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Topics in Mining, Metallurgy and Materials Engineering
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Tawfik Abdo Saleh

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Tawfik Abdo Saleh
Editor
Nanotechnology in Oil
and Gas Industries
Principles and Applications
Editor
Tawfik Abdo Saleh
Chemistry Department, and Center of Excellence
in Nanotechnology (CENT)
King Fahd University of Petroleum and Minerals
Dhahran, Saudi Arabia
ISSN 2364-3293 ISSN 2364-3307 (electronic)

Topics in Mining, Metallurgy and Materials Engineering
ISBN 978-3-319-60629-3 ISBN 978-3-319-60630-9 (eBook)
DOI 10.1007/978-3-319-60630-9
Library of Congress Control Number: 2017951115
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Preface
Nowadays, due to the different challenges presented in the oil and gas industry,
different and modern technologies have arisen to accomplish production goals and
environmental requirements. Nanotechnology in oil and gas industry is a fascinat-
ing subject of recent origin. Nanomaterials are involved in almost all stages in the
oil and gas industry, including searching, drilling, production, processing, transport,
and refining. Nanotechnology’s focus areas include: in searching, signal and data
processing; in drilling, the development of novel materials with great tensile
strength and durability and drilling muds based on nanoparticles to control viscos-
ity; in production and processing, the development of membranes, detectors, and
separators (efficient and cost-effective materials for oil/water/gas separation are
highly required); in transport, corrosion (improved inhibition), smart pipelines, and
flow improvers with modified surfaces; and in refining, the development of cata-
lysts, support materials with large surfaces, and improved efficiency and selectivity.
Principles and applications of nanotechnology in oil and gas industries book
offers detailed, up-to-date chapters on the technological developments and
nanomaterials in petroleum. The first chapter of the book encompasses the funda-
mentals and principles of the oil and gas industry. It highlights the upstream
exploration and drilling sectors followed by midstream sectors. It also covers
the downstream sectors with oil refinery processes. The second chapter gives an
overview to nanotechnology applications in petroleum refining.
The other chapters describe the designing of effective nanomaterials and cata-
lysts and desulfurization pathways with a focus on mechanisms of the upgrading
and desulfurization process. These chapters introduce principles and advances in
the nanomaterials in the refinery. Chapter 9 discusses the role of nanomaterials as
an emerging trend toward the detection of winged contaminants. Chapter 10 dis-
cusses the biogas produced from different feedstocks in anaerobic digesters.
In this book, we have tried to cover many aspects of nanomaterials for the
refinery, which is of current interest. This book is written for a large readership,
including university students and researchers from diverse backgrounds such as
chemistry, petroleum, materials science, physics, and engineering. It can be used
v
vi Preface
not only as a textbook for both undergraduate and graduate students but also as a
review and reference book for researchers in these fields. We hope that the chapters
of this book will provide the readers with valuable insight into state-of-the-art
advanced and functional nanomaterials and technologies. However, it is possible
that some topics have been left out owing to constraints on the size of the book. We
trust that the preface will be useful to students, teachers, and researchers.
Dharan, Saudi Arabia Tawfik Abdo Saleh

Acknowledgment
I would like to acknowledge the support provided by King Fahd University of

