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Selective adsorption for removing sulfur: a potential ultra-deep
desulfurization approach of jet fuels
Yuesong Shen,ab Peiwen Li,*b Xinhai Xub and Hong Liub
Received 21st October 2011, Accepted 24th October 2011
DOI: 10.1039/c1ra00944c
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Jet fuels are strategic fuels widely used in airplanes. Through appropriate reforming and shifting
processing, jet fuels can be converted into syngas, which is a suitable fuel to solid oxide fuel cells for
many auxiliary and backup power units. Integrated micro fuel processors in combination with solid
oxide fuel cell (SOFC) stacks using jet fuels have been viewed as attractive portable power sources.
Because the sulfur in jet fuels easily causes catalyst poisoning for fuel processing reactions and the
electrochemical reactions in fuel cells, ultra-deep sulfur removal in jet fuels and many other
hydrocarbon fuels has become a very important and active research subject worldwide in the last
15 years. Amongst the state-of-the-art technologies, selective adsorption for removing sulfur (SARS)
is emerged to be very attractive. SARS has been regarded as the most promising approach because it
obtains ultra-deep desulfurization efficiency at ambient temperature and atmospheric pressure
without hydrogen consumption. In this paper, we survey the current status and prospect of the SARS
technology for jet fuels, and will discuss some important issues remaining for the SARS technology in
the future. The final goal of this survey is to find/innovate a promising method for jet fuel
desulfurization, which is most suitable for supplying fuels to solid oxide fuel cell auxiliary and backup
power units.

1. Introduction
a
College of Materials Science and Engineering, State Key Laboratory of High energy efficiency and energy density, together with rapid
Materials-Oriented Chemical Engineering, Nanjing University of refueling capability, renders fuel cells highly attractive for
Technology, Nanjing, 210009, PR China. E-mail: [email protected] portable power generation.1–2 Of the various types of fuel cells,
b
Department of Aerospace and Mechanical Engineering, The University of
Arizona, Tucson, AZ, 85721-0119, USA. solid-oxide fuel cells (SOFCs) are energy convertors with a high
E-mail: [email protected] energy efficiency, low use of noble metal catalyst, and low

Yuesong Shen received his PhD Peiwen Li earned his Ph.D. (1995)
degree at Nanjing University of degree in energy and power engi-
Technology in 2010. He is an neering area from Xi’an Jiaotong
assistant professor at Nanjing University, China. He is currently
University of Technology since an assistant professor in the
2010 to present. He is currently Department of Aerospace and
a postdoctoral research associ- Mechanical Engineering at the
ate at The University of University of Arizona, USA. He
Arizona, USA. His research is interested in heat transfer
interests include catalytic mate- enhancement in industrial pro-
rials for environmental protec- cesses, turbulence drag reduction,
tion, catalytic materials for new gas turbine cooling technologies,
Yuesong Shen the multi-physics transport phe-
energy conversion, flue gas deni-
trification and ceramic-based nomena in fuel cells and electro-
structural and functional materials. He won the National Natural Peiwen Li lysis cells, and concentrated solar
Science Foundation of China in 2011. thermal power systems. Professor
Li is an active member of the American Society of Mechanical
Engineers. He is also a reviewer of papers for more than 10 technical

