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Applying Nanotechnology
to the Desulfurization
Process in Petroleum
Engineering

Tawfik A. Saleh
Department of Chemistry, King Fahd University of Petroleum and Minerals,
Saudi Arabia

A volume in the Advances in Chemical and

Materials Engineering (ACME) Book Series
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Applying nanotechnology to the desulfurization process in petroleum engineering / Tawfik A. Saleh, editor.
pages cm
Includes bibliographical references and index.
ISBN 978-1-4666-9545-0 (hardcover) -- ISBN 978-1-4666-9546-7 (ebook) 1. Petroleum--Refining--Desulfurization--
Materials. 2. Petroleum--Refining--Desulfurization--Technique. 3. Nanostructured materials. I. Saleh, Tawfik A., editor.
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154

Chapter 5
Carbon-Based Nanomaterials
for Desulfurization:
Classification, Preparation, and Evaluation

Tawfik A. Saleh Gaddafi Ibrahim Danmaliki

King Fahd University of Petroleum and King Fahd University of Petroleum and
Minerals, Saudi Arabia Minerals, Saudi Arabia

Taye Damola Shuaib Mohammed A. Al-Daous

King Fahd University of Petroleum and Saudi Aramco, Saudi Arabia
Minerals, Saudi Arabia

ABSTRACT
The special interest in ultra-low sulfur diesel (ULSD) is informed by the need to comply with the strict
government policy on low sulfur content of transportation fuels. Better knowledge of different factors
that concern deep desulfurization of fuels is important to achieve ultra-low sulfur fuels and cheaper
way of producing ULSD. Both the capital and operating cost of the adsorptive desulfurization process
is cheaper compare to the conventional hydroprocessing. The need to produce more volume of fuel such
as diesel with very low sulfur content from low grade feed stocks like heavy oil and light cycle oil (LCO)
in order to meet up with the global demand for sulfur-free fuels is pertinent. Several on-going researches
are pointing to the use of adsorbents for removal of sulfur compounds from the hydrocarbon refining
stream. In this chapter, varieties of carbon nanomaterials suitable for adsorptive desulfurization are
discussed. The approach is feasible for commercial applications with any adsorbent of an adequate
lifetime of activity as well as high capacity.

1. INTRODUCTION

Desulfurization is a vital unit operation in petroleum refining since the combustion products of sulfur
compounds are the main reason for acid rain and environmental pollution. In addition, sulfur is also a
catalyst poison during industrial processes. Compounds with sulfur are removed catalytically at high
temperature and pressure. Desulfurization is gaining a lot of attention and efforts have been channeled
towards investigating several methods that are effective and economically viable. The attention is warranted

DOI: 10.4018/978-1-4666-9545-0.ch005

Copyright © 2016, IGI Global. Copying or distributing in print or electronic forms without written permission of IGI Global is prohibited.

Carbon-Based Nanomaterials for Desulfurization

by stricter environmental regulations on the amount of sulfur that should be present in transportation fuels
(Song, 2003; Yang et al., 2004). Sulfur limit (mass percent) of 0.015, 0.035, and 0.2 for gasoline, diesel
fuel and light fuel oil, respectively has been set. A new and more stringent limit of 0.003-0.005 mass
percent (30-50 ppm) is imminent for transportation fuels in Europe and United States of America (Song,
2003; State Announcer, 2001; Babich and Monlijn, 2003). It’s worthy to note also that; desulfurization
processes have found applications in converting used tires and shale oil to fuel oils. Using calcium oxide
in binding up sulfur oxide in emissions has been achieved for stationary applications in the desulfuriza-
tion of non-transportation fuels, but the use of the harmful compounds still a challenge (Svobodal et al.,
1994). Therefore, the need to innovate effective technologies for desulfurization processes is paramount.
Several methods of desulfurization processes have been investigated for many years. The need to
achieve a lower level of sulfur in fuel oils has also called for different innovative ways of achieving deep
desulfurization where the synergy of methods yielding better results (Agarwal and Sharma, 2010; Sun-
daraman et al., 2009). Hydrodesulfurization (HDS) is a popular process, but there is wide variation in
reactivity of sulfur-containing heterocyclic compounds. Alkyl-substituted derivatives of dibenzothiophene
like 4-methyldibenzothiophene and 4, 6-dimethyldibenzothiophene from fuel oils have been reported to
be relatively unreactive towards hydroprocessing (Gate and Tropsoe, 1997). In order to achieve deep-
desulfurization and take care of attending challenges of hydrodesulfurization that include high hydrogen
consumption, energy (heat) cost, catalyst volume etc. Many other methods are combined with HDS for
better results (Rana et al., 2007). In recent years, efforts are being directed to other methods, including;
adsorptive desulfurization, oxidative desulfurization where different catalysts are used (Kumar et al.,
2012) extractive desulfurization involving ionic liquids, photochemical activation, bio-desulfurization,
ultrasonic-desulfurization, microwave desulfurization and electrochemical approach (Bhatia and Sharma,
2006; Lam et al., 2012).
Adsorptive desulfurization where adsorbents are used to remove sulfur-containing compounds
in fuel oils is holding future promise of ultra-clean sulfur-free fuel oils. Adsorption processes can
be performed at ambient temperature and pressure, thus saving a lot of energy as compared to other
methods of desulfurization (Seredych et al., 2009). Therefore, intensive research is ongoing to produce
new adsorbents with great emphasis on good selectivity, high capacity for adsorption and regeneration
of the adsorbents with special attention to the mechanism of adsorption (Yang et al., 2007). Various
materials have been reported to be good adsorbents for different adsorption processes. These materials
include; different types of zeolites and metal-impregnated zeolites such as MCM-22 zeolites (Delitata
et al., 2008), MCM-41 (lanthanum loaded, sorbents for diesel fuel) (Subhan et al., 2012), Y-zeolites
with exchanged cation (NaY) and carbon nanotubes (CNT) as a template, Ag- and Cu-beta zeolites
among others. A deep desulfurization method was presented by Daimler-Chrysler AG (2000) where
the adsorption process is used for engine fuel with TiO2, MgO, Al2O3 or SiO2 (with metal additives) as
adsorption materials. Dibenzothiophene (DBT) and 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) can
also be removed from diesel by using mesoporous carbon synthesized from silica HMS (template) and
phenolic resins (sources of carbon) (Zhou et al., 2009). Due to high thermal stability, large surface area
and well-arranged mesoporous structure (Arbia and Parvin, 2011) of carbon molecular sieves (CMK-1,
3 and 5), they have been implicated as promising adsorbents of DBT in petroleum fuels.
The following sections will highlight a general classification of carbon materials based on their con-
stituents; discuss major techniques commonly used in their preparation and evaluation of these valuable
materials towards desulfurization.

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Carbon-Based Nanomaterials for Desulfurization

2. CLASSIFICATION OF CARBON-BASED MATERIALS

This section discuses carbon-based materials and their classification based on constituents (Figure 1).

2.1 Carbon Structures as Substrates

Structure indeed determines properties. Different allotropes of low dimension can be formed from car-
bon, such as; graphene, CNT and C-60. The superiority in properties exhibited by CNT among other
1-D nanomaterials can be traced to its special stereogenic structure. Several attentions have been paid
to CNTs over the past two decades; this is due to nothing but unique mechanical, thermal, electrical
properties among other key applications in many fields of science and technology (De Volder, et al.,
2013; McEuen, et al. 2002; Terrones, 2003; Zhang, 2013).
Over the years, carbon has been used as catalyst support employed for different applications in the
chemical industry owing to its fascinating surface nature. The orientation of graphene layers can be
varied with respect to the axes of carbon nanofibres (CNFs) giving different morphologies, which make
available different pores for catalysts’ nanoparticles (Salernitano et al., 2014). Carbon paper substrate
with 3-D fibre network is appropriate in fuel cells with Silicon-Carbon composite deposited alongside
the fibre network on the electrode (Matsiu et al., 2013). Carbon blacks and typically, acetylene black,
have been deeply investigated electrochemically (Kinoshita and Bett, 1973) and gained applications in
many areas, like catalysis, energy storage and fuel cell technology (Zhang, et al., 2010). An effective
interaction (oxidation-reduction active species) is owned to a large surface area of carbon (particle size
1-50 nm, commercially available).
Although carbon black is not well defined structurally like CNT, graphene materials or nano-onions
but their activities in carbon-based nano-sensor, polymer nanocomposites (selective shape sensing), fuel
cell and energy storage are very excellent (Iijima, 1991; Molina-Ontoria, et al.,2013; Novoselov, et al.,
2014 ; Loo, et al., 2013; Li, 2009; Blanco-L_pez, et al., 2004). Correct choice of nanocarbon substrate is
very vital in electrocatalysis and fuel cells, the effects of this have been critically reviewed (Dribinskii, et
al., 1989). Pt– carbon nanomaterial composites have found application in fuel cells that is characterized
by CO2 reduction (Perathoner, et al., 2007). With adequate optimization for stable operational conditions,
carbon blacks give allowance for gas flow into catalysts’ reactive layers.