Petroleum and Minerals. I would like to express my gratitude to the many people
who saw me through this book; to all those who provided support, read, wrote,
offered comments, allowed me to quote their remarks, and assisted in the editing,
proofreading, and design. Above all, I want to thank my parents, relatives, wife,
children, and the rest of my family, who supported and encouraged me in spite of all
the time it took me away from them. Last and not least, I beg forgiveness of all those
who have been with me over the course of the months and whose names I have
failed to mention.
Many thanks.
vii
Contents
1 Insights into the Fundamentals and Principles of the Oil and Gas
Industry: The Impact of Nanotechnology . . . . . . . . . . . . . . . . . . . . 1
Tawfik Abdo Saleh and Saddam A. AL-Hammadi
2 Nanotechnology Applications in Petroleum Refining . . . . . . . . . . . . 37
Ubong J. Etim, Peng Bai, and Zifeng Yan
3 Advances in Nanocatalyzed Hydrodesulfurization of Gasoline
and Diesel Fuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Tawfik Abdo Saleh and Ibrahim Munkaila Abdullahi
4 Improvement of Hydrodesulfurization Catalysts Based on Insight
of Nano Structures and Reaction Mechanisms . . . . . . . . . . . . . . . . 97
Hui Ge, Zegang Qiu, Zhenyu Ge, and Wenpeng Han
5 Selective Sulfur Removal from Liquid Fuels Using Nanostructured
Adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 133
Diana Iruretagoyena and Raul Montesano
6 Nano-MoS2 and Graphene Additives in Oil for Tribological
Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Yufu Xu, Yubin Peng, Tao You, Lulu Yao, Jian Geng, Karl D. Dearn,
and Xianguo Hu
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts:
The Role of Supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Alimorad Rashidi, Fatemeh Mohammadzadeh,
and Sedigheh Sadegh Hassani
8 Mechanisms of Desulfurization by Nanomaterials . . . . . . . . . . . . . 211
Waqas Ahmad and Imtiaz Ahmad
ix
x Contents
9 Role of Nanomaterials as an Emerging Trend Towards the Detection

of Winged Contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
Santanu Patra, Rashmi Madhuri, and Prashant K. Sharma
10 Biogas Produced from Different Feedstocks in Anaerobic
Digesters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
Grazia Leonzio
Chapter 1
Insights into the Fundamentals and Principles
of the Oil and Gas Industry: The Impact
of Nanotechnology
Tawfik Abdo Saleh and Saddam A. AL-Hammadi
Abstract Globally, crude oil is an invaluable source of energy and raw materials
for major industries that are related to daily life. However, the oil and gas industry is
facing a significant number of environmental, technical, and industrial challenges
that require the development of different technologies to meet production goals, as
well as industrial and environmental regulations. This chapter introduces a descrip-
tion of the petroleum industry from exploration up to petrochemical production and
highlights the impact of nanotechnology in different but related processes. The oil
and gas industry can be divided into three main categories: the upstream, mid-
stream, and downstream sectors, which are also known as the refining process. The
upstream and midstream sectors include oil exploration, production, and transpor-
tation. In these sectors, nanotechnology may contribute in developing more effi-
cient, less expensive, and more environmentally sound technologies than those
which are readily available, such as developing unique nano-based sensors for the
oil well exploration process and synthesizing nanomaterials with a hydrophobic
surface for scale inhibition in oil production tubes. The downstream sector and its
related oil refinery processes include crude distillation, thermal cracking, fluid
catalytic cracking, hydrofluoric acid alkylation, hydrotreating, hydrocracking, cat-
alytic reforming, and the isomerization process. In the downstream sector, the
contribution of nanotechnology is focused on developing catalysts with a high
level of stability and performance that can be used in different catalysis processes
in refinery plants, such as the fluid catalytic cracking and hydrotreating processes.
Keywords Crude oil • Nanotechnology • Oil and gas industry • Upstream •

Midstream • Downstream and refining
T.A. Saleh (*)

Chemistry Department, and Center of Excellence in Nanotechnology (CENT), King Fahd
University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
e-mail: [email protected]; [email protected]; http://faculty.kfupm.edu.sa/CHEM/
tawfik/
S.A. AL-Hammadi
Chemical Engineering Department, and Center of Excellence in Nanotechnology (CENT),
King Fahd University of Petroleum & Minerals, Dhahran 31261, Saudi Arabia
© Springer International Publishing AG 2018 1

T.A. Saleh (ed.), Nanotechnology in Oil and Gas Industries, Topics in Mining,
Metallurgy and Materials Engineering, DOI 10.1007/978-3-319-60630-9_1
2 T.A. Saleh and S.A. AL-Hammadi
1 Overview
Crude oil is a complex mixture that contains different organic hydrocarbon mole-
cules; generally, 83–87% carbon, 11–15% hydrogen, 0.05–6% sulfur, nitrogen
0.1–2%, oxygen 0.05–1.5%, and metals < 0.1%. Several types of hydrocarbon
molecules are present in crude oil with relative percentages of each varying from
one oil type to another, thus determining the properties of each oil. The average
range of the composition by weight includes hydrocarbon alkanes (paraffin-
saturated chains) 15–60%, naphthenes (saturated rings) 30–60%, aromatics (unsat-
urated rings) 3–30%, and asphaltic 2–10%. The term petroleum covers
(i) Naturally occurring unprocessed crude oil and
(ii) Petroleum products made up of refined crude oil
Natural petroleum is refined into several types of fuels. Petroleum components can
be separated using a fractional distillation technique. As shown in Fig. 1.1, the oil
and gas industry facilities and systems can be classified into three sectors or stages:
(i) Upstream
(ii) Midstream
(iii) Downstream (Refining)
Oil and gas industry