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environmental impact.3–4 SOFCs enable direct use of higher considered to be more promising as they react at ambient
hydrocarbons,5–7 but have not been seriously considered for temperatures under atmospheric pressure without hydrogen
portable applications because of the thermal management consumption. However, expensive peroxides20,24 and regenerated
difficulties at small scales, and slow start-up and poor thermal catalysts, phase-transfer agents, and adsorbents are issues have
cyclability.1 Essentially, SOFCs can take hydrogen-enriched to be addressed for scaling up purposes in the UOAD process.25
synthesis gas (syngas) as an efficient ultra-clean fuel, which can Song and coworkers10,23,26–28 in Pennsylvania State University
be effectively converted from jet fuels. Therefore, jet fuels are have been exploring the new PSU-SARS process for deep
particularly attractive as logistic fuels for some portable power desulfurization by using different solid adsorbents. In compar-
applications based on SOFCs.8 As a consequence, reformers ison with the HDS process, the PSU-SARS in jet fuels have some
such as steam reformers, catalytic partial oxidation (CPO) significant advantages:18 (a) selective adsorption is able to
reformers, and autothermal reformers (ATR) 9–13 are typically remove sulfur in jet fuels to the level for a portable fuel cell
employed in the reforming systems to convert jet fuels to system; (b) the process is usually conducted at ambient
hydrogen-enriched syngases.14 An integrated micro fuel proces- temperature and atmospheric pressure, resulting in more energy
sor in combination with a SOFC stack using jet fuels has been efficiency and cost efficiency; (c) most of these processes don’t
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viewed as an attractive portable power source as an alternative to need to use hydrogen gas, which is the most costly item in HDS;
the package of conventional batteries needed for portable (d) the SARS process provides a clean fuel that meets the new
electronic operations for several days.8 However, jet fuels usually emission control standards with minimum harm to catalytic
contain various organic sulfur compounds with total sulfur converters. However, the challenge to the approach is to attract
content ranging from 300 to 3000 parts per million by weight and selectively adsorb sulfur compounds onto the surface of the
(ppmw); sulfur in the fuel can poison the fuel processing catalysts solid adsorbent but leave the aromatic and olefinic hydrocarbons
such as reforming and water-shift catalysts. Even trace of sulfur as well as the open-chain and cyclic paraffinic hydrocarbons
in the processed fuel can poison the anode catalysts in fuel cells. untouched.23 Thus, a key point in developing a successful SARS
Hence, sulfur must be reduced to below 1 ppm for most fuel cells, process is to develop an adsorbent that has high sulfur-
perhaps even below 60 ppb for proton exchange membrane fuel adsorption capacity and high selectivity for sulfur compounds,
cells.8,15–18 Additionally, to reduce sulfur pollution, stringent and is facile to be generated.
emission regulations, rigorous emission control standards are In this paper we focus our attention on the present status and
being imposed or raised on hydrocarbon fuels. Therefore, ultra- prospect of SARS of jet fuels for application in SOFCs. In the
deep desulfurization of jet fuels without environmental impact following, after a brief description of the SARS chemistry and
has been a very important challenge for syngas production in physical process, the current research progress of SARS
application of SOFCs. adsorbents is reviewed. The mechanism of the SARS reactions
Current desulfurization technologies mainly include hydro- is then summarized. Finally the improvement of absorbents and
desulfurization (HDS), oxidative desulfurization (ODS), extrac- future prospect of the SARS process are discussed based on our
tive desulfurization, catalytic cracking desulfurization, study.
biodesulfurization, adsorptive desulfurization (physical adsorp-
tion desulfurization, activated adsorption desulfurization), ultra-
2. The chemistry and physical process of SARS
sound-assisted oxidative desulfurization (UAOD), selective
adsorption for removing sulfur (SARS), etc.17–20 Targeting for SARS is a new approach for ultradeep desulfurization by
providing fuels (H2 and CO) in solid oxide fuel cells for auxiliary selective adsorption for removing sulfur using adsorbents at
power units, the jet fuel desulfurization technology of particular ambient temperatures and atmospheric pressure without using
interest in this study must be simple and convenient, possess no hydrogen.23 The chemistry of SARS process is illustrated in
separation process. It also must be able to obtain sufficient Fig. 1 and 2. Adsorbents are usually comprised of transition
ultradeep desulfurization efficiency at room temperature and metals supported on base oxides. Ni/ZnO and Ni/Al2O3–SiO2
atmospheric pressure without hydrogen consumption. are prototypical formulations most often in literature and
At present, HDS is a conventional approach that is being patents.19,29-31 As shown in Fig. 1 and 2, Ni functions as
employed by the refineries to produce low-sulfur gasoline and adsorptive desulfurization sites.
diesel in order to meet environmental regulations.17–19 However, Pretreatment of the Ni-based adsorbents with H2 gas:
the current HDS technology is not applicable for reducing sulfur
content in logistic fuels to a level for a portable fuel cell NiO + H2 A Ni + H2O (1)
application. On the other hand, the HDS process needs to work
at higher temperature and higher pressure using hydrogen gas, Selective adsorption for removing sulfur from thiophene
which is not suitable for the on-board or on-site desulfurization (C4H4S) and 1-benzothiophene (C8H6S):
for fuel cell applications. Therefore, some alternative non-
hydrodesulfurization techniques such as ODS, extractive desul- Ni + C4H4S A NiSsurf + C4H6 (2)
furization, catalytic cracking desulfurization, biodesulfurization,
adsorptive desulfurization and son on, are being explored in
recent years to produce ultra-low-sulfur fuels. Amongst various
alternative desulfurization approaches regarding ultra-deep
adsorption capacity of sulfur, selectivity for sulfur compounds,
and working temperatures, the UAOD21–22 and SARS23 are Fig. 1 Schematic illustration of SARS of thiophene with Ni/ZnO.19,29–31

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activated carbons, and ionic liquids are being evaluated for the
SARS processes under ambient conditions. In this section, we
summarized the developments of the above-mentioned adsor-
bents.
Fig. 2 Schematic illustration of SARS of 1-benzothiophene with Ni/
Al2O3–SiO2 (Adapted from Ref. 19). 3.1 Zeolites-based adsorbents

Ni + C8H6S A NiSsurf + C8H8 (3) Zeolites have attracted much attention for desulfurization of
liquid fuels due to their big surface area, polarity, surface acidity
Fig. 3 shows the technological process of SARS. Selective and basicity, and size-selective adsorption property. Especially
adsorptive desulfurization is performed on a fixed-bed flow the Y zeolites are the most interesting and attractive. Yang and
apparatus. The adsorbent with different particle sizes is packed coworkers32–35 have prepared a serial of ions (containing Cu+,
in custom-made stainless steel columns with different lengths and Ag+, Ni2+, Zn2+ and Na+) exchanged zeolites for selective
diameters. The packed columns are placed in a multichannel adsorption desulfurization of diesel, gasoline, and jet fuels. They
found the p-complexation-based sorbents desulfurization per-
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convection oven. The temperature of the oven is measured with a