Figure 1. Classification of carbon-based materials

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Carbon-Based Nanomaterials for Desulfurization

2.2 Carbon with Single Nano-Metal

Carbon possesses ordered structure which provides its framework with good porosity. However, their
uses are limited due to poor solubility, thus limited functionalized nanocomposites of metals and CNTs
can be achieved (Ebbesen et al., 1996). However, the increasing development of CNTs chemistry makes
possible the preparation of hybrid materials (metals and CNT) with enhanced performance (Ding et al.,
2012; Li et al., 2011). These hybrid materials can function as chemical sensors due to their high conduc-
tive (electrical) power and selective chemical nature. Another vital property they possess is reasonably
large surface area, which provide them with good catalyst, sites in reaction catalysis (Ding et al., 2012).
Nanomaterials of low dimension can now be used for electronic applications, chemical sensors, adsorption
(desulfurization) e.t.c (Geim AK, 2009). In the same manner, graphene supported metal nanoparticles
also performs well (Huang et al., 2012; Bai and Shen, 2012).
Metal-carbon interactions play critical roles in catalytically growing carbon nanotubes and graphene
via CVD as well as in controlling the structures of these carbon allotropes and, consequently, have been
intensively investigated in order to elucidate the catalytic mechanisms(Jourdain and Bichara, 2013;
Mattevi, 2011; Li, 2010; Ding, 2008; Edwards, 2013; Seah, 2014; Cheng and Guo, 2002). Fe and Cu
are two metal systems exhibiting distinct interactions with carbon (Naidich, 1981). With partially filled
3d-orbitals, Fe exhibits a high affinity for carbon. Carbon has a finite solubility in Fe at high tempera-
tures (0.022% carbon by weight in α-Fe at 727 o C and 2.14% carbon by weight in γ-Fe at 1147 oC) and
forms metastable iron carbide (Fe3C, 6.67% carbon by weight) with Fe (Jourdain and Bichara, 2013;
Mattevi, 2011).
Due to its strong interactions with carbon, Fe was among the first catalysts and has been most inten-
sively used for CVD growth of single-wall carbon nanotubes (SWCNTs). In contrast, with completely
filled d-orbitals, Cu displays a low affinity for carbon. The carbon solubility in Cu is much lower than
in Fe (~ 0.008% carbon in Cu by weight at 1085 oC) and there is no carbide formation (Jourdain and
Bichara, 2013; Mattevi, 2011). Due to the weak Cu-C interactions, Cu was once considered unsuitable
for CVD growth of carbon nanotubes (Deck and Vecchio, 2006). However, this notion did not stop the
exploration of using Cu as the catalyst. In fact, it has been demonstrated that Cu can catalyze the growth
of SWCNTs (Yoshida et al., 2009; Zhou, 2006) and, furthermore, it is a better catalyst for developing
SWCNT system using quartz and silicon as substrates (Li et al., 2010 and Cui et al., 2010). In terms of
the metal-catalyzed CVD growth of graphene, the different interactions with carbon between Fe and
Cu result in the formation of few-layer graphene (FLG) on Fe foil (Xue et al., 2011) and monolayer
graphene on Cu foil (Li et al., 2009). With the formation of methane, carbon hydrogenation reverses
the reaction for CVD growth of carbon nanotubes and graphene using methane as the carbon source. It
was demonstrated that Fe is an active catalyst in producing methane and in etching channels in graphite.
Though an initial study showed that Cu was inactive in catalyzing the hydrogenation of graphite, Cu was
later found to be active in catalytic etching channels in graphite (Baker, 1981 and 1995).
Metals of transition series are good options for growing graphene or CNTs. The metal-carbon system
can be built by performing the growth and contacting in a single step with the same metal. However, a
pressing challenge here is oxide layer formation on exposure of nanoparticles of metal to air as it tarnishes
and form oxide coating. The formation of the oxide coatings is largely due to large surface-volume ratio,
which translates to high oxidation process. The oxidation process at the metal surface can, however, is

157
 
Carbon-Based Nanomaterials for Desulfurization

prevented in the procedure (Geim AK, 2009). Scanning electron microscope (SEM) reveals the porosity
of carbons is paramount to their adsorptive properties. Figure 2 shows SEM images of different carbon
structures such as activated carbon (AC), CNT and graphene.

2.3 Carbon-Based Composites

The good surface chemistry, stable structure and very large surface area are factors enabling the fine
surface templating property of graphitic supports (carbon nanospheres (CNSs), CNT, and graphene) and
their decoration with metal nanoparticles (Iwamoto and Grimblot, 1997). The composites formed show
enhanced or even synergistic activity in their applications (Salem and Hamid, 1997). The surface
chemistry of the composites, however, is not fully established and still open to further studies (Nagai
et al., 2000).
Carbon nanomaterial composites made by decorating carbon (graphene, carbon nanospheres, and
carbon nanotubes) with transition metals (oxides or salts) are receiving great attention. Carbon-supported
metal nanoparticles (MNPs) for example; cobalt, iron, or nickel based nanoparticles (CoOx–CoP/C or
FeOx–CoP/C) have been confirmed to be catalytically active for oxygen reduction reaction (ORR); this
is due to the nature of the transition metals oxide nanoparticles (Stephanie, et al., 2010). The confirma-
tion of this great activity is shown in the less activity of cobalt porphyrin (CoP/C) when it is adsorbed
on unmodified carbon. Sometimes a synergistic activity is observed (Salem, 1997).
In the investigation of the potency of activated carbon materials for desulfurization and denitrogena-
tion gas oils, MAXSORB-II adsorbent, is an effective adsorbent for organosulfur compounds’ adsorption
at ambient temperature (Mochida et al, 2004a and 2003c). This material can be prepared by activating
carbon prepared from petroleum coke with KOH. Oxidizing agents as HNO3 and H2O2 were also used

Figure 2. SEM images of nano-structured carbons of AC (a), CNT (b) and graphene (c)

158

Carbon-Based Nanomaterials for Desulfurization

to further enhance the adsorptive power of commercially available activated carbon, which is then heat
–treated (Mochida et al., 2004b, 2003d). These oxidizing agents aid the release of CO (600-800 0C) at
the carbon surface, which thus enhances the absorption power.

3. PREPARATION OF CARBON STRUCTURES

There are three main techniques of preparing carbon nanomaterials such as CNT, CNS, CNF, graphene
etc.(Iijima, 1991; Yudasaka et al., 1997; Li et al., 1996). These techniques are listed in Figure 3. Other
techniques that are commercially less developed compare to the above-mentioned three which involve the
use of flame, solar, electrolysis in their syntheses (Yuan et al., 2001; Hsu et al.,1996; Laplaze et al., 1998).
In the arc discharge technique (Figure 4), with a space of less than 1 mm between graphite electrodes,
a direct current is passed under inert environment argon at a low pressure. An illustration of arc dis-
charge technique is depicted in Figure 3. The carbon anode vaporizes on generation of plasma of very
high temperature on the application of current and the carbon material is deposited alongside other by-
products of carbon at the cathode (Popov et al., 2004; Journet et al., 1998). The production of MWNTs
with diameters ranging from 2 to 20 nm and micrometer-scaled lenght can be achieved (Ebbesen and
Ajayan, 1992). Similarly, SWNTs of above 70% yield and diameter of close to 1.4 nm can be prepared
(Journet et al., 1997).
In the laser ablation technique, the principle is not so different from the arc discharge. The heating
is done in a furnace with the aid of pulsed laser source under inert surrounding. In this technique, high
temperature carbon vapor is generated from the surface of the graphite as illustrated in the Figure 5
(Journet et al., 1997). The carbon vapor is transported by the flowing helium or argon and then collected
on copper-collector as illustrated in Figure 3.
These first two techniques produce high quality carbon nanomaterials in a large amount. However,
some shortcomings have been identified; the reliance on high temperature graphitic surface evaporation

Figure 3. Techniques used in preparation of carbon structures

159
 
Carbon-Based Nanomaterials for Desulfurization

Figure 4. Schematic representation of arc discharge technique for synthesis of carbon nanomaterials

Figure 5. Schematic representation of laser ablation technique for carbon synthesis

160

Carbon-Based Nanomaterials for Desulfurization

of carbon that is not cost effective as this leads to high-energy consumption and the adhering impurities,
which will require further purification of the carbon nanomaterials produced by such methods (Popov
et al., 2004).
In view of the above challenges of the two techniques mentioned previously, chemical vapor deposi-
tion (Figure 6) is the most commonly used technique. CVD ensure a better control of carbon (e.g. CNT)
growth than laser ablation and arc discharge, this makes it a more feasible method (Dai, 2002). It makes
use of hydrocarbons as precursors in the presence of metal catalysts at temperature ranging from 500
to 1000 0C. The hydrocarbons get decomposed at this relatively low temperature and thus the growth of
CNTs as the system cools. This techniques is simpler in that lower temperature is involved because the
precursor is not solid thus consumes less energy (Journet, 1998). Of a vital advantage of CVD worthy
of mentioning is that, it is very versatile. Virtually all the major components involved in the growth can
be switched; catalyst and precursor can be in liquid or solid form, the particular precursor to be used,
possibility of incorporating other materials like nitrogen, temperature and pressure of the reaction etc.
(Nikolav et al., 1999). The choice of catalyst plays important role in decomposition and dispersion of
liquid hydrocarbon as precursor to allow in situ decomposition. It allows for better dispersion if liquid
hydrocarbon is used or in solid form for large-scale synthesis if loaded on large surface area template as
well as a well-patterned growth with nanoparticles (Allen et al., 2009; Hart and Slocum, 2006).
Graphene is commonly prepared by four techniques (Anton et al., 2007; EMTSEV, 2009; Reina,
2009; Lomeda, 2008) listed below:

• Direct sonication of graphite or scoth tape approach (known as mechanical cleavage of graphite);
• Growth on SiC (epitaxial);
• Metal substrates CVD;
• Graphite oxide reduction.