facilities and systems
Downstream
Upstream Midstream
(Refining)
Various facilities for

Transportation of oil and Oil and condensates are
production and
natural gas from the processed into marketable
stabilization of oil and
extraction site to the products with defined
gas.The reservoir and
refineries. However, this specfications like gasoline,
drilling community uses
sector is often included diesel and feedstock
upstream for the
as an extension of either for the petrochemical
wellhead, well, completion
the upstream or indusrty. Refinery off sites
and reservoir,and
downstream sector, like tank storage and
downstream of the
depending on the source. distribution terminals are
wellhead as production or
included in this segment,
processing. Exploration
or part of a separate
and upstream / production
distributions operation.
together is referred to as
E&P.
Fig. 1.1 General classification of oil and gas industry facilities and systems
1 Insights into the Fundamentals and Principles of the Oil and Gas Industry:. . . 3
2 Upstream Exploration and Drilling Sectors
The upstream exploration and drilling sectors of oil and gas process commonly
involves the following:
2.1 Oil Well Exploration
Exploration can be defined as a searching for hydrogen deposits under the surface of
the earth using different methods, and this process can be done by petroleum
geologists. Due to the facts that the extraction of oil resources decays with time
and the accessibility to the easily recoverable oil resources has been diminished
significantly, more complicated techniques are required in order to enhance the
field characterization performance and ultimately increase the amount of oil recov-
ered. The extraction of oil and gas can be maximized by having sufficient infor-
mation and a clear understanding of the targeted reservoir properties. Despite using
any of the current sophisticated methods for oil recovery like thermal techniques,
gas injection, water-flooding, and chemical flooding, a huge quantity of oil and gas
will ultimately not be extracted. Besides the inefficiency of these methods of oil
recovery, these conventional processes are not favorable economically (Himes et al.
2006; Jones 2015). Since the operations in the deep wells are carried out in a very
harsh environment, conventional electrical sensors are not normally able to be
sustained in such difficult conditions. The available techniques provide limited
information, shallow penetration, and are not able to fulfill the reservoir’s charac-
terization requirements. Clearly, there is a necessity to use unconventional tech-
niques and exceptional materials to overcome these technical challenges and to
effectively explore unconventional oil and gas reservoirs. In addition, these tech-
niques and materials should meet environmental regulations and address safety
issues.
Researchers are trying to improve a new generation of sensors which are small
and hard enough to sustain under harsh conditions and to provide accurate temper-
ature, pressure, and oil and gas flow rate measurements. They also are able to
penetrate deep into the wells and obtain a clear picture of the interaction between
rocks and hydrogen deposits without being interrupted by the presence of electro-
magnetic fields. In addition, a high level of reservoir characteristics performance
requires advanced computational and imaging techniques.
In nanotechnology, different synthesis methods can be used to produce effec-
tive nanomaterials which can contribute to making unique sensors and imaging
contrast agents. The optical, magnetic, and electrical properties of these
nanomaterials can be changed greatly when compared with their bulk counterparts.
Besides, they can form percolated structures electrically and geometrically at low
volume fractions. A combination of the nanoparticles and smart fluids can generate
a very effective sensor that can work properly in very difficult conditions and
provide accurate measurements of temperature, pressure, oil flow rate, and stress in
deep wells. Nanomaterial has great potential for use as markers for imaging when it
is combined with advanced computational techniques and magnetic probes. The
reservoir characterization and the pore sizing can be enhanced when the
nanomaterial segregates into various fluid regions by chemical techniques. The
pore size, high surface area, and mobility of the nanoparticles are absolutely
essential in such imagining. Researchers are developing nanosensors which have
the ability to provide information and data about fluid-type recognition, fluid-flow
monitoring, and which are able to penetrate into deep wells and perform reservoir
characterization. Furthermore, hyperpolarized silicon nanoparticles also have
potential applications in oil imaging and exploration. A nano-CT machine could
also play an important role in providing data on the pore-size distribution and
images for shale and gas sand. The goal of nanotechnology in this field is to develop
a nanorobot which is capable of comprehensively mapping and measuring the
effective characteristics of the reservoir.
2.2 Wellheads and Drilling
The oil well exploration is followed by the drilling of a natural gas or oil well. Then,
there should be a verification of whether the available natural gas is commercially
suitable in terms of quantity. At this stage, the well can be completed to allow
petroleum to be extracted to the surface.
Wellheads can be defined as components at the surface of an oil or gas well that
provide the structural and pressure-containing interface for the drilling and produc-
tion tools. Wellheads are used to provide the suspension point and pressure seals for
the casing strings which run from the bottom of the hole-sections to the surface
pressure control equipment. In this stage, the well hole is strengthened with casing,
the pressure and temperature are evaluated for the formation, and the proper
equipment is installed to ensure an efficient flow of natural gas from the well
which is controlled with a choke (Devold 2013).
Nanotechnology offers innovative techniques for drilling processes which
depend on water-based fluid. These methods could make a dramatic change in the
drilling process performance, are low in cost, and can be applied using straightfor-
ward methods. Besides, nanotechnology-based solutions have less impact on the
environment since the fluid used does not contain toxic chemical materials, which is
the case with conventional fluid drilling. Nanomaterials can be applied to plug
pores in the shale formation, which prevents the formation of a filter cake, which is
usually responsible for fluid loss reduction and the formation of fractures.
Nanoparticles can be added to the used drilling fluid to minimize the thickness of
the filter cake by reducing the permeability of the shale formation. As a result,
nanotechnology is a potential solution which could play an important role in
increasing the drilling process quality and enhancing the wellbore stability.
Various nanotechnology techniques can be implemented to enhance the down-