digital temperature display. To ensure that the adsorbents such formance decrease as follows: Cu+Y . Ag+Y . Ni2+Y . Zn2+Y
as supported reduced metals are in the reduced form, the . Na+Y. While Bhandari et al.36 obtained the zeolites
adsorbent bed must be pretreated with reducing atmosphere at desulfurization performance decrease as follows: Ni2+Y .
a designed rising temperature. For an example of reducing Cu+Y . Fe2+Y . Zn2+Y . Na+Y. Xue et al.37 reported the
schedule, the Ni-based adsorbent was pretreated with H2 gas at a zeolites desulfurization performance decrease as follows: Ce4+Y
flow rate of 50–60 ml min21 at ambient pressure, heated slowly . Ag+Y . Cu+Y . Na+Y. Zhang et al.38 observed the other
(2 uC min21) up to 230 uC, and kept at this temperature for zeolites-based adsorbents desulfurization performance decrease
about 1 h in H2 flow.8 The oven temperature is then decreased to as follows: AgY # CuZnY . ZnNdY . ZnY . CuY . NiNdY
the desired adsorption temperature. The flow of reducing = NaY. From comparative analysis of the above results, it can be
atmosphere is stopped and jet fuel is passed through the seen that the same two adsorbents even obtain the converse
adsorption bed by use of an HPLC pump or advection pump desulfurization performance, indicating that the desulfurization
at the desired flow rate. performance is not merely determined by the chemical composi-
tion of the adsorbents.
Song and coworkers27 synthesized a serial of transition metal
3. SARS adsorbents
ion-exchanged Y zeolites (with Cu, Ni, Zn, Pd, and Ce ions) for
As the technological core of the SARS process, the absorbent removing sulfur from Jet fuels. They found that Ce-exchanged Y
has been attracting wide attention. A wide variety of adsorbents zeolites exhibited better adsorption capacity of sulfur and high
such as ion-exchanged zeolites, supported metals, metal oxides, selectivity for sulfur compounds as compared to the selectivity of
aromatics, and the sulfur compounds are adsorbed over Ce-
exchanged Y zeolites via direct sulfur–adsorbent (S–M) interac-
tion rather than via p-complexation. Li et al.39 further revealed
that Ce(IV)Y adsorbed thiophene not only through physical
adsorption, but largely via direct S–M (d) interaction. Zhang
et al.38 further confirmed that the desulfurization efficiency
follows the order direct adsorption . oxidation–adsorption .
direct oxidation.
Selective adsorption of sulfur compounds and aromatic
compounds in a hexadecane on commercial zeolites, including
NaY, USY, HY and 13X, has been investigated by adsorption and
flow calorimetry techniques.40 Among the investigated zeolites,
NaY has the highest saturation sorption capacity for the sulfur
compounds. A linear correlation between the heat of adsorption
and the amount of S adsorbed was found for NaY. Competitive
adsorption using a mixture of anthracene, DBT and quinoline
indicates that NaY selectively adsorbs quinoline while anthracene
and DBT have similar affinity to NaY. It suggests that NaY is
difficult to adsorptively separate sulfur compounds from aromatic
hydrocarbons with the same number of the aromatic rings.
Yang and coworkers33 further studied the effect of ion
exchange technique on desulfurization performance. The inves-
tigated techniques include liquid-phase ion exchange (LPIE),
vapor-phase ion exchange (VPIE), and solid-state ion exchange
Fig. 3 Schematic representation of adsorption desulfurization system (SSIE) techniques. They found that the sorbent capacities
designed for the PSU-SARS study.8 for total sulfur removal followed the order Cu(I)–Y(VPIE) .

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Ni(II)–Y(SSIE) . Ni(II)–X(LPIE) . Zn(II)–X(LPIE) . Zn(II)– sub-ppmv levels.43 However, this type of desulfurization is able
Y(LPIE). The best sorbent, Cu(I)–Y(VPIE), has breakthrough to obtain high efficiency only at high temperatures. ZnO14 and
adsorption capacity of 0.395 mmol-S g21 of sorbent for ZnO–based sorbents such as ZnO stabilized by Fe2O344–45 and
commercial jet fuel (364.1 ppmw S). TiO246–47 are widely employed in desulfurization applications at
Takahashi et al.34 found that the sorbent capacities for higher temperatures. ZnO-based sorbents have low structural
thiophene at the low pressure followed the order Cu–Y and Ag– stability at high temperatures, because of the reduction to
Y & Na–ZSM–5 . activated carbon . Na–Y . modified alumina volatile zinc, as well as zinc migration and agglomeration
and H–USY. The separation factors of thiophene over benzene (at occurred on the sorbent particle surface. Thus, the improvement
low concentrations of thiophene) calculated from pure component of thermal stability of ZnO has become an important issue.
adsorption isotherms exhibited the trend Ag–Y . Na–ZSM–5 . Zhang et al.48 reported that the desulfurization performance of
Cu–Y # activated carbon & Na–Y & H–USY # modified Zn–Fe–O/Al2O3 sorbent was definitely improved by the addition
activated alumina. The above results illustrate that the different of cerium at low temperatures ranging from 35–90 uC, and the
composition of the tested real fuel (such as different fuel additives) spent adsorbent is easy to be regenerated. Li et al.49 also
significantly affects the desulfurization performance, and the confirmed that the desulfurization activity of nanosized Ce–ZnO
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adsorption capacities of metal ion exchanged zeolites is higher was greatly improved by doping Ce, because cerium additive
than those of activated carbon and modified activated alumina. decreased particle size of the nanosized ZnO. However, in the
current authors’ opinion, the promotional effect may also be a
3.2 Supported metals result of direct interaction between Ce and thiophene sulfur. This
is because that ceria possesses high oxygen storage capacity and
Nickel adsorbent supported on silica-alumina (Ni/SiO2–Al2O3)
perfect redox properties, and also sulfur compounds have
exhibited an excellent performance in SARS from jet fuels.17
more affinity to oxidation than their analogue hydrocarbons in
Sulfur compounds in this approach are selectively removed by a
diesel fuels. Therefore, there might be a consequence of high
direct sulfur–adsorbent interaction rather than p-complexation.18
conversions of sulfides to sulfones and sulfoxides. These
The adsorptive desulfurization of fractionated light JP-8 over the
substances have different polarity compared to sulfide that can
Ni/SiO2–Al2O3 adsorbent having particle sizes between 0.15 and
be used for selective removal of organic sulfur compounds with
0.25 mm offered a sulfur breakthrough adsorption capacity of
the solid adsorbent. Furthermore, as a result of big size effect of
about 11.5 mg of S g21 of adsorbent without developing any
cerium ion, cerium enhances the thermal and structural stability
significant pressure drop across the beds. Kim et al.41 found that
of the nanosized ZnO. As mentioned above, it seems that the
the sorption selectivity of the nickel-based sorbent for various
desulfurization performance of complex metal oxides is much
compounds at room temperature increases in the order of Nap #
better than that of single metal oxide sorbent.
1-MNap , 4, 6-DMDBT , DBT , quinoline , indole, as shown
Activated alumina has good adsorptive properties and has
in Fig. 4. But the Nickel-based adsorbents usually have much
been used for selective removal of sulfur compounds from fuels.
higher capacity for removing sulfur at high temperature, such as
Srivastav et al.50 found that the surface carbon-oxygen
200 uC. 42 On the other hand, storage and pretreatment of the
functional groups of alumina were effective in the adsorption
reduced metals under reducing atmosphere are important issues
of DBT. But Kim et al.41 observed that the activated alumina is
for scale-up techniques in desulfurization.
not very successful for separating the thiophenic compounds
from aromatics. They found that the adsorptive selectivity of the
3.3 Metal oxides
activated alumina increases only in the order of Nap # 1-MNap
Current technologies using metal oxide-based sorbents can , 4,6-DMDBT # DBT % indole , quinoline, as shown in
reduce sulfur concentration from several thousand ppmv to Fig. 5. Therefore, low temperature desulfurization performance