Figure 6. Schematic illustration of carbon vapor deposition (CVD)

161
 
Carbon-Based Nanomaterials for Desulfurization

Some other approaches being reported are; electrochemical process using graphite electrode and
unwrapping of carbon nanotubes (Kosynkin et al., 2009; Liu et al., 2008). The most common approach
for large-scale preparation is the reduction of graphite oxide by, firstly, oxidize graphite with acids then
convert the oxide formed to graphene by reduction. The reduction process can be carried out thermally,
chemically or photo catalytically (McAllister et al., 2007; Lomeda et al., 2008; Williams et al., 2008).

4. EVALUATION

4.1 Properties

Carbon nanomaterial, graphene for example, is a monoatomic layer of carbon atoms that is sp2 hybrid-
ized (Geim and Novoselov, 2007). The good electrical properties in ballistic transport of electrons can be
traced to its 2D pattern (Novoselov et al., 2004). Graphene also possesses large surface-volume ratio, fast
electron transfer mechanism, good tensile strength and very interesting elastic character (Park and Ruoff,
2009; Rao et al., 2009; Yang et al., 2010). A very good stacking is possible with graphene, thus, layers
can be varied from single to many of up to 10 layers and the resulting materials are equally interesting.
Multi-walled carbon nanotubes (MWNTs) comprise of several single-walled nanotubes Single-
walled carbon nanotubes (SWNTs). The one dimensional SWNTs like graphene sheet (0.4 to 2.0 nm
diameter) are rolled-up to form MWNTs (2 to 100 nm diameter) (Baughman et al., 2002; Yang et al.,
2010). Largely, MWNTs can possess several surface morphologies such as hollow tubes, stacked cups,
carbon filaments etc (Kiselev et al.,1998; Iijima, 1991; Delgado et al., 2008; Allen et al., 2008). The
classification of SWNTs can be done based on chiral vectors (ch = na1 + ma2 = (n, m)) where n and m
are integers that correspond to the two graphene vectors (Figure 7) (Avouris, 2002) as shown in Figure
6. The following are few classes:

• Zigzag (m = 0);
• Arm-chair (n = m);
• Chiral (n ≠ m).

The particular class and vectors provide information about electronic properties; if (n – m) gives a
multiple of 3, then the SWNTs of arm-chair type is metallic.
Depending on the diameter of SWNTs, which have inverse proportionality with band gap, SWNTs are
good semiconductors and have metallic character. Normally, MWNTs also have similar characteristics
with SWNTS because the effect of a cylinder on its adjacent cylinder is very minute (Baughman et al.,
2002; Charlier, 2002). However, the lack of definite control of chiralities for individual nano-cylinders
results into MWNTs with SWNTs of different chiralities, thus a metallic properties similar to graphite
(turbostratic) will be observed (Cao, 2004).

4.2 Applications towards Desulfurization

The very unique dimensions of CNTs (1-D) and graphene (2-D) are enabling features for their outstanding
electrical conductivity and stability. They are of good surface chemistry for easy decoration with desired
functionalities, which in turn guaranteed their use in adsorption (desulfurization), electrochemical and

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Carbon-Based Nanomaterials for Desulfurization

Figure 7. Schematic representation of a graphene sheet with unit hexagonal lattice vectors (a1 and a2)

other applications. This include energy generation via fuel cells and photovoltaic (Brandon et al., 2003;
Kauffman et al., 2010), energy storage (batteries, super-capacitors, hydrogen storage) (An et al., 2001)
field-effect transistors (Katz, 2004; Kruger et al., 2010) sensors and biosensors (Kauffman and Star,
2008; Ronkainen et al., 2010; Yang et al., 2010). However, there are challenges, like the non-uniformity
of materials and their hybids (Jacobs et al., 2010), lack detailed understanding of structure as related
to property and possible contaminants from synthetic precursors/catalysts (Dai, 2002; Kruusma, 2007;
Pumera and Miyahara, 2009). These are tasking challenges but provide an avenue for further detailed
studies. In the following sections, the systems and processes used for desulfurization by carbon-based
materials are highlighted.
Graphene and carbon nanotubes are considered good candidates for the removal of liquid phase
aromatic sulfur compounds and of gas phase hydrogen sulfide through the adsorption method by metal
oxide/graphene or nanotube composites. More specifically, the effects of their oxides as substrates are
promising for liquid phase sulfur removal. Their structures that possesses π orbitals can adsorb aromatic
sulfur compounds through π-π interactions.

4.2.1 Testing Systems

• Batch System: Adsorptive desulfurization studies of organosulfur compound removal from naph-
tha (550 ppmS) feed stocks can be carried out in a batch system. The use of adsorbents such as ze-
olites (5A and 13X) and activated carbon is effective. These two adsorbents (carbon and zeolites)
demonstrated a unique performance in their adsorption capabilities; activated carbon has larger
capacity but the percentage of sulfur removal (65% at 80 0C) is lower compare to the zeolitic ad-
sorbent with relatively smaller capacity but a larger percentage of sulfur (100% at room tempera-
ture and 800g adsorbent/L feed) can be removed. In line with these observations and for industrial
application, a two-bed approach gives a better desulfurization process (Salem and Hamid, 1997).

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Carbon-Based Nanomaterials for Desulfurization

• Fixed Bed System: Adsorption studies in a fixed bed set-up can be achieved also with the use
of different adsorbents. Alumina, carbon-supported nickel as well as activated carbon can to a
large extent remove sulfur and nitrogen from diesel feed with aromatics, nitrogen and sulfur com-
pounds. Activated carbon shows better selectivity in removing refractory sulfur and nitrogen com-
pounds especially with alkylated dibenzothiophene (4, 6-DMDBT) (Kim et al., 2006; Ko et al.,
2007). A superior selectivity for nitrogen removal is observed with alumina as compare to the
other two adsorbents. This selectivity with alumina is great when basic nitrogen compound is
involved hydrocarbon streams.

4.2.2 Types of Desulfurization Process

There is no generalized classification for desulfurization techniques. However, some classification can
be made based on the involvement of hydrogen, what happened to sulfur compound during desulfuriza-
tion and whether desulfurization occurs physically or chemically or both. Considering the change that
happened to sulfur compounds; three situations are possible; either the sulfur compounds get decom-
posed and removed, removed from process stream without decomposing or decomposed only. From the
perspective of the hydrogen involvement; a broad classification desulfurization process can be made;
hydrodesulfurization (HDS)-based and non HDS-based groups (Babich and Moulijn, 2003). Hydrogen
is involved in the decomposition of sulfur compounds for all HDS-based processes while the non HDS-
based processes do not involve hydrogen for desulfurization to occur. However, to eliminate sulfur, in
most cases, hydrogen is involved with few exceptions as in the case of selective oxidation. Catalytic
conversion of sulfur compounds and subsequent removal of sulfur is a well-established desulfurization
process. Such processes are hydroprocessing, distillation, extraction, adsorption, oxidation, precipitation,
etc. (Figure 8). Their different combinations have been identified as promising.
During the process of desulfurization, sulfur compounds, for instance, benzothiophene or diben-
zothiophene can be removed from the stream and then decomposed separately in a vessel. A very low
level of sulfur in transportation fuels can be achieved through this process. This process provides an
insight for removing sulfur compounds in fuels through distillation with the help of catalysts. It’s also
possible that some sulfur products (solid or gas) are generated with just decomposition of of organosulfur
compounds with only the hydrocarbons (without sulfur) remaining in the process stream (example is
hydro desulfurization). The last class is just a simple removal of organosulfur compounds from process
stream. This can be done by conversion of the organosulfur compounds to different compounds that can
be removed easily if direct removal is difficult or impossible; however, disposal of the removed sulfur
compounds becomes a great challenge for this type of class. This classification is depicted in Figure 9.

• Extractive Desulfurization: Extractive desulfurization employs the use of solubility as the key
factor for organosulfur removal. Organosulfur compounds tend to be more soluble in some specif-
ic solvents. The sulfur compounds, due to this reason, are transferred from oil feed into the solvent
and therefore hydrocarbons are easily separated with the aid of a separator. The sulfur compound
free hydrocarbons can now be further charged for the next process or discharged as final product.
The mixture of organo-sulfur compounds and the solvent used for it extraction will then be sub-
jected to distillation thus solvent is recovered and can be re-used.

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Carbon-Based Nanomaterials for Desulfurization

Figure 8. Classification of desulfurization processes base on the nature of the process

Figure 9. Classification of desulfurization process according to the changes that occur with sulfur
compounds

Depending on the number of extraction cycles, several solvents have been identified to be suitable
for this purpose with sulfur compound removal of up to 90%. Acetone, glycols, nitrogenous-solvent
(Horri, 1996), ethanol are good solvents for extractive desulfurization because they have their boiling
points different from those of organo-sulfur compounds and relatively cheap (Forte, 1996; Funakoshi
and Aida, 1998).