hole tool performance including the polycrystalline diamond compact bits. A
nanodiamond is an interesting option to increase the PDC abrasion resistance and
to boost its durability. One method to increase PDC diamond density and to
decrease the metallic binder is that nanodiamond may reduce the localized micro-
structural stress when its coefficient of thermal expansion CTE is compatible with
that in the micron diamond.
Bit balling Nanomaterials drilling mud with the hydrophobic film forming capa-
bility on the bit and stabilizer surfaces is used to eliminate the bit and stabilize
balling. Due to their high surface area, nanomaterials fluid could be used for drilling
in shale which is very reactive, highly pliable, and tenacious.
Due to the fine and very thin film forming capability of nanomaterials, the
nanomaterials-based fluid may
(i) Allow a reduction of the frictional resistance between the pipe and the borehole
wall as a result of formation of a thin lubricating film in the wall-pipe interface.
(ii) Facilitate formation of an ultra-thin bed of a ball-bearing type surface between
the pipe and the borehole wall which allows easy sliding of the drill string
along the nanomaterial-based ball-bearing surface.
Removal of toxic gasses H2S can diffuse to drilling fluid from formations during
drilling of gas and oil wells. H2S is to be eliminated from the mud to prevent
corrosion of pipelines and equipment. For example, zinc oxide nanoparticles and
bulk zinc oxide have the potential to remove H2S from water drilling mud.
2.3 Logging While Drilling
Logging while drilling (LWD) is a method for the extraction and collection of data
and information during the drilling process. It measures the formation properties,
well geometry, and the drilling process properties. It makes measurements while
the tools are drilling which provides directional surveys and drilling mechanics
data. Compared with wireline measurement, LWD has similar measurement capa-
bilities, although it differs in numerous other aspects. LWD can work in harsh
environments. On the other hand, wireline measurements are small, delicate,
powered through cable, offer high-speed performance, and are affected by the
entirety of the challenging environment. The main advantage of these processes
is monitoring and controlling the operations while the drilling is taking place.
There are many available LWD measurement techniques such as natural gamma
ray (GR), borehole caliper, resistivity, and sonic and neutron porosity. Nowadays,
the majority of the neutron porosity that is implemented in LWD uses He-3
detectors in order to detect neutrons in the whole. The main advantages of He-3
detectors are that they are mechanically robust, operate at high temperatures, and
fulfill the well logging requirements; however, their available quantity is very
limited and they could be depleted in the next few years. However, a good
alternative for the He-3 detector is the Li-6 scintillation detector, which can be
used as an LWD tool. This detector can be improved using nanotechnology
techniques in order to work more efficiently and substantially. Nanostructured
glass-ceramics of Li-6 scintillations can work far better than the current Li-6
scintillation materials. Nano-logging can be the main contributor in this field and
can improve the next generation of LWD tools, especially in neutron porosity
logging.
3 Upstream Production Sectors and Nanotechnology
3.1 Manifolds/Gathering
The well streams are brought to the main production facilities over a network of
pipelines and manifold net systems. The aim of the pipelines is to allow for
production setup or well sets. Thus, the best reservoir utilization well flow compo-
