); the size of the
image is 41  42 Å2; (b) a cobalt-promoted MoS2 nanocluster; and (c) DFT calculations showing the location of metallic states. Taken from ref. 76.

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Support interaction also influences the degree of stacking adsorption that leads to direct desulfurization, in which the
of MoS2 and Co–Mo–S structures. Very weak support S-atom interacts directly with the surface of sulfide phases.
interaction resulted in the multi-stacking of type II Co–Mo–S However, zeolites do not permit a good dispersion of the
phases. It has been reported that the degree of stacking in active phase. Zeolites as cation exchangers should have
MoS2 and Co–Mo–S phases can be controlled by tailoring intrinsic difficulties to disperse molybdate salt precursors
support properties. Stable, single-slab MoS2 has been which are anionic. In addition, the size of the zeolites pores
observed on the alumina substrate. These slabs with a high is too small (o1 nm) to accommodate the active phase and
MoS2-edge dispersion accommodate more Co-atoms to ensure the access of bulky reactants like 4,6-DMDBT. Unlike
form higher active single-slab type II Co–Mo–S structures. zeolites, the pore size of ASA is not a limiting factor for active
A few studies have focused on the acidic and basic natures phase dispersion and for the diffusion of the large reactant
of the support and its effect on the nature of inter- molecules to the active sites located within the pores. Recently,
action with the active metal. TiO2 mixed oxide has received mesostructured systems such as MCM-41, Al-MCM-41,
relatively higher attention because it records higher activity. SBA-15 and SB-16 have received considerable attention as
NiMo/Ti–Al–O catalysts were more active than NiMo/Al2O3 supports for Co(Ni) and promoted Mo(W) sulfide catalysts.92–94
catalysts for the model compound HDS of DBT, 4-MDBT The high surface area of these nanoporous systems (pore size
and 4,6-DMDBT.69 HDS tests of straight-run distillate gas 5–10 nm) allows high CoMo or NiMo loading without the
oil showed that sulfide catalysts supported on Ti–Al–O restricted access of the zeolite structure to bulky molecules.94
composite (11 mol%) reduce the sulfur level of diesel fuel Thus, the performance of these catalysts is expected to be high
from 500 to 50 ppm under conventional HDS conditions.82,83 due to their defined textural properties (pore size 5–30 nm,
Ti-containing mixed oxide support not only enhanced wall thickness 3–5 nm) and high dispersion of nano-sized
light molecule HDS but also clearly promoted crude oil MoS2, as shown in Fig. 10. Substantially more active catalysts
HDS.89 than alumina-supported ones can be obtained by using these
Based on theoretical calculations and experiments, it has materials as support. The surface acidity of these materials can
been shown that both DBT and 4,6-DMDBT adsorbed be modified by the incorporation of additives such as Al, Ti,
horizontally on the catalyst surface and, therefore, the low Zr, etc. into the silica framework during synthesis.88,94,95
reactivity of 4,6-DMDBT compared with DBT came from Carbon-supported catalysts have also been found to
the reduced access of hydrogen to the C–S–C bridge after record high HDS activity with reduced deactivation by coke
adsorption.90 In addition, zeolites and amorphous silica– deposition due to the lower acidity of the carbon support.96,97
alumina (ASA) supports have been widely used for the HDS Rapid sintering of the active phase under reaction conditions
of S-containing compounds. For the sulfide phases deposited and its unsuitability for regeneration (after deactivation) are
on these substrates the specific rate constant for the HDS of the major disadvantages of using this support.
refractory sulfur compounds such as 4,6-DMDBT was found Unsupported transition metal sulfides have also been
to be substantially higher than on the conventional alumina- studied in recent years as potential new catalysts for hydro-
supported catalysts. For instance, when using ASA mixed treating reactions. The catalysts tested include sulfides of the
with a NiMo alumina catalyst, a 2.5-fold increase in the type RuS2, V2S3, Rh2S3, NbS3, and mixed sulfides of Co–Mo,
4,6-DMDBT HDS was found.91 As both ASA and zeolite Ni–Mo, Ni–W, Ni–Mo–W, Fe–W, Fe–Mo and Ni–Ru.
substrates show Brønsted acidity, the enhancement in the Among them, RuS2, Rh2S3 and NbS3 were found to exhibit
performance was associated to the Brønsted acidity-induced improved HDS performance over the traditional Co–Ni and
isomerization of 4,6-DMDBT to 3,6-DMDBT on the acid sites Mo–W sulfides.98 Unsupported Ni–Mo–W sulfide catalysts
of these substrates. It is likely that the methyl substituents in exhibited at least 3 times higher activity than the conventional
the 3- and 6-positions do not sterically hinder the vertical alumina-supported NiMo and CoMo catalysts.2Unsupported

Fig. 10 TEM image of the mesoporous SBA-15 (a) showing a well-ordered hexagonal array of mesopores when the electron beam is parallel to
the main axis of the cylindrical pores. HRTEM image of the sulfide CoMo/SBA-15 catalyst showing the slabs of the CoMoS phase.