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Carbon-Based Nanomaterials for Desulfurization

• Desulfurization by Precipitation: Desulfurization can also be achieved via precipitation by

forming an insoluble complex of organosulfur compounds and then eliminating them. When a
pi acceptor (e.g. tetranitro fluorine) is missed with alkylated-DBT (e.g.4, 6-DMDBT) in fuels, an
insoluble complex is formed which can be conveniently removed by filtration and the tetranitro
fluorine is recovered by adsorption process with the aid of suitable adsorbent (Meille et al., 1997;
Milenkovic et al., 1999). This approach does not remove a significant amount of sulfur (< 25%) as
some other hydrocarbons in the feed compete in complex formation (Hernandez-Maldonado and
Yang, 2004a; 2004b; 2004c).
• Bio-Desulfurization (BDS): This process involves the use of micro-organisms (e.g. bacteria) for
removal of organosulfur compound. In this process, the sulfur is removed from its parent com-
pound under mild condition and with availability of oxygen and water without degradation of
carbon structure present. One very vital feature of this process is that it does not require hydrogen
thus a cheaper process than HDS.
• Selective Oxidative Desulfurization: Desulfurization by selective oxidation involves oxidation
of organosulfur compounds and then purification (Aida et al., 2000). Processes like sulphCo and
photochemical desulfurization employ oxidation as a vital operation. Organosulfur compound can
be oxidized selectively and processes like adsorption, distillation or decomposition by heating can
subsequently be used to separate the oxidized oganosulfur compounds from the process stream.

The combination of distillation with selective oxidation is not reported in any literature until date.
Considering the principle involved, the approach is promising since sulfones, sulfuroxides are the products
of oxidation of organosulfur compounds, and they increase their boiling points. (Ford et al., 1997). This
process can therefore be likened to the conventional distillation process provided that only separation
of organosulfur compounds is desired and subsequent treatment will be done separately. However, the
formation of carbonmonoxide and carbon (IV) oxide as by-products and process safety are major issues.

• Adsorptive Desulfurization: This is the use of adsorbents for removing sulfur compounds in the
fuels. The efficiency of this process lies in the ability of the adsorbents to selectively remove the
target sulfur compounds from oil processing stream, durability and regenerability of adsorbent
and capacity for adsorption. Desulfurization via adsorption (ADS) can be broadly classified into
two based on the nature of interaction of the sulfur compounds and the adsorbent: physical and
chemical adsorption. These two classes are briefly explained below.
• Physical Adsorption (Physisorption): In physical adsorptive desulfurization, organosulfur com-
pounds adhere to the surface of the solid adsorbent without chemical reaction thus the hydrocar-
bon refining stream is free of sulfur. Adsorbent regeneration is done by passing suitable solvent on
the adsorbent or heating to get rid of adhered sulfur compounds. Several good materials have been
used as adsorbents, namely; activated carbon, transition metals supported on zeolites and different
metal oxides supported on carbon structures (Ma et al., 2002 and 2005; Velu et al., 2003; Kim et
al., 2006). Both denitrogenation and desulfurization can be done simultaneously using activated
carbon for adsorption process. For every 1 gram of adsorbent, 0.04 g and 0.1 g of nitrogen and sul-
fur can be removed from fuel respectively at a temperature close to the room (Sano et al., 2004a;
2004b). Nitrogen and organosulfur compounds are removed in the first stage of the two-step pro-

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Carbon-Based Nanomaterials for Desulfurization

cess shown in Figure 8. Only very little amount of sulfur is removed at this stage but nitrogen is
removed to a large extent. The HDS step removes most of the sulfur and the final adsorption step
get rid of remnant nitrogen and sulfur present.

Adsorptive desulfurization processes only decrease the concentration of organosulfur compounds in.
Further downstream operation, like hydro processing, needs to be performed at high pressure in order to
remove sulfur to achieve ultra-low diesel fuel. For commercial application, certain process parameters
have to be set at optimum points. These parameters include but not limited to; fuel feed to adsorbent
ratio, particle size of the adsorbent, adsorption cycles, temperature of reactivation etc. To further enhance
desulfurization process, a combined adsorption and HDS (Landau et al., 2008) for denitrogenation and
desulfurization can be performed as illustrated in Figure 10.

• Chemical Adsorption (Chemisorptions): In chemical (reactive) adsorption desulfurization pro-

cess, the sulfur in the fuel feed combines and reacts to form compound such as hydrogen sulfide
(H2S) which is then adsorbed on the surface of the adsorbent (Figure 9). For diesel fuel desulfur-
ization, the reaction to form H2S can occur at temperature of 500-700K and pressure of 19-35 bars
in the presence of transition metal catalyst. In view of this, many hybrid materials of transition
metals supported on carbon, zeolites and several other solid porous materials have been prepared
(Slater et al., 2002; Park et al., 2008; Landau et al., 2008). A simple adsorption scheme together
with reactivation of spent adsorbent is as illustrated in Figure 11.

SUMMARY AND OUTLOOK

Recently, there has been a remarkable growth in research on achieving ultra-low sulfur level in trans-
portation fuels. Several research groups from different academic institutions and industrial research

Figure 10. An illustration of combined adsorption and hydrodesulfurization (two-step) process

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Carbon-Based Nanomaterials for Desulfurization

Figure 11. Simplified adsorptive desulfurization process flow

laboratories have published a great number of rich scientific papers. Lower harmful exhaust emissions
can easily be achieved with ULSD thereby enhancing air quality. The desulfurization of least active
dibenzothiophene (DBT) derivative like 4, 6-DMDBT (sterically hindered) can now be easily achieved
by optimizing certain factors such as; kinetics and thermodynamics, feed quality, inhibitory effects,
catalytic sites, etc. In the future, the need to produce more volume ULSD from low grade feed stocks
like heavy oil and LCO to meet up with the global ULSD demand is pertinent. Other needs like better
calorific value, reduced aromatics content and density are also worthy of expectation. These, are chal-
lenging, but with enormous economic gain. In order to achieve this great milestone, adsorptive method
of desulfurization can play a very big role. ADS does not require hydrogen so it is cheap. It is capable
of desulfurizing organ-sulfur compound (e.g. DBT) preferentially. The ADS can be used to achieve a
sulfur level of less than 10ppm from the initial sulfur content of 500ppm in diesel fuel.

ACKNOWLEDGMENT

The authors would like to acknowledge the support provided by King Abdulaziz City for Science and
Technology (KACST) through the Science & Technology Unit at King Fahd University of Petroleum
& Minerals (KFUPM) for funding this work through project No. 13-PET393-04 as part of the National
Science, Technology and Innovation Plan.

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REFERENCES

Agarwal, P., & Sharma, D. K. (2010). Comparative studies on the biodesulfurization of crude oil with
other desulfurization techniques and deep desulfurization through integrated processes. Energy & Fuels,
24(1), 518–524. doi:10.1021/ef900876j
Aida, T., Yamamoto, D., Iwata, M., & Sakata, K. (2000). Development of oxidative desulfurization
process for diesel. Review on Heteroatom Chemistry, 22, 241–256.
Allen, B. L., Kichambare, P. D., & Star, A. (2008). Synthesis, characterization, and manipulation of nitro-
gen-doped carbon nanotube cups. ACS Nano, 2(9), 1914–1920. doi:10.1021/nn800355v PMID:19206432
Allen, B. L., Shade, C. M., Yingling, A. M., Petoud, S., & Star, A. (2009). Graphitic nanocapsules.
Advanced Materials, 21, 4692–4695.
An, K. H., Kim, W. S., Park, Y. S., Moon, J.-M., Bae, D. J., & Lim, S. C. et al. (2001). Electrochemical
Properties of High-Power Supercapacitors Using Single-Walled Carbon Nanotube Electrodes. Journal
of Advanced Functional. Materials (Basel), 11, 387–392.
Anbia, M., & Parvin, Z. (2011). Desulfurization of fuels by means of a nanoporous carbon adsorbent.
Chemical Engineering Research & Design, 89(66A), 641–647. doi:10.1016/j.cherd.2010.09.014
Anton, N. S., Mehdi, M. Y., Romaneh, J., Ouseph, P. J., Cohn, R. W., & Sumanasekera, G. U. (2007).
Electrostatic deposition of graphene. Nanotechnology, 18, 13530–13534. PMID:21730375
Atanasova, P., Vladov, Ch., Halachev, T., Fierro, J. L. G., & López, A. A. (1995). Influence on the phos-
phorus concentration and the method of preparation on the hydrodesulfurization activity of P-Ni-W/
alumina catalysts. Bulletin des Sociétés Chimiques Belges, 104(4), 219–223.
Avouris, P. (2002). Molecular electronics with carbon nanotubes. Accounts of Chemical Research, 35(12),
1026–1034. doi:10.1021/ar010152e PMID:12484790
Babich, I. V., & Moulijn, J. A. (2003). Science and technology of novel processes for deep desulfuriza-
tion of oil refinery streams: A review. Fuel, 82(6), 607–631. doi:10.1016/S0016-2361(02)00324-1
Babich, I. V., & Moulijn, J. V. (2003). Science and technology of novel processes for deep desulfurization
of oil refinery streams: A review. Fuel, 82(6), 607–631. doi:10.1016/S0016-2361(02)00324-1
Bai, S., & Shen, X. (2012). Graphene-inorganic nanocomposites. Royal Society of Chemistry Advances,
2, 64–98.
Baker, R. T. K. (1995). A review of in-situ electron microscopy studies of metal/metal oxide graphite
interactions. Journal of Adhesion and Adhensives, 52(1-4), 13–40.
Baker, R. T. K., & Chludzinski, J. J. Jr. (1981). Catalytic gasification of graphite by chromium and copper
in oxygen, steam and hydrogen. Carbon, 19(2), 75–82. doi:10.1016/0008-6223(81)90110-X
Baughman, R. H., Zakhidov, A. A., & de Heer, W. A. (2002). Carbon nanotubes--the route towards ap-
plications. Science, 297(5582), 787–792. doi:10.1126/science.1060928 PMID:12161643