sition, such as gas, oil, and water, is selected from the available wells. For gas
gathering systems, the individual gathering lines are metered into the manifold.
However, for multiphase flows or combinations of gas, oil, and water, the inflated
cost of the multiphase flow meters leads to the use of software flow rate estimators,
where well test data is used to calculate the actual flow (Devold 2013).
Stimulation In viscoelastic surfactant stimulation fluid, high-molecular-weight
cross-linked polymer fluids are being used to stimulate oil and gas wells. The
advantages of such fluids are their exceptional viscosity, thermal stability, proppant
transportability, and fluid leak-off control. On the other side, the disadvantages of
such materials include the amount of polymer residue they leave behind which can
damage formation permeability and fracture conductivity.
Therefore, the nanoparticles could be good alternatives because of their high
surface morphology and high surface reactivity. These materials can stabilize fluid
viscosity at high temperatures and produce a pseudo filter cake of viscous visco-
elastic surfactant stimulation fluid which reduces the rate of fluid loss and improves
fluid efficiency.
Scale inhibition The formation of scales inside the production tubing can be
inhibited by using nanomaterials with a hydrophobic surface such as epoxy paint
surfaces which can reduce the chances of scale deposition. An example of this type
of material is nano SO2/epoxy adhesive solution. Another example is nanomaterial
coated with a low surface energy polymer, called aminopropyl.
3.2 Separation
In the case where the well produces a combination of gas, oil, and water, with
various contaminants, then it is necessary to install the separation processes. The
production separators are available in various forms and designs, with the classic
variant being the gravity separator. Where the wells have pure gas production, for
example, then the gas is taken directly for gas treatment and compression.
3.3 Gas Compression
In the case where the gasses from the separators have lost a significant degree of
pressure, then the gasses should be recompressed for transportation. To facilitate
this, turbine compressors gain their energy by using up a relatively small proportion
of the natural gas which they compress. The turbine can serve to operate a
centrifugal compressor, containing a type of fan which compresses and pumps
the natural gas through the pipeline. Note that gas from a pure natural gas wellhead
has sufficient pressure to feed directly to a pipeline transport system, thus there is no
need for it to be recompressed.
3.4 Oil and Gas Storage and Export
The final step before the oil or gas leaves the platform consists of
(i) Storage
(ii) Pumps
(iii) Pipeline terminal equipment
In production sites, the oil and gas is piped into a refinery terminal. Gas can be
difficult to store locally, consequently, underground mines, caverns, and salt
deposits are used to store gas. The gas pipeline is fed from the high-pressure
compressors.
On the other hand, on platforms with no pipelines, oil is then stored in onboard
storage tanks to be transported using a shuttle tanker. The oil is stored in storage
cells around the shafts on concrete platforms and in tanks on floating platforms. A
separate storage tanker can be used for some floaters. Ballast handling is necessary
to balance the buoyancy when the oil volume varies. For onshore, fixed roof tanks
are usually used for crude and floating roofs for condensate. In addition, rock
caverns are used. Oil pipelines are usually driven by separate booster pumps. For
long pipelines, intermediate compressor stations and pump stations are