Fig. 4 Breakthrough curves of aromatic, sulfur and nitrogen com- Fig. 5 Breakthrough curves of aromatic, sulfur and nitrogen com-
pounds over Ni/SiO2–Al2O3.41 pounds over the activated carbon.41

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and high selectivity for sulfur compounds of metal oxides will be for SARS as a new approach to ultra-deep desulfurization of
an interesting research topic in the future SARS. diesel fuels at room temperature.
The total sulfur adsorption amounts (normalized per adsor-
3.4 Activated carbons bent weight) were obtained after solving the following equa-
tion:35,53–54
Activated carbons, as cheap porous materials with very high
  ð t  
surface areas, large pore volume and rich surface functional u_ rfuel Xi C ðt Þ
qbreakthrough or saturation~ 1{ dt (4)
groups, have been widely used in deodorization, decolorization, madsorbent MWsulfur o Ci
purification of drinking water, treatment of waste water, and
adsorption and separation of various organic and inorganic where q is the total sulfur adsorbed amount (mmol g21), u_ is the
chemicals.18,51 Activated carbons are also found to be effective in feed volumetric flow rate (mL min21), rfuel is the fuel density (g
adsorptive desulfurization of liquid hydrocarbon fuels. Kim mL21) at room temperature, Xi is the total sulfur fraction (by weight)
et al.41 found that the adsorption capacities based on the in the feed, Ci is the total sulfur concentration in the feed (ppmw S),
adsorbent weight at room temperature increase in the order of madsorbent is the weight of the sorbent bed (g), MWsulfur the molecular
activated alumina , Ni/SiO2–Al2O3 , activated carbon for total weight of sulfur, C(t) the effluent total sulfur concentration (ppmw S)
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sulfur as shown in Fig. 6, indicating that the activated carbon is at time t (min). The breakthrough adsorption amounts were
the best adsorbent for total sulfur removal at room tempera- obtained at the point where the fuel total sulfur concentration was
tures. They also observed that the activated carbon shows the less than approximately 1 ppmw S.
highest adsorption capacity and selectivity for sulfur com- To facilitate the quantitative analysis and discuss the adsorp-
pounds, especially for the sulfur compounds with methyl groups, tion selectivity of carbon materials for each compound, a
such as 4,6-DMBT. The adsorption selectivity trend for selectivity factor was used, which is defined as52
selectivity increases in the order Nap , 1–MNap , DBT ,
qi =qr
4,6–DBT , quinoline , indole, as shown in Fig. 7. Zhou et al.52 air ~ (5)
Ce,i =Ce,r
studied the effects of structural and surface properties of carbon
materials on the adsorption of benzothiophene (BT), diben- where qi and qr are the adsorptive capacities of adsorbent for
zothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) and compound i and reference compound r at equilibrium, respec-
4,6-dimethyl-dibenzothiophene (4,6-DMDBT) in the presence of tively. Ce,i and Ce,r are the concentrations of compound i and
10 wt% of aromatics in liquid alkanes that simulate sulfur reference compound r, respectively in liquid phase at equilibrium.
compounds in diesel fuels. They found that different carbon
materials have significantly different sulfur-adsorption capacities 3.5 Ionic liquids
and selectivities that depend not only on textural structure
but also on surface functional groups. The oxygen-containing Ionic liquids have been examined for possible applications related
functional groups on the surface appear to play an important to green chemical processes, such as liquid/liquid extraction, gas
role in increasing sulfur-adsorption capacity. The adsorption- separations, electrochemistry and catalysis.55–63 These liquids are
selectivity trend of the carbon materials for various compounds easy to handle because of non-volatility, non-flammability, and
increases in the order of BT , naphthalene , 2-methylnaphtha- high thermal stability. As novel liquid adsorbents, ionic liquids
lene , DBT , 4-MDBT , 4,6-DMDBT. This selectivity trend broaden the concept of PSU-SARS which is limited base on solid
for sulfur compounds is dramatically different and almost adsorbents. The ionic liquids have been applied for selective sulfur
opposite from that for adsorption over nickel-based adsorbents. removal from fuels in recent years, because the ionic liquids are
The high-adsorption capacity and selectivity for methyl DBTs easy to be regenerated from adsorbed S-containing compounds by
indicate that certain activated carbons are promising adsorbents distillation or by dissolution in water, where ionic liquids are

Fig. 6 Breakthrough curves for total sulfur over the three different Fig. 7 Breakthrough curves of aromatic, sulfur and nitrogen com-
adsorbents.41 pounds over the activated alumina.41