169
 
Carbon-Based Nanomaterials for Desulfurization

Bernier, P., & Ajayan, P. M. (1994). Application of Carbon Nanotubes as Supports in Heterogeneous
Catalysis. Journal of the American Chemical Society, 116(17), 7935–7936. doi:10.1021/ja00096a076
Bhatia, S., & Sharma, D. K. (2006). Emerging role of bio-refining of heavier crude oils and integra-
tion of bio-refining with petroleum refineries in the future. Petroleum Science and Technology, 24(10),
1125–1159. doi:10.1080/10916460600817447
Blanco-López, M. C., Gutiérrez-Fernández, C., Lobo-Castañón, M. J., Miranda-Ordieres, A. J., Tuñón-
Blanco, P. (2004). Electrochemical sensing with electrodes modified with molecularly imprinted polymer
films. Analytical and Bioanalytical Chemistry, 378(8), 1922 –1928.
Brandon, N. P., Skinner, S., & Steele, B. C. (2003). Recent advances in materials for fuel cells. Annual
Review of Materials Research, 33(1), 183–213. doi:10.1146/annurev.matsci.33.022802.094122
Cao, G. (2004). Nanostructures and Nanomaterials: Synthesis, properties and applications. United
Kingdom: Imperial College. doi:10.1142/p305
Charlier, J. C. (2002). Defects in carbon nano tubes. Accounts of Chemical Research, 35(12), 1063–1069.
doi:10.1021/ar010166k PMID:12484794
Cheng, G., & Guo, T. (2002). Surface segregation in Ni/Co bimetallic nanoparticles produced in
single-walled carbon nanotube synthesis. The Journal of Physical Chemistry B, 106(23), 5833–5839.
doi:10.1021/jp025530r
Cui, R. L., Zhang, Y., Wang, J. Y., Zhou, W. W., & Li, Y. (2010). Comparison between copper and iron as
catalyst for chemical vapor deposition of horizontally aligned ultralong single-walled carbon nanotubes
on silicon substrates. Journal of Physical Chemistry, 114(37), 15547–15552.
Daenen, M., De Fouw, R., Hamers, B., Janssen, P., Schouteden, K., & Veld, M. (2003). The Wondrous
World of Carbon Nanotubes. A Review of Current Carbon Nanotube Technologies. Eindhoven Univer-
sity of Technology, 89.
Dai, H. (2002). Carbon nanotubes: Opportunities and challenges. Surface Science, 500(1-3), 218–241.
doi:10.1016/S0039-6028(01)01558-8
Daimler–Chrysler AG. (2000). Method for desulfurization engine fuel on board a motor vehicle // W.O
2000/20531.
De Volder, M. F. L., Tawfick, S. H., Baughman, R. H., & Hart, A. J. (2013). Carbon nanotubes: Pres-
ent and future commercial applications. Science, 339(6119), 535–539. doi:10.1126/science.1222453
PMID:23372006
Deck, C. P., & Vecchio, K. (2006). Prediction of carbon nanotube growth success by the analysis of
carbon-catalyst binary phase diagrams. Carbon, 44(2), 267–275. doi:10.1016/j.carbon.2005.07.023
Delgado, J. L., Herranz, M. A., & Martin, N. (2008). The nano-forms of carbon. Journal of Materials
Chemistry, 18(13), 1417–1426. doi:10.1039/b717218d

170

Carbon-Based Nanomaterials for Desulfurization

Delitala, C., Cadoni, E., Delpiano, D., Meloni, D., Melis, S., & Ferino, I. (2008). Liquid-phase thiophene
adsorption on MCM-22 zeolite and activated carbon. Microporous and Mesoporous Materials, 110(2-3),
197–215. doi:10.1016/j.micromeso.2007.06.018
Ding, F., Larsson, P., Larsson, J. A., Ahuja, R., Duan, H. M., Rosen, A., & Bolton, K. (2008). The im-
portance of strong carbon-metal adhesion for catalytic nucleation of single-walled carbon nanotubes.
Nano Letters, 8(2), 63–68. doi:10.1021/nl072431m PMID:18162001
Ding, M., Tang, Y., & Star, A. (2012). Understanding Interfaces in Metal–Graphitic Hybrid Nanostruc-
tures. The Journal of Physical Chemistry Letters, 4(1), 147–160. doi:10.1021/jz301711a
Dribinskii, A. V., Tarasevich, M. R., & Kazarinov, V. E. (1989). Electrocatalysis on carbon materials.
Materials Chemistry and Physics, 22(3-4), 377–400. doi:10.1016/0254-0584(89)90006-0
Ebbesen, T. W., & Ajayan, P. M. (1992). Large scale synthesis of carbon nanotubes. Nature, 358(6383),
220–222. doi:10.1038/358220a0
Ebbesen, T. W., Hiura, H., Bisher, M. E., Treacy, M. M. J., Shreeve-Keyer, J. L., & Haushalter, R. C. (1996).
Decoration of carbon nano tubes. Advanced Materials, 8(2), 155–157. doi:10.1002/adma.19960080212
Edwards, R. S., & Coleman, K. S. (2013). Graphene film growth on polycrystalline metals. Accounts of
Chemical Research, 46(1), 23–30. doi:10.1021/ar3001266 PMID:22891883
Emtsev, K. V., Bostwick, A., Horn, K., Jobst, J., Kellogg, G. L., & Ley, L. et al. (2009). Towards wafer-
size graphene layers by atmospheric pressure graphitization ofsilicon carbide. Nature Materials, 8(3),
203–207. doi:10.1038/nmat2382 PMID:19202545
Ford, J. F., Rayne, T. A., & Adlington, D. G. (1967). Desulfurization of hydrocarbons using oxidative
and hydro-treatments. US Patent, 3341448.
Forte, P. (1996). Process for the Removal of Sulfur from Petroleum Fractions. US Patent, 5582714.
Funakoshi, I., & Aida, T. (1998). Process for recovering organic sulfur compounds from fuel oil. US
Patent, 5753102.
Gates, B. C., & Tropsoe, H. (1997). Reactivity in deep catalytic hydro-desulfurization: Challenges,
opportunities, and the importance of 4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene.
Polyhedron, 16(18), 3213–3217. doi:10.1016/S0277-5387(97)00074-0
Geim, A. K. (2009). Graphene: Status and prospects. Science, 324(5934), 1530–1534. doi:10.1126/
science.1158877 PMID:19541989
Geim, A. K., & Novoselov, K. S. (2007). The rise of graphene. Nature Materials, 6(3), 183–191.
doi:10.1038/nmat1849 PMID:17330084
Hart, A. J., & Slocum, A. H. (2006). Rapid growth and flow-mediated nucleation of millimeter-scale
aligned carbon nanotube structures from a thin-film catalyst. The Journal of Physical Chemistry B,
110(16), 8250–8257. doi:10.1021/jp055498b PMID:16623503