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Ni–Mo–W sulfide composition is commercially used for deep as 3-hexylthiophene (221 1C) is much higher than that of
HDS of diesel under the commercial trade name NEBULA.99 thiophene (ca. 85 1C). This simple approach means it can be
Apart from the unsupported transition metal sulfides, the easily separated from the main gasoline stream by distillation.
hydrotreating activities of carbides and nitrides of Mo and The high-boiling compounds produced can be blended into the
W have also been investigated. These materials are stable diesel pool and desulfurised by conventional hydrotreating, as
under the hydroprocessing reaction conditions, which form the octane number is not important for diesel.
surface sulfide and remain active in HDS reactions with In the OATS process, there are two basic factors to be
time-on-stream.100 tackled: (i) the selection of the alkylation agent, as a suitable
Unsupported metal phosphides have also received much carbochain can raise the boiling points of the alkylated
attention due to their high activity for hydrodesulfuriza- thiophenes to an appropriate level; and (ii) the choice of the
tion (HDS) and hydrodenitrogenation (HDN) of petroleum catalyst would have less influence if a gasoline feed is
feedstocks.101–103 It has been shown that MoP and WP have employed because olefins are present. Several alcohols and
moderate activity and Ni2P has excellent activity in hydro- alkenes, such as methanol, propene/propanol, butene and
processing. The overall activity was found to be in the order: propene, have been chosen as the alkylation agents.132 The
Fe2P o CoP o MoP o WP o Ni2P in the simultaneous HDS alkylation catalysts include supported BF3, AlCl3, ZnCl2,
of dibenzothiophene and HDN of quinoline.104 or SbCl5, phosphoric acid, Hb zeolite and mesoporous
materials.133,134 In most cases, OATS studies have focused
5. ‘Non-HDS’ based desulfurisation alternatives on the conversion of thiophenes. Some insights into the
mechanism of the reaction and certain detailed functions of
Significant advances have been made over the past few years the catalysts have also been illustrated. Besides improving the
on developing new alternatives to the conventional catalytic activities of the catalysts for thiophene alkylation, the most
HDS reactions for removing sulfur from liquid fuels to ultra important problem is to prevent alkene oligomerization and
low levels. Higher temperatures and pressures, more active aromatics alkylation, as these parallel reactions decrease the
catalysts, longer residence times, and/or additional reactors efficiency of the OATS and increase the losses in gasoline
are required to increase the effectiveness of the HDS process. yield. As shown by previous studies,135 thiophene alkylation,
In view of this, efforts have been also made to develop new aromatics alkylation and hexene oligomerization coexist
processes for desulfurisation, particularly to remove those through the carbocation mechanism, and the only difference
highly refractory sterically hindered S-compounds under mild between them is the extent of their reaction. The reactivity is
operating conditions. Among these, oxidative desulfurisation known to be associated with the acidity of the catalysts. In
(ODS),105–111 biodesulfurisation (BDS),112–117 and S-extraction other words, variation in catalyst acidity would lead to a
using solvents118–125 and ionic liquids126–130 have been investi- change in the activity of all three reactions.
gated. The fundamentals and the advantages and limitations Alkylation is carried out in an OATS reactor and the
of these methodologies are given in the sub-sections below. alkylate is then sent to a conventional distillation column
where it is separated into a light S-free naphtha and a heavy
5.1 Shifting the boiling point by alkylation
S-rich stream. The light naphtha is sent directly to the gasoline
A simple procedure for removing organosulfur compounds pool and the heavy stream is preferably hydrotreated. By
from oil fractions is to increase their boiling temperature. means of OATS technology, over 99.5% of the sulfur can be
These heavier compounds can then be separated from light removed from the gasoline stream.136 It has been reported that
fractions by distillation and concentrated in the heavy boiling sulfur can be reduced in gasoline from 2330 ppm to fewer than
part of refinery streams. British Petroleum used this concept in 20 ppm with a loss of only two octane.136 Another advantage
an advanced process for desulfurising FCC gasoline streams of the OATS process is that it consumes less hydrogen because
called olefinic alkylation of thiophenic sulfur (OATS).131 This only a relatively low volume of the FCC gasoline stream is
process consists in the alkylation of thiophenic compounds via hydrotreated. Fortunately, under the conditions used, the
a reaction with the olefins present in the stream (Fig. 11). The alkylation of the S-containing compounds is much faster than
boiling temperature of the resulting S-containing alkylate such that of aromatics. One of the disadvantages of the OATS

Fig. 11 Schematic diagram of alkylation of thiophene with 1-olefins to obtain alkylthiophenes with much higher boiling points.

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process is that the alkylated sulfur compounds produced

require more severe hydrotreating conditions to eliminate
sulfur.

5.2 Desulfurisation by adsorption

The organosulfur compounds present in liquid fuels can be
removed by adsorption on a solid sorbent. Based on the
mechanism of S-compound interaction with the surface of
the sorbent, the adsorption can be physical or chemical:
physical adsorption is usually called adsorptive adsorption,
whereas chemical adsorption is called reactive adsorption
desulfurisation. Adsorptive desulfurisation is based on the
interaction of the organosulfur compounds on the solid sorbent
surface by weak (van der Waals) forces. Therefore, the
sorbent can be easily regenerated, usually by flushing the spent
sorbent with an inert gas, resulting in a high organosulfur
compound concentration flow. On the other hand, reactive Fig. 12 Structure of the C300 metal oxide framework (MOF) (left)
and extent of DBT adsorption at constant temperature (31 1C) for
adsorption desulfurisation occurs through the formation of
different MOF sorbents. Y-zeolite is also included for comparison
true chemical bonds of the S-containing compounds and the (right). 1 g sorbent per 100 g solution, initial S concentration 0.9908%
sorbent. Sulfur is fixed in the sorbent, usually as sulfide, and DBT (1724 ppm).
the S-free hydrocarbon is released into the purified fuel stream.
Regeneration of the spent sorbent is usually conducted in
the presence of air, which oxidizes the sulfide into SOx. The
efficiency of the desulfurisation is determined mainly by the
sorbent adsorption capacity, selectivity for organosulfur
compounds, durability and regenerability.