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As stated above, different adsorbents exhibit different

adsorption capacities and selectivities. In general, the adsorption
performance of adsorbents usually depends on chemical
composition and surface physical and chemical properties of
adsorbents, such as active sites and their density, surface area,
pore size and distribution, functional groups and so on, which
are functions of chemical components and their compatibility,
the preparation process, and activation conditions. A funda-
mental understanding of the effect of surface physical and
chemical properties on adsorption capacity and selectivity will be
important for designing and developing more efficient adsor-
bents for selective adsorptive desulfurization.
As the different adsorbents are suitable for selective removal
of sulfur compounds from different hydrocarbon species, a
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jet fuel usually includes many coexisting sulfur-containing

hydrocarbon species; therefore a combination of two or more
Fig. 8 Absorption capacities of EMIM+BF42, BMIM+PF62 and adsorbents used might be more efficient for a practical ultradeep
BMIM+BF42.64 SARS process. The size and composition of a given adsorbent
bed depend on the composition of the fuel and servicing period
air- and moisture-stable at low temperature and non-corrosive. required in the particular application. According to the
Hence, the ionic liquids can be used in multiple cycles for the operating temperatures, the reported selective adsorptive desul-
removal of S-containing compounds from fuels. furization processes can also be classed into high temperature
Zhang et al.64 reported that the ionic liquids, 1-ethyl-3- process (.600 uC), medium temperature process (150–550 uC),
methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazo- and ambient temperature process.18 The high and medium
lium hexafluorophosphate and 1-butyl-3-methylimidazolium temperature processes involve a chemical reaction or absorption,
tetrafluoroborate were effective for the selective removal of and the adsorbents include metal oxides and reduced metals. The
sulfur-containing compounds from transportation fuels such as ambient temperature process usually involves physical or
gasoline at room temperature. They found the local structure of chemical adsorption on the surface, and the adsorbents include
the ionic liquids appears to have a significant effect on their zeolites, activated carbons, ionic liquids and other mesoporous
interaction with the aromatic compounds. S-containing com- materials.
pounds with a C5 aromatic ring are favorably absorbed over C6 At present, researches on the adsorbents for ultra-deep
aromatics, while S-containing non-aromatic compounds are desulfurization of real jet fuels are still not systematic as shown
poorly absorbed. As shown in Fig. 8, the absorption capacity in Table 1. Especially, the desulfurization performance at low
follows the general order thiophene & methylthiophene . temperature, such as room temperature, is not ideal. Low
toluene & trimethylbezene . isobutylthiol, hexane, 2-methyl- temperature desulfurization performance of adsorbents should
pentane, methylcyclopentane. It appears that adsorption is be the key for its wide application in SARS of jet fuels in the near
favored for molecules with higher density of aromatic p future. Hence, in developing a successful SARS process for ultra-
electrons. The absorption capacity of the ionic liquids for deep desulfurization of jet fuels, the major challenge is to develop
S-containing compounds is sensitive to the structure of both the a novel efficient, environmentally friendly and cheap adsorbent
anion and cation of the ionic liquids, which is manifested by the that has higher sulfur adsorption capacity and selectivity at
significant inhibiting effect of methyl group substitution on the low temperature under atmospheric pressure without hydrogen
aromatic ring. consumption, and is easy for regeneration. Anyway, more

Table 1 Adsorptive capacity of different sorbents for Jet fuels

Adsorbent Fuel description Sulfur in fuel (ppmw) Adsorption condition Breakthrough capacity (mg-S g21)

Cu(I)–Y(VPIE)33 Jet fuel 364 Room temperature 12.6

Zn(II)–Y(LPIE)33 Jet fuel 364 Room temperature 1.4
Zn(II)–X(LPIE)33 Jet fuel 364 Room temperature 2.8
CuCl/AC65 JP-5 1172 Room temperature LHSV: 2.3 h21 1.0
PdCl2/Al2O365 JP-5 1172 Room temperature LHSV: 2.3 h21 2.1
PdCl2/AC65 JP-5 1172 Room temperature LHSV: 2.3 h21 3.2
Ni/SiO2–Al2O35 Light JP-8 380 220 uC, LHSV: 2.4 h21 13.5
KYNiE-366 Light JP-8 380 80 uC 4.5
KYNi8IWI66 Light JP-8 380 80 uC 2.4
NiY–Zeolite67 JP-8 736 80 uC for 4–5 h 2
CuY–Zeolite67 JP-8 736 80 uC for 4–5 h 0.3
ZnY–Zeolite67 JP-8 736 80 uC for 4–5 h 0
CeY–Zeolite67 JP-8 736 80 uC for 4–5 h 2.7
PdY–Zeolite67 JP-8 736 80 uC for 4–5 h 2.6
HY–Zeolite67 JP-8 736 80 uC for 4–5 h 1.3
Ce–Y27 JP-8 750 80 uC 4.5