recommended to be used due to the distance involved in crossing mountain ranges
(Devold 2013).
3.5 Midstream sectors
The midstream sectors involve

(i) The transportation of oil and natural gas from the extraction site to the
refineries by pipeline, rail, barge, oil tanker, or truck.
(ii) Storage.
(iii) The wholesale marketing of crude or refined petroleum products.
(iv) Pipelines and other transport systems are utilized to move crude oil from
production sites to refineries and deliver the various refined products to
downstream distributors. Natural gas pipeline networks aggregate gas from
natural gas purification plants and deliver it to downstream customers, like
local utilities. This type may include natural gas processing plants which
purify the raw natural gas and remove and produce elemental sulfur and
natural gas liquids as finished end products.
4 Introduction to Downstream Sectors
The downstream sector usually includes the processes that are related to the crude
oil refinery process, raw natural gas purification processes, and the network that is
responsible for the marketing and distribution of these process products. The
common products that are derived from the oil and natural gas are gasoline, petrol,
kerosene, jet fuel, diesel oil, heating oil, fuel oils, lubricants, waxes, asphalt, natural
gas, liquefied petroleum gas, and hundreds of petrochemicals (Leffler 2008; Fahim
et al. 2009; Krylov et al. 1998; Vassiliou 2009; Meyers 2016). The material in the
next sections is mainly focused on the oil refinery process and its configurations.
5 Oil Refinery Process
The downstream oil refinery processes are summarized in Fig. 1.2 (Jones and
Pujado 1992). The discussion of each unit will be provided in the following main
headings. A simple basic classification of oil refinery processes based on their
nature is depicted in Fig. 1.3.
Fig. 1.2 A simplified block diagram of the refinery processes
5.1 Crude Distillation Unit
Crude oil contains a mixture of hydrocarbons with various boiling points. Thus, the
distillation process can separate the crude oil into different hydrocarbon groups
depending on their boiling point. In the oil refinery, there are two types of distil-
lation unit which are, namely, atmospheric and vacuum distillation units (Jones
2006). Main types of crude distillation units in downstream sectors of oil refinery
processes are presented in Fig. 1.4.
5.1.1 Atmospheric Crude Distillation Unit
The atmospheric crude distillation unit (ACDU) is the first unit in any petroleum
refinery, where the processing of crude begins. In this unit, crude oil is distilled and
separated into various valuable products (naphtha, kerosene, diesel, light and heavy
oil, atmospheric gas oil (AGO)). These products are exposed to further processing
downstream or become an input for conversion units in the rest of the refinery
configuration. The main components of this unit are an atmospheric distillation
Classification of Oil Refinery

Processes based on their Nature
Physical and thermal processes Chemical processes

(non-catalyzed processes) (catalyzed process)
Fluid Catalytic Cracking

Crude Distillation
Hydrofluoric acid (HF) Alkylation
Atmospheric crude distillation
Process
Vacuum crude distillation
Hydrotreating Process
Thermal Cracking
Hydrocracking Process
Thermal cracking coking
Catalytic Reforming
Visbreaking thermal cracking
Isomerization Process
Fig. 1.3 Classification of oil refinery processes based on their nature
column, called a fractionation column, side stripper columns, a furnace, a desalter,

integrated heat exchangers, and pump and crude oil storage, as shown in Fig. 1.5.
It is necessary to increase the temperature of the crude oil before entering the
distillation column, and this can be done by using a series of heat exchangers or a
preheat train where the heat is recovered from the column product streams and by
exchanging with condensing streams from the fractionation column.
The crude oil usually contains salts, such as magnesium and chlorides of
calcium, which have negative effects on the downstream refinery equipment due
to the corrosive properties of these salts. Thus, the first goal of the atmospheric
crude distillation unit (ACDU) is to remove the salt from the crude oil, reduce the
causes of corrosion, prevent fouling, plug as much as possible, and to prepare the
crude for further smooth processing. For this task, the crude oil is pumped to the
first heat exchanger to increase its temperature up to (50–150 C) using recovered
process heat. Increasing the crude oil temperature reduces its viscosity and surface
tension, and this facilitates the subsequent mixing and separation processes. The
crude oil is mixed with a water stream to dissolve the salt and the mixture is sent to
the desalter drum to separate the salt water from the crude oil. This separation
process occurs according to the electrostatic liquid/liquid separation mechanism,
where a high voltage is applied to remove the suspended water salt globules from
Downstream sectors
(Oil Refinery Processes)
Crude Distillation Units
Vacuum Crude Distillation Atmospheric Crude Distillation
Main components:
Main components: Atmospheric distillation column,
Atmospheric distillation column, called fractionation column, side
fired heater, integrated heat stripper columns, furnace, desalter,
exchangers, pumps. integrated heat exchangers, pumps
and crude oil storage.
Main operating conditions:

(0.033–0.040) bar and temperature Main operating conditions:
of 420 °C, inside the distillation
column. 1 bar and temperature of (350 °C –
370 °C), inside the distillation
column.
Fig. 1.4 Main types of crude distillation units in downstream sectors of oil refinery processes
the crude oil. The pressure inside the desalter drum must be maintained at a high
value to prevent the partial vaporization of crude oil, resulting in the creation of a
hazardous environment and unstable conditions. The effluent water from the
desalter is disposed of by sending it to the oily water sewer.
The downstream of the desalter unit is heated further using another heat
exchanger to a temperature of 200–280 C. Then, the crude oil temperature is
increased up to (340–390 C) using a furnace (fired heater), resulting in vaporizing
a portion of the crude oil and having a stream with two phases (liquid/gas). The
heated crude oil is directed to the bottom part of the distillation column which is
called the flash zone, where the two phases are separated.
At a pressure of about 1 bar and a temperature of (350–370 C) inside the
distillation column, the vaporized portion of the crude oil moves up the column
through trays, while the liquid portion leaves the flash zone of the column by a
stream stripper section. In the distilling process, the crude oil should not be
subjected to temperatures >370 C to avoid thermal cracking of the high-molecular-
weight components forming the petroleum coke. The formation of coke may plug
Fig. 1.5 The atmospheric crude distillation unit (ACDU)
the tubes in the furnace that heats the feed stream to the fractionation column,
piping both from the furnace to the fractionation column and also in the column.
The fractionation column inlet oil temperature is constrained between 370 and
380 C, producing residual oil from the bottom part of the fractionation column,
where the hydrocarbons boil at a temperature higher than 370–380 C.
In every tray, the distillate vapor is in countercurrent contact with the liquid
reflux stream which is generated from a condenser at the top of the distillation
column and from the side stripper columns. The various fractions of the vaporized
crude oil are gradually condensed with the column elevation on the trays based on
their boiling point. As a result, the lighter portions of the crude oil condense on the
higher trays, such as naphtha, methane, ethane, propane, and butane while the
heavier portions, like fuel oils, condense on the lower ones. Using special trays
(draw-off trays), distillate products are withdrawn from the side of the column into
smaller side stripper columns. The side stream distillates are heavy gas oil, light gas
oil (diesel), and kerosene (jet fuel), and they leave the atmospheric distillation
column and enter the top of their respective stripper tower. Like the atmospheric
distillation column, the stripper columns have between 4 and 6 fractionation trays,
where there is liquid/vapor contact in every single tray. To draw off the hydrocar-
bons from the side stripper columns with specific properties, a steam is introduced
at the bottom of the stripper column which exits at the top and enters into the
distillation tower. The side stream stripper towers are usually compacted into one
column to make the flow from the side stream draw-off tray to its stripper tower
more easy and direct.
The naphtha vapor leaves the top of the column and is collected in the overhead
drum. The unestablished naphtha from the fractionation column is transferred to the
naphtha stabilizer section to separate the stabilized overhead vapors which are
condensed to recover liquefied petroleum gas (LPG). Then, LPG is treated in a
caustic and amine treating unit. The stabilized naphtha then undergoes further
separation to produce light, medium, and heavy naphtha. A portion of the side
stream’s product and naphtha vapor are condensed and returned as a liquid reflux to
the distillation column.
The purpose of the flowing liquid reflux is creating a driving force for the
separation of different crude fractions, controlling the temperature in the trays,
and minimizing the heat loss in the column by recovering some energy from the
condensed vapor streams. For further illustration, inside the tower are a series of
trays that have perforations which allow the vapors to rise, as shown in Fig. 1.6. In a
typical design, the trays are constructed with a device called a bubble cap which
forces the vapor to bubble through a layer of collected liquid that is several inches
deep on each tray. As it rises through the liquid, the vapor transfers some of its heat
to the liquid. The heat transfer causes the vapor to cool slightly and some of the
heavier components of the vapor to condense into a liquid. As a result of the heat
transfer from the vapor, the liquid on the tray gains heat, some of its lighter
components are driven off as a vapor which rises up to the next tray. This process
is continuously repeated.
In the flash zone, the stripping steam flow is introduced into a countercurrent
with the flow of the crude oil residue. This steam decreases the amount of liquid/
vapor separation, resulting in enhancing the crude oil flashing (Gary et al. 2007).
The residual oil can’t be distilled further due to the range of the temperature and
pressure limitations in the atmospheric crude distillation unit (ACDU), so the
residual is sent to the vacuum crude distillation unit (VCDU) for further distillation
under different operating conditions.
Fig. 1.6 A tray in the