5.2.1 Adsorptive desulfurisation. Many studies have been

conducted to develop adsorbents for the desulfurisation of
transportation fuels using zeolites,123,137,138 mesoporous
materials139 and activated carbons.140–143 Salem and Hamid144
studied the removal of sulfur from naphtha with a 550 ppm
initial S-content in a batch reactor using activated carbon, Fig. 13 Simplified adsorptive desulfurization process flow.
zeolite 5A, and zeolite 13X as sorbents. Activated carbon
recorded the highest capacity, albeit a low level of sulfur of DBT adsorption is much higher on the MOF sample than
removal. Zeolite 13X was superior for sulfur removal from on the benchmarked Y-type zeolite.145
low sulfur streams at room temperature. According to these An adsorptive desulfurisation process called IRVAD was
results, a two-bed combination was proposed for industrial developed and targeted to remove a wide spectrum of organo-
application. The first bed contains activated carbon and sulfur compounds from various refinery streams including
removes up to 65% of the sulfur at 80 1C. The second bed is FCC gasoline.147 The process is based on moving bed techno-
loaded with zeolite 13X and provides almost 100% sulfur logy and uses a solid sorbent, which is counter-currently
recovery at room temperature if the sorbent/feed ratio is brought into contact with an S-rich hydrocarbon stream.
around 800 g L 1. The desulfurised hydrocarbon stream is produced at the top
It has recently been shown145,146 that metal–organic frame- of the adsorber, whereas the spent sorbent is withdrawn at the
works (MOFs) are excellent candidates for eliminating the bottom. The spent sorbent is circulated into the reactivation
refractory dibenzothiophene (DBT) and alkyldibenzo- reactor where organosulfur compounds and some adsorbed
thiophenes that are predominantly present in the feed after hydrocarbons are desorbed from the sorbent surface. The
hydrotreatment. Experimental results have shown that the regenerated sorbent is recirculated back to the adsorber
extent of DBT adsorption at temperatures close to ambient (Fig. 13). Alumina is used as the sorbent and operates up to
(31 1C) is about nine times higher on the Basolite C300 240 1C at low pressure with a hydrocarbon/sorbent weight
(Cu3(C9H3O6)2) MOF system than on the benchmarked ratio of around 1.4. Under these conditions, the efficiency of
Y-type zeolite and activated carbons. Experiments designed the IRVAD process has been proven in pilot plant experiments
for this comparison were conducted with DBT over a wide for FCC feedstock (1276 ppm S) and coker naphtha (2935 ppm),
concentration range (10–1700 ppmw of sulfur) and the providing at least a 90% reduction in sulfur content.148
temperature was kept constant and close to ambient (31 1C).
Under these conditions, the amounts of sulfur retained at 5.2.2 Reactive adsorption. In the reactive adsorption
equilibrium, expressed as g of sulfur per kg of sorbent, are desulfurisation process, the S-containing molecules present
shown in Fig. 12. From this figure, it is evident that the extent in the feed are converted to H2S and hydrocarbons, and the

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Fig. 14 Scheme for the reactive adsorption desulfurization.

Fig. 15 General process flow of extractive desulfurization.
H2S is subsequently retained by the sorbent.149–151 The general
pathway of S-removal by reactive adsorption is described by the appropriate solvent. As shown by the process flow (Fig. 15),
reaction shown in Fig. 14. Several combinations such as the oil and solvent are first mixed in a tank where the sulfur
Cu–ZnO, Ni–Al2O3, Ni–ZnO, Ni–SiO2, Ni–SBA-15 have been compounds are transferred from the oil phase into the solvent
used for this purpose, but the best performance has been due to their higher solubility in the solvent. The solvent–fuel
observed for the Ni–ZnO system. Nickel reacts first with the mixture is then fed into a separator in which the desulfurised
S-containing molecules under hydrogen to form NiS and then oil is separated from the solvent. The desulfurised hydro-
these sulfide ions are transferred to ZnO to form ZnS. In the carbon stream can then be used either as a component to be
course of the adsorption, the S-atom is removed from the blended into the final product or as a feed for further
molecule and retained by the sorbent on which it forms a transformations. The organosulfur compounds are separated
sulfide phase, whereas the hydrocarbon is returned to the final by distillation and the solvent is recycled. The most attractive
product without any structural changes. The spent sorbent is feature of extractive desulfurisation is its application at low
continuously withdrawn from the reactor and transferred to the temperature and low pressure. To make the process efficient,
regenerator section. In a separate regeneration vessel, the sulfur the solvent must be carefully selected to satisfy a number of
is burned off the sorbent and SO2 is sent to the sulfur plant. requirements. The organosulfur compounds must be highly
Conoco-Phillips Petroleum Co. developed a technology soluble in the solvent whose boiling temperature is quite
called S-Zorb for the deep desulfurisation of diesel by reactive different from that of the sulfur-containing compounds, and
adsorption.152 In this process, the diesel stream is contacted it must be inexpensive for process viability.
with the sorbent in a fluid bed reactor in the presence of It has been reported that the sulfur content of a hydrotreated
hydrogen. The sulfur-loaded sorbent is regenerated in a separate middle distillate can be reduced sevenfold (from 0.2% to
reactor and reused. Sulfur is typically reduced to about 5 ppm 0.029%) and the aromatics content threefold (from 27.1% to
from feedstocks containing 500 ppm sulfur. Feedstocks 8%) by extraction with solvents such as methanol, furfural
containing greater than 2000 ppm could also be deeply and ethylene glycol.153 Other solvents commonly used for sulfur
desulfurised to ultra low sulfur levels by this process. Depending extraction are acetonitrile, lactones like gamma butyrolactone,
upon the feedstock, the process operating conditions can vary DMF, N-containing solvents like amines and pyrrolidones, or
in the range: pressure = 20–35 bar; temperature about 350 1C. sulfur-containing solvents like DMSO and sulfolane.
For an optimized composition of the Ni/ZnO sorbent equal to As stated, the efficiency of extractive desulfurisation is
13 wt% Ni, it has been reported that fewer than 0.03 ppm of limited mainly by the solubility of the organosulfur compounds
sulfur were present in the effluent for one year for a kerosene in the solvent. Solubility can be enhanced by choosing an
feed containing 51 ppm of sulfur when working at a liquid appropriate solvent taking into account the nature of the
space hourly velocity (LSHV) of 0.27 h 1. sulfur compounds to be removed. This is usually achieved
The principal limitation of the reactive adsorption desulfuri- by preparing mixtures of two or more solvents. Preparation of
sation process is the rapid overloading of the sorbent in the such mixtures of solvents is a complex task and intrinsically
case of refinery streams with high S-content. High S-content non-efficient since its composition depends markedly on the
requires either a large amount of sorbent or a suitable process spectrum of the organosulfur compounds present in the feed
configuration based on fast kinetics of the deactivation– stream. Solubility can also be enhanced by transforming the
regeneration reactions. Both sorbent capacity and sorbent organosulfur compounds to increase their solubility in a polar
performance can be optimized by an appropriate composition solvent. One way to do this is by selectively oxidizing the
of the sorbent applied. For low S-containing streams (usually organic sulfur compound (thiophene, BTs, DBTs) to sulfones
involving the removal of the last ppm S) reactive adsorption possessing higher polarity.
requires the treatment of large volumes of sulfur diluted
reactant. This results in a high energy penalty due to the
5.3.1 Ionic liquids. Ionic liquids (ILs) have been suggested
pumping of the hydrocarbons through the reactor. To minimize
over the past years as candidates for the desulfurisation of
this effect, it seems appropriate to apply structured low-pressure
various motor fuels by extraction.154 ILs containing Cu(I) and
drop reactors (i.e. monolith reactors), and also to combine
Ag(I) ions were found to be particularly suited due to their
reactive adsorption desulfurisation with other processes that
tendency for forming p complexes with thiophene derivatives.
pre-concentrate sulfur.
An interesting example is the application of ILs obtained by
reacting 1-butyl-3-methylimidazolium chloride [BMIM][Cl]
5.3 S-removal by extraction
with anhydrous powdered CuCl, containing CuCl2–, u2Cl3–,
The concept of extractive desulfurisation means that organo- and Cu3Cl4– anions resistant to moisture and air, for the
sulfur compounds are more soluble than hydrocarbons in an desulfurisation of a model fuel.155 These systems revealed a