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Fig. 9 Schematic representation for desulfurization of 4,6-dimethyl-

dibenzothiophene with molybdenum-based (A) and copper(I)-based (B)
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adsorbents. Case (B) corresponds to p-complexation.33

efforts should be focused on improving the room temperature

desulfurization performance of adsorbents in SARS of jet fuels
for portable power applications in the near future. Fig. 10 Copper ions occupying faujasite six-ring window sites (A); s–
donation of p–electrons of thiophene to the 4 s orbital of copper(I) (B); d-
p* back-donation of electrons from 3d orbitals of copper(I) to p* orbitals
4. Mechanism of SARS reaction of thiophene (C). Here 3d represents dxy, dyz, or dxz, or three of the five
3d orbitals.33,87,88
4.1 p-complexation
For industrial adsorption processes, chemical complexation
effect rather than any electronic effect. Yang and coworkers54
bonds are generally stronger than van der Waals interactions,
further studied a novel adsorbent of PdCl2/AC for desulfuriza-
yet weak enough to be broken by traditional engineering means
tion of a model jet fuel, and proposed a theory about edge sites:
such as increasing temperature and/or decreasing pressure.68
there were a large number of peripheral sites on the edges of the
Therefore, a tremendous opportunity exists for developing new
supported metal salt which was well dispersed on the carbon
sorbents by using weak chemical bonds, including various forms
support, and the edge sites provided an ideal combination of
of complexation bonds.32,34 On the basis of the principles of
sites for the benzothiophene molecule: PdCl2 for the thiophene
p-complexation, Yang and coworkers have been developing a
ring and carbon for the benzene ring. Adsorption of a
number of new sorbents for many applications, including
substituted methylbenzothiophene molecule on such an edge
desulfurization,32,34,69–76 olefin/paraffin, diene/olefin, and aro-
site is depicted in Fig. 11. In this depiction, benzene ring is
matics/aliphatics separations.77–86 For desulfurization, they
adsorbed strongly on the surface of carbon, while the thiophene
prepared transition metal ion exchanged zeolites to selectively
ring is bonded to the adjacent Pd2+ site by p-complexation. By
remove organosulfur molecules from different fuels like diesel,
binding cooperatively in this manner, stronger adsorption and
gasoline and jet fuels.
hence higher adsorbed amounts were achieved.
Yang and coworkers72 found that the methyl groups in
4-methyldibenzothiophene (4-MDBT) and 4,6-dimethyldiben-
4.2 Direct sulfur–adsorbent (S–M) interaction
zothiophene (4,6-DMDBT) create a steric effect that hinders the
capacity of HDS catalysts to chemisorb the sulfur atoms as Song and coworkers8,89–91 found that the p-complexation could
depicted in Fig. 9(A).33 However, such steric hindrance is not not explain the reason why the modified zeolites were able to
present for adsorption by p-complexation. Fig. 9(B) depicts effectively adsorb trace of sulfides from gasoline with many
the mechanism involved during p-complexation between 4,6- aromatics and olefins. For exploring selective adsorption, they
DMDBT and a copper(I) cation. In the complexation mechan- are interested in the coordination geometries of thiophene in
ism, the cation can form the usual s bonds with their empty organometallic complexes. Fig. 12 shows eight coordination
s-orbitals and, in addition, their d-orbitals can back-donate configurations of thiophene in organometallic complexes.92–95
electron density to the antibonding p-orbitals (p*) of the sulfur Among the coordination configurations, g1S and S–m3 are the
rings (see Fig. 10).33,87,88 Experimental data and molecular two specific configurations where thiophene coordinates directly
orbital (MO) calculations have shown that p-complexation with with the metal through sulfur-metal interaction, suggesting there
cuprous ions is stronger with organo-sulfur molecules (i.e., are likely adsorbents that are able to adsorb the thiophenic
thiophenic molecules) than with aromatics without sulfur (e.g., compounds selectively through g1S or S–m3 –bonding. Four
benzene).34 p-complexation configurations of g1C, g2, g4 and g5 are formed
From the above results, it can be seen that the charge- via interactions between thiophene and metal species through
compensating anion has a very strong effect on the p-complexa- one or more CLC double bonds. Two configurations of g4, S–m2
tion by the cation for the sorbents.54,74 But the effect of the and g4, S–m3 involve both p-complexes and direct S–M bonds. As
substrate on the metal salt is much weaker. For the metal salt, a illustrated above, it seems that the selectivity for sulfur
geometric effect is the dominant reason for the strong synergistic compounds of the absorbent should be improved greatly if

1706 | RSC Adv., 2012, 2, 1700–1711 This journal is ß The Royal Society of Chemistry 2012
 View Article Online

Fig. 11 Depiction of synergistic effect in adsorption of methylben-

zothiophene on PdCl2/AC.54

thiophene coordinates with the metal species merely through

direct S–M interaction.
Song and coworkers’ experiment27 revealed that Ce-exchanged
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Y zeolites exhibited higher selectivity for sulfur compounds as