171
 
Carbon-Based Nanomaterials for Desulfurization

Hernandez, Y., Nicolosi, V., Lotya, M., Blighe, F. M., Sun, Z., & De, S. et al. (2008). High-yield pro-
duction of graphene by liquid-phase exfoliation of graphite. Nature Nanotechnology, 3(9), 563–568.
doi:10.1038/nnano.2008.215 PMID:18772919
Hernandez-Maldonado, A. J., Stamatis, S. D., Yang, R. T., He, A. Z., & Cannella, W. (2004). New sor-
bents for desulfurization of diesel fuels via pi-complexation: Layered beds and regeneration. Industrial
& Engineering Chemistry Research, 43(3), 769–776. doi:10.1021/ie034108+
Hernandez-Maldonado, A. J., & Yang, R. T. (2003). Desulfurization of commercial liquid fuels by
selective adsorption via pi-complexation with Cu(I)-Y zeolite. Industrial & Engineering Chemistry
Research, 423103–423110.
Hernandez-Maldonado, A. J., & Yang, R. T. (2004a). Desulfurization of diesel fuels by adsorption via
pi-complexation with vapor phase exchanged (VPIE) Cu(I)-Y zeolites. Journal of the American Chemi-
cal Society, 126(4), 992–993. doi:10.1021/ja039304m PMID:14746446
Hernandez-Maldonado, A. J., & Yang, R. T. (2004b). Desulfurization of diesel fuels via pi-complexation
with nickel(JI)-exchanged X- and Y-zeolites. Industrial & Engineering Chemistry Research, 43(4),
1081–1089. doi:10.1021/ie034206v
Hernandez-Maldonado, A. J., & Yang, R. T. (2004c). New sorbents for desulfurization of diesel fuels
via pi-complexation. The American Institute of Chemical Engineers Journal, 50, 791–801. doi:10.1002/
aic.10074
Horii, Y., Onuki, H., Doi, S., Mori, T., Takatori, T., Sato, H., et al. (1996). Desulfurization and denitra-
tion of light oil by extraction. US Patent, 5494572.
Hsu, W. K.; Terrones, M.; Hare, J. P.; Terrones, H.; Kroto, H. W.; Walton, D. R. M. Electrochemical
formation of carbon nanostructures. Chemical Physics Lettters, 262, 161-166.
Huang, X., Qi, X., Boey, F., & Zhang, H. (2012). Graphene-based composites. Chemical Society Reviews,
41(2), 666–686. doi:10.1039/C1CS15078B PMID:21796314
Iijima, S. (1991). Helical microtubules of graphitic carbon. Nature, 354(6348), 56–58. doi:10.1038/354056a0
Irvine, R. L. (1998). Process for desulfurizing gasoline and hydrocarbon feedstocks. US Patent, 5730860.
Irvine, R. L., Benson, B. A., Varraveto, D. M., & Frye, R. A. NPRA (1999, March 21-23). Proceedings
of the Annual Meeting, AM-99-42, San Antonio, Texas.
Irvine, R. L., Varraveto, D. M. (1999). Adsorption process for nitrogen and sulfur. Petroleum Technol-
ogy Quarter Summer 3, 37- 40.
Ivanov, V., Fonseca, A., Nagy, J. B., Lucas, A., Lambin, P., Bernaerts, D., & Zhang, X. B. (1995).
Catalytic production and purification of nanotubulles having fullerene-scale diameters. Carbon, 33(12),
1727–1738. doi:10.1016/0008-6223(95)00132-1
Iwamoto, R., & Grimblot, J. (1997). Acidity and hydrogenation properties of Mo-P-alumina catalysts
prepared by a sol-gel method. Journal of Catalysis, 172(1), 252–255. doi:10.1006/jcat.1997.1855

172

Carbon-Based Nanomaterials for Desulfurization

Jacobs, C. B., Peairs, M. J., & Venton, B. J. (2010). Carbon nanotubes electrochemical sensors for bio-
molecules. Analytica Chimica Acta, 662(2), 105–127. doi:10.1016/j.aca.2010.01.009 PMID:20171310
Jourdain, V., & Bichara, C. (2013). Current understanding of the growth of carbon nanotubes in catalytic
chemical vapour deposition. Carbon, 58, 2–39. doi:10.1016/j.carbon.2013.02.046
Journet, C., Bernier, P. (n. d.). Production of carbon nanotubes. Journal of Applied Physics A, 67, 1-9.
Journet, C., Maser, W. K., Bernier, P., Loiseau, A., de la Chapelle, M. L., & Lefrant, S. et al. (1997).
Large-scale production of single-walled carbon nanotubes by the electric-arc technique. Nature, 388(6644),
756–758. doi:10.1038/41972
Katz, H. E. (2004). Chemically Sensitive Field-Effect Transistors and Chemiresistors: New Materi-
als and Device. Structures. Journal of Electroanalytical Chemistry, 16(22), 1837–1842. doi:10.1002/
elan.200403071
Kauffman, D. R., Shade, C. M., Uh, H., Petoud, S., & Star, A. (2009). Decorated carbon nanotubes with
unique oxygen sensitivity. Nature Chemistry, 1(6), 500–506. doi:10.1038/nchem.323 PMID:21378918
Kauffman, D. R., & Star, A. (2008). Carbon Nanotube Gas and Vapor Sensors. Angewandte Chemmie
International Edition, 47(35), 6550-6570.
Kauffman, D. R., Tang, Y., Kichambare, P. D., Jackovitz, J. F., & Star, A. (2010). Long-Term Perfor-
mance of Pt-Decorated Carbon Nanotube Cathodes in Phosphoric Acid Fuel Cells. Energy & Fuels,
24(3), 1877–1881. doi:10.1021/ef100013v
Kim, J. H., Ma, X., Zhou, A., & Song, C. (2006). Ultra clean desulfurization and denitrogenation of
diesel fuel by selective adsorption over three different adsorbents: A study on adsorptive selectivity and
mechanism. Catalysis Today, 111(1-2), 74–83. doi:10.1016/j.cattod.2005.10.017
Kinoshita, K., & Bett, J. A. S. (1973). Potentiodynamic analysis of surface oxides on carbon blacks.
Carbon, 11(4), 403–411. doi:10.1016/0008-6223(73)90080-8
Kiselev, N. A., Sloan, J., Zakharov, D. N., Kukovitskii, E. F., Hutchison, J. L., Hammer, J., & Kotosonov,
A. S. (1998). Carbon nanotubes from polyethylene precursors: Structure and structural changes as re-
vealed by HREM. Carbon, 36, 1149–1157. doi:10.1016/S0008-6223(98)00092-X
Kongkanand, A., Martínez Domínguez, R., & Kamat, P. V. (2007). Single wall carbon nanotube scaffolds
for photoelectrochemical solar cells. capture and transport of photogenerated electrons. Nano Letters,
7(3), 676–680. doi:10.1021/nl0627238 PMID:17309316
Kosynkin, D. V., Higginbotham, A. L., Sinitskii, A., Lomeda, J. R., Dimiev, A., Price, B. K., & Tour, J.
M. (2009). Mechanically Assisted Exfoliation and Functionalization of Thermally Converted Graphene
Sheets. Nature, 458, 872–876. doi:10.1038/nature07872 PMID:19370030
Kruger, M., Buitelaar, M. R., Nussbaumer, T., Schonenberger, C., & Forro, L. (2001). Electrochemical
carbon nanotube field-effect transistor. Applied Physics Letters, 78(9), 1291–1293. doi:10.1063/1.1350427

173
 
Carbon-Based Nanomaterials for Desulfurization

Kruusma, J., Mould, N., Jurkschat, K., Crossley, A., & Banks, C. E. (2007). Single walled carbon
nanotubes contain residual iron oxide impurities which can dominate their electrochemical activity.
Electrochemistry Communications, 9(9), 2330–2333. doi:10.1016/j.elecom.2007.06.024
Kumar, S., Srivastava, V. C., & Badoni, R. P. (2012). Oxidative desulfurization by chromium promoted
sulfated zirconia. Fuel Processing Technology, 93(1), 18–25. doi:10.1016/j.fuproc.2011.08.017
Kymakis, E., & Amaratunga, G. (2007). Single-wall carbon nanotube/conjugated polymer photovoltaic
devices. Applied Physics Letters, 80(1), 112–114. doi:10.1063/1.1428416
Lam, V., Li, G., Song, C., Chen, J., Fairbridge, C., Hui, R., & Zhang, J. (2012). A review of electrochemi-
caldesulfurization technologies for fossil fuels. Fuel Processing Technology, 98, 30–38. doi:10.1016/j.
fuproc.2012.01.022
Laplaze, D., Bernier, P., Maser, W. K., Flamant, G., Guillard, T., & Loiseau, A. (1998, January). Carbon
nanotubes: The solar approach. Carbon, 36(5-6), 685–688. doi:10.1016/S0008-6223(98)00025-6
Lee, C., Wei, X., Kysar, J. W., & Hone, J. (2008). Measurement of the elastic properties and intrinsic Strength
of monolayer graphene. Science, 321(5887), 385–388. doi:10.1126/science.1157996 PMID:18635798
Lemaire, M. (1999). Energy & Fuels, 13, 881. doi:10.1021/ef980262a
Li, D.-C., Dai, L., Huang, S., Mau, A. W. H., & Wang, Z. L. (2000). Structure and growth of aligned
carbon nanotube films by pyrolysis. Chemical Physics Letters, 316(5-6), 349–355. doi:10.1016/S0009-
2614(99)01334-2
Li, J. (2009). In P. Serp & J. L. Figueiredo (Eds.), Carbon Materials for Catalysis (pp. 507–533).
Li, W. Z., Xie, S. S., Qian, L. X., Chang, B. H., Zou, B. S., & Zhou, W. Y. et al. (1996). Large scale syn-
thesis of aligned carbon nanotubes. Science, 274(5293), 1701–1703. doi:10.1126/science.274.5293.1701
PMID:8939858
Li, X., Cai, W., An, J., Kim, S., Nah, J., & Yang, D. et al. (2009). Large-area synthesis of high-quality
anduniform graphene films on copper foils. Science, 324(5932), 1312–1314. doi:10.1126/science.1171245
PMID:19423775
Li, X., Qin, Y., Picraux, S. T., & Guo, Z.-X. (2011). Noncovalent assembly of carbon nanotube-inorganic
hybrids. Journal of Materials Chemistry, 21(21), 7527–7547. doi:10.1039/c1jm10516g
Li, Y., Cui, R. L., Ding, L., Liu, Y., Zhou, W. W., & Zhang, Y. et al. (2010). How catalysts affect the
growth of single-walled carbon nanotubes on substrates. Advanced Materials, 22(13), 1508–1515.
doi:10.1002/adma.200904366 PMID:20437500
Liu, N., Luo, F., Wu, H., Liu, Y., Zhang, C., & Chen, J. (2008). One-step ionic-liquid-assisted elec-
trochemical synthesis of ionic-liquid-functionalized graphene sheets directly from graphite. Advanced
Functional Materials, 18(10), 1518–1525. doi:10.1002/adfm.200700797
Lomeda, J. R., Doyle, C. D., Kosynkin, D. V., Hwang, W. F., & Tour, J. M. (2008). Diazonium func-
tionalization of surfactant-wrapped chemically converted graphene sheets. Journal of the American
Chemical Society, 130(48), 16201–16206. doi:10.1021/ja806499w PMID:18998637