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high ability to desulfurise gasoline. For instance, the ionic along with easy regeneration and good reusability, are also
liquid BMIMCu2Cl3 extracted 23% of S-containing com- useful for industrial application.
pounds, whereas 1-ethyl-3-methylimidazolium tetrafluoro- In addition, a new approach for the desulfurization was
borate [BMIMBF4] extracted no more than 11%. Potent recently proposed using supported ionic liquid phase (SILP)
complex-forming agents dissolved in gasoline hinder the systems and a comparison of extraction was made between
extraction of sulfur compounds with IL. biphasic and SILP phase. These SILP systems were prepared
In a study on the ability of 1,3-dimethylimidazolium dimethyl by dispersing the ionic liquid as a thin film on highly
phosphate [MMIM][DMP], 1-ethyl-3-methylimidazolium diethyl porous silica, which exhibited a significantly higher extraction
phosphate [EMIM][DEP] and 1-butyl-3-methylimidazolium performance owing to their large surface area, reducing the
dibutyl phosphate [BMIM][DBP] to extract sulfur from diesel sulfur content to less than 100 ppm in one stage. Multistage
fuel over a wide range of sulfur concentrations, it was revealed extraction with this SILP technology offers very efficient
that the solubility of DBT and BT in aqueous solutions of utilization of ionic liquids and circumvents mass transfer
ILs at 25 1 varies in the following order: [BMIM][DBP] 4 limitations. However, leaching of the small quantity of ionic
[EMIM][DEP] 4 [MMIM][DMP].156 The most suitable IL for liquid from the support should be avoided and hence clever
the desulfurisation of diesel fuel was found to be [EMIM][DEP], engineering of the ionic liquid loading and solid support is
which is fairly highly reactive toward sulfur, poorly soluble in required.163
fuel, and affects only slightly other properties of the fuel. The One of the principal challenges nowadays to be addressed
ILs synthesized from organic acids (formic, acetic, and benzoic) before ILs can be used routinely is cost. In general, ILs are
and N-containing bases (aniline, piperidine, and diethylamine) more expensive in comparison to common organic solvents.
seem quite interesting.154 After the threefold extraction of However, because ionic liquids can be recycled and their
catalytic cracking gasoline with the aforementioned ILs, the cost is decreasing drastically along the last few years, a
sulfur content of the latter decreased from 240 to 30 ppm, and wider application is expected for the removal of refractory
the content of aromatic hydrocarbons, from 26 to 14%. Ionic S-containing compounds present in transportation fuels.
liquids can be regenerated by treating the extract with
an excess of low-boiling paraffins and repeatedly used for 5.4 Oxydesulfurisation (ODS)
desulfurisation. A high efficiency of ILs in the desulfurisation
Oxidative desulfurisation (ODS) is a relatively new technology
of diesel fuel was proven by the example of ILs containing
for the deep desulfurisation of light oil. This desulfurisation
1-butyl-3-methylimidazolium as cation and tetrafluoroborate,
process includes two stages: (i) oxidation in a first step; and (ii)
hexafluorophosphate, octyl sulfate, ethyl sulfate, and dimethyl
liquid extraction at the end. It is evident that the greatest
phosphate.126 The suggested scheme involving the steps of
advantages of the ODS process are low reaction tempera-
extraction and regeneration of ILs reduced the sulfur content
ture and pressure, and that expensive hydrogen is not used in
of diesel fuel from 500 to 10 ppm.
the process. Another feature of ODS is that the refractory
In the absence of oxidants, the ILs themselves fail to provide
S-containing compounds in ODS are easily converted by oxida-
a high degree of sulfur removal.154,157,158 For example, the
tion. Therefore, ODS has great potential as a complementary
ionic liquid [HMIm]BF4 removes only 6% of the sulfur, but in
process to traditional HDS for producing deeply desulfurised
the presence of hydrogen peroxide it recorded a sulfur removal
light oil.
of 65, 70, and 93% at 70, 80, and 90 1C, respectively.157
However, a very high H2O2/S ratio is necessary to reach these
sulfur removal levels. This drawback can be avoided by using 5.4.1 Description of ODS processes. S-containing com-
catalysts: the tungsten and molybdenum peroxo complexes,159 pounds present in fuels are oxidized in the liquid phase by
Fenton-like catalyst160 or phosphotungstic acid161 can remove an appropriate oxidant to form compounds that can be easily
the bulk of sulfur with a low hydrogen peroxide sulfur extracted from oil due to their increased relative polarity. The
ratio. This finding provides evidence in favour of combining oxidant reagents used for this purpose include peroxy organic
catalytic oxidation and extraction. acids, hydroperoxides, nitrogen oxides, peroxy salts and ozone,
In a recent study, the extractive desulfurisation performance among others. These oxidants donate O-atoms to the
of low viscosity ILs based on the dicyanamide ([N(CN)2] ) S-containing molecules to form sulfoxides or sulfones (Fig. 16).
anion was reported.162 Interestingly, these systems present The oxidation reaction is carried out by contacting the oxidant
much shorter extraction equilibrium times than other with the oil for a time until the oxidized S-containing
previously reported ILs, that is, less than 5 min for all the compounds are formed. The reaction is then stopped before
ILs at room temperature, which is important for generating a the oxidant attacks other, less reactive, oil components. The
high production yield at industrial scale. Compared with cyclic oxidant can then be regenerated for re-use. Washing, extrac-
thiophenium [S2][N(CN)2] and tetrahedral trialkylsulfonium tion and chemical post-treatment will remove any unused
[EtMe2S][N(CN)2], the aromatic imidazoliums [BMI][N(CN)2] oxidant that remains in the light oil (Fig. 17). The oxidized
and [EMI][N(CN)2] were more efficient. For [BMI][N(CN)2], compounds are extracted from the oil by contacting oxidized
the S-removals from gasoline and diesel fuel were 48.5 oil with a non-miscible solvent that is selective for the relatively
and 68.7%, respectively, in a single extraction at 25 1C, polar-oxidized S-containing compounds. The oxidized com-
IL : oil = 1 : 1 (w/w), 5 min; negligible S-content could be pounds and solvent are separated from the oil by decantation,
obtained after 3–5 extraction cycles. The insensitivity of the whereas the solvent is separated from the mixture of solvent
extraction efficiency to temperature and initial S-content, and oxidized compounds by a simple distillation for recycling.