compared to the selectivity of aromatics in the adsorptive
desulfurization of a mode jet fuel and a real JP-8 fuel, for which
a comparative study indicated that the sulfur compounds
are adsorbed over Ce-exchanged Y zeolites via direct sulfur-
Fig. 13 Electron density isosurfaces corresponding to molecular struc-
adsorbent (S–M) interaction rather than via p-complexation.
tures of benzothiophene and 2,3,7-trimethylbenzothiophene by molecu-
Meanwhile, they also performed a computational analysis for the
lar simulation with MOPAC.8
electronic properties by using molecular orbital package from
CAChe software system (MOPAC).23 The calculated results
results are shown in Fig. 14.41 It shows clearly that the negative
showed that the highest occupied molecular orbital (HOMO) of
electrostatic potential are dominantly located on the two sides of
thiophene, benzothiophene and dibenzothiophene is located
the molecular plane (except quinoline), and the value of the
more on the sulfur atom, whereas the HOMO of alkyl benzenes
negative electrostatic potential increases in the order of Nap ,
and naphthalene on the conjugated six-member ring. These
1-MNap , DBT , 4,6-DMDBT , indole , dihydroindole.
results suggest that it may be possible to achieve preferential
Evidently, the methyl group at the aromatic ring enhances the
adsorption by interaction of sulfur atom with certain metal
negative electrostatic potential on the two sides of the molecular
species through the interaction of HOMO on sulfur with lowest
plane because the methyl group is an electron donor to the
unoccupied molecular orbital (LUMO) on metal species.
aromatic ring.
Song and coworkers27 further observed that the selectivity for
2-methy benzothiophene (2-MBT) was higher in the static
4.3 Active sites for adsorption
adsorption studies, while the adsorption selectivity decreased in
the order of 5-methyl benzothiophene (5-MBT) . benzothio- According to the p-complexation mechanism, the p-complexation
phene . 2-MBT under dynamic conditions. This trend was adsorbents exhibit low selectivity for sulfur compounds as a result
correlated to the electron density on sulfur atoms derived from of competitive adsorption of aromatic compounds, while accord-
computer-aided molecular orbital calculations.27 The electron ing to the adsorption mechanism of direct S–M interaction, the
density isosurfaces of BT and 2,3,7-TMBT are shown in Fig. 13.8 adsorbents possess high selectivity for sulfur compounds, but the
The computer simulation clearly demonstrates the existence of steric hindrance make them difficult to remove sulfur from
steric hindrance due to the presence of methyl groups at 2 and 7 DMDBT etc. However, the contradiction is not irresolvable. On
positions of the BT ring. The electrostatic potential color- the one hand, thiophene has two lone pairs of electrons on the
mapped on the electron density with values at the color sulfur atom; one pair lies on the six-electron p system and the
boundaries for the seven molecules was calculated and the other lies in the plane of the ring. Thiophene can act either as an
n-type donor by donating the lone pairs of electrons that lie in the
plane of the ring to the adsorbent (direct S–M s bond) or as a
p-type donor by utilizing the delocalized p electrons of the
aromatic ring (p bond) to form a p-type complex with the metal
ions.27 On the other hand, the adsorption capacity and selectivity
of adsorbents can be further improved by modifying various types
of surface active sites for adsorption, such as Lewis acid sites,
useful functional groups, electronic defect centers, micro-struc-
tural defects and so on. Seredych et al.96 synthesized a serial of
novel mesoporous carbons with highly dispersed copper, cobalt,
and iron for the reactive adsorption of dibenzothiophene. The
small metal content (less than 1%) and its chelation in the
precursor polymers ensure a high dispersion of metallic centers.
Fig. 12 Coordination geometries of thiophene with metal species in The materials obtained are mainly mesoporous but differ
organometallic complexes.23 significantly in their porosity and surface chemistry, which is

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Fig. 14 Electrostatic potential on electron density for the examined compounds.41

linked to the effect of template constraints and chemistry and the groups at the 4 and/or 6 positions, which are major sulfur
kind of metal and is related to the differences in the carbonization compounds in commercial diesel fuel, is reduced significantly
mechanism. The high capacity of the investigated carbons in because of the steric hindrance of the alkyl groups; (c) the
adsorption of DBT from hexane is up to 130 mg S g21, which were reduced metal is easy to be oxidized and would require careful
linked to the high volume of mesopores and specific interactions passivation treatment during storage and transport, which is an
of DBT with surface acidic groups and strong interactions of issue for scaleup techniques in desulfurization; (d) the regenera-
metals with dibenzothiophene via S–M s bonds or, in the case tion of spent nickel-based adsorbents requires reduction by using
of copper, via interaction of metals with disturbed p electrons of hydrogen gas at high temperature. Although zeolites, carbon
aromatic rings of DBT. materials, and activated alumina possess perfect adsorption
According to Lewis acid–base theory, most thiophene sulfur capacity at low temperature, even at room temperature, they
compounds in jet fuels are Lewis base, which are easy to be have low selectivity for sulfur compounds from jet fuels, because
adsorbed at Lewis acid sites. Hence, it can select materials that the desulfurization efficiency is dramatically dependant on the
can form Lewis acid sites to selective adsorb thiophene sulfur physical adsorption. Herein a combination of reduced metals
compounds with the lone pair electrons in jet fuels. The Lewis modified porous materials may be promising for ultradeep
acid–base adsorption mechanism is the interaction between the desulfurization of jet fuels at room temperature under atmo-
acid sites on the surface of adsorbent and thiophene derivatives. spheric pressure.
Xue et al.37 confirmed that AgY–zeolite shows stronger Currently, selection of adsorbent active components and the
adsorption of the soft bases TP and 1-BTP than CuY–zeolite effect of chemical composition on desulfurization performance
because Ag+ is a softer acid than Cu+, and Ag+ and Cu+ can have already been investigated maturely. It has already obtained
combine with TP and 1-BTP mainly by p bonds and form p-type many different desulfurization orders in sulfur-adsorption
complexes. Ce4+ is a hard acid and prefers to combine with TP capacity and selectivity for different adsorbents. However, it
and 1-BTP by the direct S–M s bond rather than by the p bond. can be even observed that different scientists obtain the converse
active orders from the same two adsorbents in SARS of the
5. Prospect of SARS process same fuels. Thus, with only studies to the effect of chemical
composition on desulfurization performance it is insufficient to
5.1 Improvement of SARS adsorbents fully reveal the nature of selective adsorptive desulfurization by
Among various alternative adsorbents, supported reduced adsorbents, and thereby difficult to summarize the general action
metals are considered to be more promising for SARS process rules. In our previous work,98 we found that even the same
because of much higher sulfur-adsorption capacity and selectiv- chemical component in different structure exhibits different
ity for sulfur compounds in comparison of other adsorbents.8 performance, such as TiO2 for denitrification, the TiO2–anatase
Representative Ni/SiO2–Al2O3 exhibits an excellent performance exhibits more than 90% denitrification efficiency in NH3–SCR of
in removing sulfur from jet fuels.97 However, nickel-based NO, but the TiO2–rutile possesses less than 15% denitrification
adsorbents have some drawbacks:41,52 (a) desulfurization is efficiency. Therefore, chemical composition is only the basic
merely able to obtain high efficiency at high temperature, and factor for affecting material performance, whereas material
the supported metals possess low thermal stability at high structure is also a very important factor. Once the chemical
temperature; (b) the adsorptive selectivity of nickel-based composition of adsorbents is chosen, materials structure can
adsorbents for alkyl dibenzothiophenes with one or two alkyl significantly affect the physical and chemical properties.