174

Carbon-Based Nanomaterials for Desulfurization

Loo, A. H., Bonanni, A., & Pumera, M. (2013). Biorecognition on graphene: Physical, covalent, and
affinity immobilization methods exhibiting dramatic differences. Asian Journal of Chemistry, 8(1),
198–203. doi:10.1002/asia.201200756 PMID:23090869
Ma, X., & Schobert, H. H. (2000). Molecular simulation on hydrodesulfurization of Thiophenic compounds
over MoS2 using ZINDO. Journal of Molecular Catalysis A Chemical, 160(2), 409–427. doi:10.1016/
S1381-1169(00)00278-8
Ma, X., Sun, L., & Song, C. (2002). A new approach to deep desulfurization of gasoline, diesel fuel
and jet fuel by selective adsorption for ultra-clean fuels and for fuel cell applications. Catalysis Today,
77(1-2), 107–116. doi:10.1016/S0920-5861(02)00237-7
Ma, X., Velu, S., Kim, J. H., & Song, C. (2005). Deep desulfurization of gasoline by selective adsorption
over solid adsorbents and impact of analytical methods on ppm level sulfur quantification for fuel cell
applications. Applied Catalysis B: Environmental, 56(1-2), 137–147. doi:10.1016/j.apcatb.2004.08.013
Matsui, M., Horiba, T., Yamamoto, O., Takeda, Y., Seki, N., & Imanishi, N. (2013). Carbon paper
substrate for silicon-carbon composite anodes in lithium-ion batteries. Journal of Power Sources, 241,
744–750. doi:10.1016/j.jpowsour.2013.05.090
Mattevi, C., Kim, H., & Chhowalla, M. (2011). A review of chemical vapour deposition of grapheme
on copper. Journal of Materials Chemistry, 21(10), 3324–3334. doi:10.1039/C0JM02126A
Mc Allister, M. J., Li, J.-L., Adamson, D. H., Schniepp, H. C., Abdala, A. A., & Liu, J. et al. (2007).
Single sheet functionalized graphene by oxidation and thermal expansion of graphite. Chemistry of
Materials, 19(18), 4396–4404. doi:10.1021/cm0630800
McEuen, P. L., Fuhrer, M. S., & Park, H. K. (2002). Single-walled carbon nanotube electronics. IEEE
Transactions on Nanotechnology, 1(1), 78–85. doi:10.1109/TNANO.2002.1005429
Meille, V., Shulz, E., Vrinat, M., & Lemaire, M. (1997). Hydrodesulfurization of alkyldibenzothiophenes
over a NiMo/Al2O3 catalyst: Kinetics and mechanism. Journal of Catalysis, 170(1), 29–36. doi:10.1006/
jcat.1997.1732
Milenkovic, A., Shulz, E., Meille, V., Lofferda, D., Forissier, M., Vrinat, M., & Sautet, P. (2004). Charge
transfer complexes between tetranitrofluorenone and polyaromatic compounds from gasoil: A combined
DFT and experimental study. Physical Chemistry, 6, 1169–1180.
Molina-Ontoria, A., Chaur, M. N., Plonska-Brzezinska, M. E., & Echegoyen, L. (2013a). Preparation and
characterization of soluble carbon nano-onions by covalent functionalization, employing a Na-K alloy.
Chemical Communications (Cambridge), 49(24), 2406–2408. doi:10.1039/c3cc39077b PMID:23411670
Nagai, M., Goto, Y., Ishii, H., & Omi, S. (2000). XPS and TPSR study of nitrided molybdena-alumina
catalyst for the hydrodesulfurization of dibenzothiophene. Applied Catalysis A, General, 192(2), 189–199.
doi:10.1016/S0926-860X(99)00341-5
Naidich, J. V. (1981). The wettability of solids by liquid metals. Progress in Surface Membrane Science,
14, 353–484. doi:10.1016/B978-0-12-571814-1.50011-7

175
 
Carbon-Based Nanomaterials for Desulfurization

Nikolaev, P., Smalley, R. E., Bronikowski, M. J., Bradley, R. K., Rohmund, F., Colbert, D. T., & Smith,
K. A. (1999). Gas-phase catalytic growth of single-walled carbon nanotubes from carbon monoxide.
Chemical Physics Letters, 313(1-2), 91–97. doi:10.1016/S0009-2614(99)01029-5
Novoselov, K. S., Geim, A. K., Morozov, S. V., Jiang, D., Zhang, Y., & Dubonos, S. V. (2004). Electric
field effect in atomically thin carbon films. Science, 306(5696), 666–669. doi:10.1126/science.1102896
PMID:15499015
Park, J. G., Ko, C. H., Yi, K. B., Park, J. H., Han, S. S., Cho, S. H., & Kim, J. N. (2008). Reactive ad-
sorption of sulfur compounds in diesel on nickel supported on mesoporous silica. Applied Catalysis B:
Environmental, 81(3-4), 244–250. doi:10.1016/j.apcatb.2007.12.014
Park, S., & Ruoff, R. S. (2009). Chemical methods for the production of graphenes. Nature Nanotech-
nology, 4(4), 217–224. doi:10.1038/nnano.2009.58 PMID:19350030
Perathoner, S., Gangeri, M., Lanzafame, P., & Centi, G. (2007). Nanostructured electrocatalytic Pt-
carbon materials for fuel cells and CO2conversion. Kinetics and Catalysis, 48(6), 877–883. doi:10.1134/
S0023158407060171
Popov, V. N. (2004). Carbon nanotubes: Properties and applications. Materials Science and Engineering
R Reports, 43(3), 61–102. doi:10.1016/j.mser.2003.10.001
(2001). Quality requirements for liquid fuels [in Estonian]. State Announcer. App., 66, 2765–2775.
Rana, M. S., Sa’mano, V., Ancheyta, J., & Diaz, J. A. I. (2007). A review of recent advances on pro-
cessing technologies for upgrading of heavy oils and residual. Fuel, 86(9), 1216–1231. doi:10.1016/j.
fuel.2006.08.004
Rao, C. N. R., Sood, A. K., Subrahmanyam, K. S., & Govindaraj, A. (2009). Graphene: The new two-
dimensional nanomaterial. Angewandte Chemie International Edition, 48(42), 7752–7777. doi:10.1002/
anie.200901678 PMID:19784976
Reina, A., Jia, X., Ho, J., Nezich, D., Son, H., & Bulovic, V. et al. (2009). Large area, few-layer graphene
films on arbitrary substrates by chemical vapor deposition. Nano Letters, 9(1), 30–35. doi:10.1021/
nl801827v PMID:19046078
Ronkainen, N. J., Halsall, H. B., & Heineman, W. R. (2010). Electrochemical biosensors. Chemical
Society Reviews, 39(5), 1747–1763. doi:10.1039/b714449k PMID:20419217
Salem, A. B. S. H. (1994). Naphtha desulfurization by adsorption. Industrial & Engineering Chemistry
Research, 33(2), 336–340. doi:10.1021/ie00026a025
Salem, A. B. S. H., & Hamid, H. S. (1997). Removal of sulfur compounds from naphtha solutions using
solid adsorbents. Chemical Engineering & Technology, 20(5), 342–347. doi:10.1002/ceat.270200511
Salernitanoa, E., Giorgi, L., & Dikonimos, M. (2014). Direct growth of carbon nanofibers on carbon-based
substrates as integrated gas diffusion and catalysts layer for polymer electrolytes fuel cells. International
Journal of Hydrogen Energy, 39(27), 15005–15016. doi:10.1016/j.ijhydene.2014.07.060