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both S- and N-containing compounds from oil fractions.164

Later, in 1988, a process was described for purifying hydro-
carbon aqueous oils containing both S- and N-containing
compounds, 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).165 The oxidized products consist of a liquid phase and a
by-product that is a semisolid-like residue with high S-content.
However, interest has substantially increased in the early
2000s, in parallel with more restrictive limitations on sulfur
concentration in fuels, and the need to remove refractory
organosulfur compounds.

Organic hydroperoxides
Organic hydroperoxides, and most specifically tert-butyl
hydroperoxide (TBHP) have been widely employed for
sulfur removal from oil fractions. An ODS process based on
Fig. 16 Simplified scheme showing the oxidation of DBT. The oxidant this oxidant was first patented by EniChem/UOP166,167 and
donates O-atoms to the DBT molecule present in the organic phase to then by Lyondell Chemicals.168,169 EniChem/UOP removes
form first sulfoxide and then sulfones (these oxidized compounds sulfones by adsorption, whereas the Lyondell process uses
accumulate mainly in the polar phase). extraction for sulfone separation. The major drawbacks of
TBHP oxidant are: (i) the high cost of tert-butyl hydro-
peroxide, and the waste treatment of the tert-butyl alcohol
by-product generated, as well as sulfone waste treatment, and
(ii) the low amount of active oxygen by mass unit (17–10%),
for this reason the transportation of this compound is very
expensive, and it is therefore recommendable to install a
hydrocarbon oxidation unit on-site to produce hydroperoxides,
with an ensuing increase in capital costs. The oxidation of
sulfur compounds with organic hydroperoxides takes place in
the presence of catalysts. The active centre 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), among which molybdenum
catalysts remain prominent.170–175 However, molybdenum
tends to be leached to the reaction medium, where the catalyst
Fig. 17 Schematic biphasic simultaneous oxidation/extraction ODS is not very stable and the main part of the catalytic activity is
reaction of DBT. due to solubilized molybdenum. Other much more stable
catalysts, such as Co/Mn,171 Ti–silica169 and Ti-MCM-41176
catalysts, have been proposed. The best results have been
More details about the process can be found in our recent
obtained with Ti-based systems, as their silylation improves
review.112
catalyst activity and life.176
The second step of this process involves removing the oxidized
compounds by contacting the oil with a selective extraction
Organic peracids
solvent. A simple L–L extraction technique using water-soluble
polar solvents (i.e. acetonitrile, DMF and DMSO) is usually Peracids are powerful oxidizing agents, and can oxidize
employed. Acetonitrile is particularly suited mainly because it sulfur compounds. These compounds are highly reactive and
has a relatively low boiling point (82 1C) and is easily separated corrosive, and hence they are produced in situ by reacting
from the sulfones by distillation. When acetonitrile is contacted hydrogen peroxide with a carboxylic acid, usually formic acid
with light oil, a large quantity of aromatics is extracted simul- or acetic acid. The peracids are powerful oxidizing agents, and
taneously with the sulfones. The addition of water, however, are able to oxidize sulfur compounds. These compounds are
suppresses the extraction of the sulfones. The solvents should highly reactive and corrosive, for this reason they are
therefore be sufficiently polar to be selective for polar com- produced in situ by reaction of hydrogen peroxide and a
pounds in the process of extraction. Methanol, for instance, has carboxylic acid, usually formic acid or acetic acid. The first
sufficient polarity, but its density, 0.79 g cm 3, is about the same studies have been based on the direct use of peracids in the
as that of standard light oil, making separation very difficult. oxidation of sulfur compounds.177–179 However, the amount
Other properties to be considered include boiling point, freezing of oxidizing agent used is very high in comparison to the sulfur
point, and surface tension. removed. For this reason, it was imperative to incorporate
The first ODS process was proposed in 1974 by using NO2 catalysts capable of oxidising the sulfur compound more
as oxidant followed by extraction with methanol to remove efficiently. The most common option is the use of transition