1708 | RSC Adv., 2012, 2, 1700–1711 This journal is ß The Royal Society of Chemistry 2012
 View Article Online

However, the effect of material structure on desulfurization

performance of the absorbents has rarely been systematically
studied so far, which severely restricts the development and
application of novel adsorbents with features of high efficiency,
environmental benign and low cost.
Adsorptive performance of adsorbents not only depends on
the solid acidity, unbond d electrons and empty hybrid orbital of
the active components, but also on the microstructure and
structural defects of the solid adsorbents, such as the crystal
structure, solid solution, grain boundary stress, non-stoichio-
metric defects, pore structure, dispersion and refinement of
grains, and uneven surface atomic steps, kinks, impurities,
dangling bonds and so on, which can cause a variety of chemical
defects to provide reactants with chemical adsorption energy or
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increase the interface and active sites for chemical adsorption.

Furthermore, the geometry and surface state of the active
components changing can induce the variation of chemical
adsorption energy, and thus cause changes in adsorption
capacity and selectivity. Adsorbent supports can also affect the
adsorptive properties of adsorbent active components; particu- Fig. 15 Electrostatic potential on electron density for the examined
larly increase the solid acid sites. Moreover, support can act as compounds.101
structural promoter to increase the surface area, prevent
sintering of the active components and improve the structural specific surface, more active sites and their density, more useful
stability of the active component; or act as electronic regulators functional groups, more structural defect centers and perfect
to adjust electronic structure (combined-state), surface properties size-selective adsorption property. According to the adsorption
and crystal structure of the active components, thereby enhance mechanism of direct sulfur-adsorbent (S–M) interaction, it is
the activity of the adsorbents. also promising to obtain perfect selectivity of sulfur compounds
The specific structure of an adsorbent is generally determined at low temperature by ionic modifications. i.e., via specific ions
by its synthesis and preparation. Shan et al.99–100 found that to modify the above mesoporous materials into novel adsorbents
ultrasound was able to improve ion exchange degree, reduce the for ultradeep desulfurization, which is under research in the
ion exchange time and impregnation time, decrease metal authors’ team.
particle size and increase the metal dispersion on the adsorbent
surface, which contributed better desulfurization performance. It 5.2 Future prospect of SARS technology
illustrates that the perfect desulfurization performance of
adsorbent in SARS process can be further obtained by grafting The limited situated adsorption capacity and regeneration of the
novel preparation technology. Recently, Liu and coworkers101 adsorbents are important issues to be considered for scaleup
developed a strategy for the fabrication of novel p-complexation techniques in refineries.22 This requires us to find solutions when
adsorbents by grafting Cu(I)-containing molecular precursor an adsorbent reaches its saturated adsorption in the SARS
onto b-cyclodextrin (CD). Isolated Cu(I) sites are successfully process and lost further desulfurization capability, or if
generated on CD (Fig. 15A). The resulting materials provide a adsorption alone can not technologically reach the ultradeep
molecular-level dispersion of Cu(I) (denoted as Cu–CD). Such an desulfurization levels for jet fuels.
extreme disperse state of Cu(I) is quite different from conven- Some new technology may speed up the desulfurization of
tional ones (e.g. CuCl), and can avoid the possible aggregation of hydrocarbon fuels; for example using ultrasound. Gunnerman
active species that usually occurs in Cu(I)-containing oxides and et al.102 invented a novel ultrasound-assisted desulfurization of
salts. They demonstrated that Cu–CD materials exhibit excellent fossil fuels in the presence of dialkyl earths, they found that the
adsorptive desulfurization capacity in thiophene capture through emerging mixture separates spontaneously into aqueous and
the p-complexation mechanism, which is much better than CuCl organic phases under ultrasound, from which the organic phase is
supported on CD via the conventional thermal dispersion readily isolated as the desulfurized fossil fuel. For another
method (Cu/CD). example, acidic alumina shows promising results as an adsorbent
As stated above, study on material structure and exploring in the UAOD process,22 the sulfur concentration in JP-8 jet fuel
novel preparation methods of adsorbents will be the key in can be reduced from the original 850 ppm to 1 ppm at an
developing new adsorbents of high performance. In view of the oxidation time of 10 min at ambient temperature and atmospheric
significant synergistic effect between the carbon substrate and pressure. It is encouraging that we may further improve the
the supported p-complexation sorbent,54 it is inferred that a high desulfurization performance via ultrasound technologies when the
sulfur-adsorption capacity at low temperature could be due to situated capacity of an adsorbent still can not reach the desired
the geometric effect. In comparison with activated carbons and ultra low sulfur level. To prove this hypothesis the authors’ team
zeolites, it is promising to obtain perfect low temperature is exploring for ultradeep desulfurization by ultrasound-
desulfurization performance by designing and synthesizing a assisted selective adsorptive desulfurization (UASAD) using a
serial of novel mesoporous materials with better merits of bigger novel mesoporous solid adsorbent at room temperature and

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SARS processes. We expect that with our significant efforts and

study, an attractive ultradeep desulfurization method could be
widely applied in practical devices in the near future.

Acknowledgements
The support from the Office of Naval Research of the USA and
the University of Tennessee SimCenter under the contract
#8500011366 is gratefully acknowledged.

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