176

Carbon-Based Nanomaterials for Desulfurization

Sano, Y. (2004a). Adsorptive removal of sulfur and nitrogen species from a straight run gas oil over ac-
tivated carbons for its deep hydrodesulfurization. Applied Catalysis B: Environmental, 49(4), 219–225.
doi:10.1016/j.apcatb.2003.12.007
Sano, Y., Choi, K. K., Korai, Y., & Mochida, I. (2004b). Selection further activation of activated carbons
for removal of nitrogen species in gas oil as a pretreatment for its deep hydrodesulfurization. Energy &
Fuels, 18(3), 644–651. doi:10.1021/ef034080e
Sano, Y., Sugahara, K., Choi, K. H., Korai, Y., & Mochida, I. (2005). Two-step adsorption process for
deep desulfurization of diesel oil. Fuel, 84(7-8), 903–910. doi:10.1016/j.fuel.2004.11.019
Savage, D. W., Kaul, B. K., Dupre, G. D., O’Bara, J. T., Wales, W. E., & Ho, T. C. (1995). Deep desul-
furization of distillate fuels. US Patent, 5454933.
Schlapbach, L., & Züttel, A. (2001). Hydrogen-storage materials for mobile applications. Hydrogen-storage
materials for mobile applications. Nature, 414(6861), 353–358. doi:10.1038/35104634 PMID:11713542
Seah, C. M., Chai, S. P., & Mohamed, A. R. (2014). Mechanisms of graphene growth by chemical vapour
deposition on transition metals. Carbon, 70, 1–21. doi:10.1016/j.carbon.2013.12.073
Seredych, M., Lison, J., Jans, U., & Bandosz, T. J. (2009). Textural and chemical factors affecting ad-
sorption capacity of activated carbon in highly efficient desulfurization of diesel fuel. Carbon, 47(10),
2491–2500. doi:10.1016/j.carbon.2009.05.001
Shafi, R., & Hutchings, G. J. (2000). Hydrodesulfurization of hindered dibenzothiophenes:an overview.
Catalysis Today, 59(3-4), 423–442. doi:10.1016/S0920-5861(00)00308-4
Shin, W. H., Jeong, H. M., Kim, B. G., Kang, J. K., & Choi, J. W. (2012). Nitrogen-doped multi-walled
carbon nanotubes for lithium storage with extremely high capacity. Nano Letters, 12(5), 2283–2288.
doi:10.1021/nl3000908 PMID:22452675
Sinnott, S. B., & Andrews, R. (2001). Carbon nanotubes: Synthesis, properties and applications. Critical
Reviews in Solid State and Material Sciences, 26(3), 145–249. doi:10.1080/20014091104189
Song, C. (2003). An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel
fuel and jet fuel. Catalysis Today, 86(1-4), 211–263. doi:10.1016/S0920-5861(03)00412-7
Stephanie, N. S., Goubert, R., Xiuling, Z., & Andrzej, W. (2010). Synthesis and characterization of carbon-
supported transition metal oxide nanoparticles-Cobalt porphyrin as catalysts for electroreduction of oxy-
gen in acids. Electrochemistry Communications, 12(11), 1457–1461. doi:10.1016/j.elecom.2010.06.004
Sundaraman, R., Peduzzi, E., & Song, C. (2009). Catalytic cracking of oxidized sulfur compounds in
gas oil stream. Prepr Pap Am Chem Soc Div Fuel Chem, 54(2), 954–955.
Svoboda, K., Lin, W., Hannes, J., Korbee, R., & van den Beek, C. M. (1994). Low temperature flue
gas desulfurization by alumina-CaO regenerable sorbents. Fuel, 73(7), 1144–1150. doi:10.1016/0016-
2361(94)90251-8
Terrones, M. (2003). Science and technology of twenty-five century: Synthesis, properties and applica-
tions. Annual Review of Materials Research, 33, 419. doi:10.1146/annurev.matsci.33.012802.100255

177
 
Carbon-Based Nanomaterials for Desulfurization

Thess, A., Smalley, R. E., Roland, L., Nikolaev, P., Dai, H., & Petit, P. et al. (1996). Crystalline ropes of me-
tallic carbon nanotubes. Science, 273(5274), 483–487. doi:10.1126/science.273.5274.483 PMID:8662534
Velu, s., Ma, X., Song, C. (2003). Selective adsorption for removing sulfur from jet fuel over zeolite
based adsorbents. Industrial Engineering and Chemical Research, 42(21), 5293–5304.
Viculis, L. M., Mack, J. J., & Kaner, R. B. (2003, February 28). A chemical route to carbon nanoscrolls.
Science, 299(5611), 1361. doi:10.1126/science.1078842 PMID:12610297
Wang, Y. H., Yang, F. H., Yang, R. T., Heinzel, J. M., & Nickens, A. D. (2006). Desulfurization of high
sulfur jet fuel by π-Complexation with copper and palladium halide sorbents. Industrial & Engineering
Chemistry Research, 45(22), 7649–7655. doi:10.1021/ie060922w
Wang, Y. H., Yang, R. T., & Heinzel, J. M. (2008). Desulfurization of jet fuel by π-complexation with
metal halides supported on MCM-41 and SBA-15 mesoporous materials. Chemical Engineering Science,
63(2), 356–365. doi:10.1016/j.ces.2007.09.002
Williams, G., Seger, B., & Kamat, P. V. (2008). TiO2-graphene nanocomposites. UV-assisted photocata-
lytic reduction of graphene oxide. ACS Nano, 2(7), 1487–1491. doi:10.1021/nn800251f PMID:19206319
Xie, X., Ju, L., Feng, X., Sun, Y., Zhou, R., & Liu, K. et al. (2009). Controlled fabrication of high-quality
carbon nanoscrolls from monolayer graphene. Nano Letters, 9(7), 2565–2570. doi:10.1021/nl900677y
PMID:19499895
Xue, Y. Z., Wu, B., Guo, Y. L., Huang, L. P., Jiang, L., & Chen, J. Y. et al. (2011). Synthesis of large-
area,few-layer graphene on iron foil by chemical vapor deposition. Nano Research, 4(12), 1208–1214.
doi:10.1007/s12274-011-0171-4
Yang, F. H., Hernandez-Maldonado, A. J., & Yang, R. T. (2004). Selective adsorptipion of organosulfur
compounds from transportation fuels by π-complexation. Separation Science and Technology, 39(8),
1717–1731. doi:10.1081/SS-120035937
Yang, R. T. (2003). Adsorbents: Fundamentals and Applications. New York: Wiley. doi:10.1002/047144409X
Yang, R. T., Hernandez-Maldonado, A. J., & Yang, F. H. (2003). Desulfurization of transportation fu-
els with zeolites under ambient conditions. Science, 301(5629), 79–81. doi:10.1126/science.1085088
PMID:12843388
Yang, R. T., Takahashi, A., & Yang, F. H. (2001). New sorbents for desulfurization of liquid fuels by pi-
complexation. Industrial & Engineering Chemistry Research, 40(26), 6236–6239. doi:10.1021/ie010729w
Yang, W., Ratinac, K. R., Ringer, S. P., Thordarson, P., Gooding, J. J., & Braet, F. (2010). Carbon nano-
materials in biosensors: Should you use nanotubes or graphene? Angewandte Chemie International
Edition, 49(12), 2114–2138. doi:10.1002/anie.200903463 PMID:20187048
Yang, X., Cao, C., Klabunde, K. J., Hohn, K. L., & Erickson, L. E. (2007). Adsorptive desulfurization
with xerogel-derived zinc-based nanocrystalline aluminum oxide. Industrial & Engineering Chemistry
Research, 46(14), 4819–4823. doi:10.1021/ie0701928

178
 
Carbon-Based Nanomaterials for Desulfurization

Yoshida, H., Shimizu, T., Uchiyama, T., Kohno, H., Homma, Y., & Takeda, S. (2009). Atomic-scaleanalysis
on the role of molybdenum in iron-catalyzed carbon nanotube growth. Nano Letters, 9(11), 3810–3815.
doi:10.1021/nl9019903 PMID:19731921
Yuan, L., Saito, K., Hu, W., & Chen, Z. (2001). Ethylene flame synthesis of well-aligned multi-walled
carbon nanotubes. Chemical Physics Letters, 346(1-2), 23–28. doi:10.1016/S0009-2614(01)00959-9
Yudasaka, M., Komatsu, T., Ichihashi, T., & Iijima, S. (1997). Single wall carbon nanotube formation by
laser ablation using double-targets of carbon and metal. Chemical Physics Letters, 278(1-3), 102–106.
doi:10.1016/S0009-2614(97)00952-4
Zhang, Q., Huang, J. Q., Qian, W. Z., Zhang, Y. Y., & Wei, F. (2013). The Road for Nanomaterials Indus-
try: A Review of Carbon Nanotube Production, Post-Treatment, and Bulk Applications for Composites
and Energy Storage. Small, 9(8), 1237–1265. doi:10.1002/smll.201203252 PMID:23580370
Zhang, Q., Yu, Z., Du, P., & Su, C. (2010). Carbon nanomaterials used as conductive additives in lithium
ion batteries. Recent Patents on Nanotechnology, 4(2), 100–110. doi:10.2174/187221010791208803
PMID:20415660
Zhou, H., Li, G., Wang, X., Jin, C., & Chen, Y. (2009). Preparation of a kind of mesoporous carbon
and its performance in adsorptive desulfurization. Journal of Natural Gas Chemistry, 18(3), 365–368.
doi:10.1016/S1003-9953(08)60117-6
Zhou, W. W., Han, Z. Y., Wang, J. Y., Zhang, Y., Jin, Z., & Sun, X. et al. (2006). Copper catalyzing
growth of single-walled carbon nanotubes on substrates. Nano Letters, 6(12), 2987–2990. doi:10.1021/
nl061871v PMID:17163745

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