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Electronic Supplementary Material (ESI) for Catalysis Science & Technology
This journal is © The Royal Society of Chemistry 2011

metal salts, and specifically tungsten salts180 which are very

active and selective in the oxidation of sulfur compounds
with peracids. Modified active carbons are also catalysts for
this reaction.181,182 In the presence of active carbon with
carboxylic groups, more sulfur is removed (495%) from the
fuel than in their absence (60%).181 A second option is the use
of transition metal salts that can form radicals from peracids
(R–COOO), like Co183 or Fe.184 These radicals are very
reactive and with a high oxidation capacity. The peracids
of short carboxylic acids used in these reactions are highly
polar and form two immiscible liquid phases in the reactor, so
there are diffusional limitations between the fuel and polar
phase with the oxidizing agent. Accordingly, studies have been
Fig. 18 Biphasic oxidation reaction catalyzed by metallic peroxides.
conducted on the use of the phase transfer compound.
The presence of the phase transfer compound facilitates the
transfer of products and reagents at the polar–apolar interface, remain, which make this reaction slow for industrial applica-
substantially increasing the mass transfer along the interface.185 tion. Some interesting approaches have been studied, such as
the use of microemulsions196 and microstructured reactors.197
In both cases the distances between bulk and interface are
Hydrogen peroxide massively reduced, and diffusional limitations are therefore
Hydrogen peroxide is the best candidate as oxidizing agent minimized, if not avoided.
because it presents a high amount of active oxygen by mass The ideal catalytic systems belong to the class of hetero-
unit (47%); it is a commercial product often used at industrial geneous catalysts. Consequently, efforts are being devoted to
level; and its by-product is only water.186 A catalyst is required the development of processes using highly robust and recyclable
to ensure hydrogen peroxide efficiently oxidizes the sulfur catalysts that provide higher atom use and minimized
compounds. The first reports on ODS with hydrogen peroxide pollution levels using greener ingredients. In recent years, the
are related to the use of photosensitizers,187,188 these selective oxidation of S-containing compounds by H2O2 has
compounds are first excited under light radiation and then been carried out using a large number of redox solid catalysts
activate the sulfur compound, and these excited compounds such as Ti,107,198–203 V,204–206 W,207–210 Mo,106,210 Co/Mn,211
are oxidized by the hydrogen peroxide, with benzophenone Ag,212 Au,213 Re.214
being especially effective.188 Under these conditions, the
desulfurisation of commercial light oil was also achieved and 5.4.2 Challenges for ODS. ODS has a proven ability to
the sulfur content was reduced from 0.2 to 0.05 wt% by 48 h of remove sulfur compounds from fuels to meet strict regulation
photoirradiation. This long reaction time renders this process limits. Among different chemical oxidants the best option is
unattractive for industrial application. hydrogen peroxide; with this oxidant, the oxidation/extraction
The second group of catalysts is based on transition metal is simultaneous and can reach very high levels of sulfur
salts in a high oxidation state with Lewis acidity.188–191 These removal. However, in order to make an ODS process competitive
systems allow the oxidation of DBT in short reaction time,192 with deep HDS a three-step process is needed: (i) improve
however the complete oxidation of substituted DBT is slower, catalytic-specific activity at low H2O2/S ratios; (ii) increase the
and then long residence times are necessary for use in refinery mass transfer in a biphasic system containing the oil fraction
schemes. The main problem lies in the presence of two reaction and polar phase; and (iii) enhance the post-treatment of the
phases—an oil phase with the sulfur compound and a polar sulfones produced.
phase that contains the oxidant agent (H2O2), which is not
soluble in the oil phase. To avoid this difficulty, phase transfer
Improvement of catalytic activity at low H2O2/S ratios
catalysis has been proposed.110,111,193–195 The presence of the
phase transfer agent facilitates the transfer of products and Many catalytic systems are very active in the oxidation of
reagents at the polar–apolar interface, significantly increasing sulfur compounds. However, only some catalysts can oxidize
the mass transfer along the interface. Such a biphasic oxida- in short reaction times (o15 min) operating with a hydrogen
tion reaction follows the cycle illustrated in Fig. 18. In the peroxide sulfur molar ratio close to the stoichiometric one
polar phase, the catalyst precursor is rapidly oxidized by (H2O2/S = 2). A competitive commercial process requires
H2O2. The resulting peroxo-compound is transferred to the working with an amount of oxidant that is as small as possible.
apolar phase by H+–Q+ ion exchange with the phase transfer Liquid fuels are very complex mixtures containing alkenes
agent (Q+). The peroxo-compound in the apolar phase oxi- and aromatics, and these compounds can be also oxidized
dizes thioethers into sulfones, which can then be regenerated at consuming part of the oxidant and degrading the quality of the
the L–L interface with H2O2 or transferred to the polar phase fuel. These unwanted oxidation reactions are evident at
where it reacts with hydrogen peroxide. The sulfones obtained temperatures about 80–90 1C for this short reaction time
are then transferred to the polar phase due to the solubility of (o15 min). For this reason, the reaction has to be conducted
sulfones in a polar solution, with the subsequent production of at temperatures lower than 80 1C and with a short reaction
a sulfur-free polar phase. Mass transfer limitations still time for real fuels.

36 Catal. Sci. Technol., 2011, 1, 23–42 This journal is c The Royal Society of Chemistry 2011
Electronic Supplementary Material (ESI) for Catalysis Science & Technology
This journal is © The Royal Society of Chemistry 2011

Another important area for improvement is the relative sulfur concentration and the amount of sulfur removed;
reactivity with different sulfur compounds. The relative for instance, 1000 ppm of S removed implies a decrease of
oxidation reactivity of small peracids (formic or acetic) is around 5–6% in fuel mass. It is therefore highly expedient to
4,6-DMDBT 4 4-MDBT 4 DBT97,207 which is the opposite recover, at least in part, the hydrocarbon in the oxidized sulfur
to HDS and makes a very good complement to HDS. When a compounds.
catalyst is used, irrespectively if it is homogeneous or hetero- The first option when treating these sulfones is to eliminate
geneous, the relative oxidation reactivity is different: DBT 4 the sulfur and produce an S-free fuel. The oxidised sulfur-
4-MDBT 4 4,6-DMDBT 4 BT.105,110,203,210 The relative containing hydrocarbon is contacted with a metal to form a
reactivities of DBT and substituted DBT compounds appear metal–sulfur containing compound. This process therefore
to be related to the steric hindrance of the ethyl and methyl relies on the adsorption of oxidised sulfur compounds from
groups at positions 4 and 6 in the DBT molecule, hindering the the hydrocarbon using a metal capable of forming a metal
formation of reaction intermediates prior to oxidisation, sulfide. The metal is selected from the group consisting of Ni,
whereas it is more difficult to oxidize in terms of S–C bond Mo, Co, W, Fe, Zn, V, Cu, Mn, Hg, and mixtures thereof.
stabilization in the BT molecule.105,110,215 Consequently, the This process is different from conventional hydrodesulfurisa-
activity in the oxidation of substituted DBT compounds must tion in that the sulfur is immobilized in the form of a metallic
be improved because these compounds are present in the sulfur compound (e.g. a metal sulfide) rather than converted to
treated diesel stream, making it difficult to comply with very hydrogen sulfide. For this reason, the addition of free
restrictive environmental regulations. molecular hydrogen, as required in hydrodesulfurisation, is
overcome. The second option is the catalytic decomposition
Increasing mass transfer in the reactor on solid acids like zeolites or silica–alumina, or basic catalysts
like MgO or hydrotalcite.221,222 This catalytic conversion
The reaction is conducted in the presence of two liquid
takes place under relatively mild conditions, without the use
reaction phases: an oil phase with the sulfur compound and
of a hydrogen atmosphere. However, these processes need to
a polar phase that contains the oxidant agent (H2O2), which is
be improved.
not soluble in the oil phase. Consequently, the overall sulfur
removal rate is limited by the mass transfer between phases
with very active catalysts. For this reason, an increase in mass 6. Biodesulfurisation (BDS)
transfer clearly improves the overall sulfur removal rate. Some
One of the alternative options for removing sulfur from fossil
attempts have been made using microemulsions216,217 and
fuel is by biological methods. Sulfur atoms form 0.5–1% of the
microstructured reactors.218 Microemulsions are interesting
dry weight of bacterial cells. Microorganisms require sulfur for
from a conceptual point of view but need intense development
their growth and biological activities. Sulfur generally occurs
if they are to be applied in a refinery process. A very interesting
in the structure of some enzyme cofactors (such as Coenzyme
concept is the use of microstructured reactors. Chemical
A, thiamine and biotin), amino acids and proteins (cysteine,
microstructured reactors (MSR) are devices containing open
methionine, and disulfur bonds).223 Energy BioSystems
paths for fluid flow with dimensions in the sub-millimetre
Corporation (EBC) was initially the only commercial venture
range. Most MSR are designed as multiple parallel channels
dedicated to the development of biodesulfurisation techno-
with diameters between ten and several hundred micrometres
logy. EBC’s concept for a biodesulfurisation process was to
where the chemical transformation occurs.219 This gives a high
treat diesel, but also to produce a value-added surfactant
specific surface area in the range of 10 000 to 50 000 m2 m 3 219,220
by-product to achieve a more economical process.113,115 A number
and allows an effective mass and heat transfer when compared
of reviews have recently been published in this field,115,224 so we
to more traditional chemical reactors of E100 m2 m 3. These
will focus on a general description of the process and on some
reactor systems improve mass transfer (100 times).
improvements necessary for developing a BDS process.
Process-engineering research should focus on decreasing the
Depending on their enzymes and metabolic pathways,
volumetric reaction rate (polar solvent/oil ratio). The solvent/
microorganisms may have the ability to obtain the sulfur they
oil volume ratio is among the most important technical
need from different sources. Some microorganisms consume
bottlenecks in the development of ODS processes, and in order
the sulfur in thiophenic compounds such as DBT and reduce
to reduce the operational costs associated with the handling,
the sulfur content in fuel. In terms of DBT utilization,
separation and disposal of water, the volume ratios of solvent/
two main pathways have been reported: ring-destructive
oil should ideally be minimized.
(degradation) and sulfur-specific (desulfurisation) pathways.
To date, two ring-destructive pathways for DBT metabolism
Enhancing the post-treatment of sulfones
have been recognized.
The concentrations of sulfur compounds are very low, but the A very attractive, green option is to utilize microorganisms
refinery stream to be treated is huge, so a large amount of to do the oxidation chemistry of sulfur species as illustrated in
sulfones is produced. Some sulfones can be used as a chemical Fig. 19. The reaction takes place in the presence of water and
intermediate but in a real fuel the variety of sulfur compounds oxygen under ambient conditions, i.e., ambient temperature
is very high, and therefore the number of different sulfones is and pressure. Bacteria converting dibenzothiophene and alkyl
also high and very difficult to separate. For this reason, an sulfides are relatively well known while fewer bacteria are
adequate post-treatment of sulfones is very important. The found for benzothiophene, and only a few bacteria detected for
amount of fuel lost in the ODS process depends on the initial thiophene.223 In general, many reports of bio-desulfurization

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Electronic Supplementary Material (ESI) for Catalysis Science & Technology
This journal is © The Royal Society of Chemistry 2011

regulations for low sulfur fuels go into effect with the objective
to be competitive with emerging non-biological approaches.

6.1 Destructive biodesulfurisation

The most common pathway for DBT degradation, known as the
‘Kodama pathway’ (Fig. 20), is analogous to that of naphthalene
degradation.228 In this pathway, initial dioxygenation is
carried out at the peripheral aromatic ring of DBT, followed
by cleavage of the ring. This process leads to the accumulation
of 3-hydroxy-2-formylbenzothiophene as a water-soluble end
product, with lower carbon content than DBT. No desulfuri-
sation of the organosulfur substrate occurs in this path-
way. Denome et al.229 cloned and sequenced a 9.8 kb DNA
fragment from Pseudomonas strain C18 that encoded
DBT-degrading enzymes. Nine ORFs were identified and
designated doxABDEFGHIJ; collectively, these genes were
referred to as the DOX (DBT oxidation) pathway. The results
indicated that a single genetic pathway controls the meta-
bolism of DBT, naphthalene and phenanthrene in strain C18.
Another ring-destructive pathway that results in mineraliza-
tion of DBT is the one proposed by van Afferden et al.230
They isolated Brevibacterium sp. DO, capable of using DBT
for growth as the sole source of carbon, sulfur and energy.
During DBT mineralization three metabolites were identified:
DBT sulfoxide (DBTO), DBT sulfone (DBTO2) and benzoate.
Fig. 19 The pathway of biological desulfurization of DBT relies on
biocatalysts for specificity. NADH is reduced nicotinamide adenosine
dinucleotide; FMN is flavin mononucleotide; DSZA, DSZB, DSZC
and DSZD are the catalytic gene products of dszA, dszB, dszC and
dszD, respectively.

do not show very deep desulfurization, down to 50–200 ppm

sulfur at best. The reason for this lies in the fact that higher
bacterial activity occurs in the higher concentration range.
Therefore the potential of biodesulfurization for achieving the
10 ppm S level might be not so great. In addition, another
important aspect to be considered in the bio-system is the
competitive reactions caused by other bacteria. A successful
H2S biological process like the one from ThioPaque224 has the
great advantage that only target type bacteria seem to survive
in a very noxious environment of H2S, oxidizing H2S to
elemental sulfur efficiently. In that respect, crude and diesel
desulfurization would need an additional effort to promote the
working of target bacteria. Occasionally, reports appear on
development of new bacteria for oil desulfurization.225,226
Microbial sulfur-specific transformations have been shown
to selectively desulfurize organic S-containing molecules.227
Discoveries related to biodesulfurization mechanisms may
lead to commercial application of biodesulfurization through
engineering recombinant strains for over-expression of bio-
desulfurization genes and combining relevant industrial and
environmental traits with improvement in bioprocess design.226
Key improvements lie in the enhancement of biocatalyst
stability, faster kinetics, minimization of mass transfer limita-
tions, and temperature and solvent tolerance. Once these
advances can be achieved biocatalysis may be a cost-effective
approach to obtain low sulfur gasoline. Indeed, the challenge
shall be to reach such improvements by the time the Fig. 20 Kodama pathway of DBT degradation.

38 Catal. Sci. Technol., 2011, 1, 23–42 This journal is c The Royal Society of Chemistry 2011
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This journal is © The Royal Society of Chemistry 2011

This pathway resulted in the complete mineralization of DBT, improvements in other diesel properties such as higher cetane
with the release of the sulfur atom as sulfite stoichiometrically, number, lower aromatics content, density reduction, etc. The
which then oxidized to sulfate. There are no detailed studies of production of such high quality ULSD from low quality feeds
the enzymology or molecular biology of DBT degradation by is a tough challenge, but the economic incentive is high.
this strain. This ring-destructive pathway may be valuable in Deep S-removal means high hydrogen consumption, which
biodegradation of DBT in the environment. is a serious problem affecting the process economics in ULSD
The above ring-destructive pathways are not commercially production. The use of non-hydrogenation processes such as
useful for the petroleum industry, because use of the carbon ODS will also gain increasing importance for ULSD production
skeleton of S-containing compounds by the bacteria reduces in the future. The refractory sulfur species (e.g. 4,6-DMDBT)
the fuel’s calorific value. are preferentially attacked and desulfurised in the ODS
process. Because of the mild process conditions with no
hydrogen requirement, the capital and operating costs of the
7. Concluding remarks
ODS process will be substantially lower, and it could be used
Concerns for cleaner air and increasingly more stringent in combination with existing conventional hydrotreaters for
regulations on sulfur contents in transportation fuels will desulfurising moderately hydrotreated low sulfur diesel.
make desulfurisation more and more important. The sulfur We must begin to contemplate the use of zero-sulfur transpor-
problem is becoming more serious in general, particularly for tation fuels in the near future. One particular case, which
diesel fuels, as the regulated sulfur content is recording a lower presents a major challenge for the ultra-deep desulfurisation of
order of magnitude, while the sulfur contents of crude oils liquid hydrocarbon fuels, is a fuel processor for proton-exchange
refined in the US are becoming higher. The chemistry of diesel membrane fuel cells, which basically require zero-sulfur hydrogen
fuel processing has evolved significantly around the central streams generated by reforming liquid hydrocarbon fuels.
issue of how to produce cleaner diesel fuels in a more efficient
and eco-friendly manner. New design approaches are required
for producing affordable ultra-clean diesel and gasoline. Acknowledgements
Research on the deep desulfurisation of diesel fuel to ultra We are grateful to many of our colleagues for stimulating
low sulfur levels has recently gained considerable importance, discussions on diesel fuel desulfurization and hydrogenation.
and over the past seven years a growing number of articles We would like to acknowledge the MICINN sponsor under
have been published in the scientific literature concerning research grants ENE2007-07345-C03-01/ALT, ENE2010-21198-
various aspects of ULSD production by academic research C04-01 and CTQ2010-19157-C03-01.
institutions and industrial research laboratories. The renewed
interest in ULSD research is driven by the need to have a
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