atmospheric column with
liquid/vapor contact
5.1.2 Vacuum Crude Distillation Unit
Vacuum distillation is a separation technique where the pressure is reduced above

the liquid mixture, resulting in evaporation of the most volatile species when the
pressure is less than their own vapor pressure. Vacuum crude distillation involves
distillation of the atmospheric residue from the atmospheric crude distillation unit
(ACDU) under vacuum in order to obtain additional useful products and to reduce
the residual stock as much as possible. In a vacuum condition, distillation allows
separation at lower temperatures, resulting in reducing the possibility of crude oil
cracking and furnace tube coking, Fig. 1.7.
The vacuum crude distillation unit (VCDU) and atmospheric crude distillation
unit (ACDU) are integrated specifically for utilizing the recovered heat and design-
ing the integrated heat transfer system. The vacuum column has a larger diameter
and a different internal structure than the atmospheric column. The internal design
of the vacuum column should keep a pressure increasing from the top to the bottom
of the column and the liquid/vapor contact should be excellent. As a result, the
vacuum column contains packing materials and demister pads, which usually have
a lower pressure drop compared to the trays that exist in the atmospheric column.
This packing material consists of (1) structured sheet metal or (2) randomly dumped
packing such as Raschig rings. However, the vacuum contains a few trays to draw
off the product from the side of the column.
Fig. 1.7 A simplified diagram of the vacuum crude distillation unit (VCDU)
The vacuum condition is usually generated by a series of steam ejectors that are
working from the top of the column. The ejectors remove inert and other vapors
which exist in and pull a vacuum of about 5 mmHg absolute. The pressure in the
vacuum column typically is kept at about (25–30) mmHg, and the temperature is
maintained around 420 C.
Despite the difference in the operating conditions, the process configuration of
the VCDU has somewhat the same configuration process as the atmospheric crude
distillation unit (ACDU). The ACDU residue oil is preheated by a heat exchanger
using recover heat from the hot stream products. Then, the residue oil is partially
vaporized due to the increase in its temperature up to (400–430 C) using a fired
furnace.
The two-phase stream enters the vacuum column and flashes at a feed point
called the flash zone. The distilled vapor rises through the column and is condensed
by the circulating liquid reflux moving down the column in the same manner as the
cold reflux of the side stream in the ACDU. The products are taken off at the
appropriate sections and are cooled by
(i) Heat exchange with colder streams in the atmospheric unit
(ii) By air coolers
(iii) As heating mediums to light end reboilers
The light vacuum gas oil is withdrawn from the top side of the column while the
heavier vacuum gas oil leaves from the second side of the column. The light
vacuum gas oil is directed to other conversion units in the refinery configuration
for further processing or is used as a lube base stock. The vacuum residue can be
either directed to a coke unit, a cracking unit, and a visbreaker unit or utilized to
produce asphalt material.
5.2 Thermal Cracking Processes
The thermal cracking processes can be classified into the following main types:
(a) coking and (b) visbreaking. The thermal coking process can be classified into
various types including (1) the delayed coking process and (2) flexi-coking which is
an improved version of conventional fluid coking. Table 1.1 summarizes different
thermal cracking processes and their conditions. The following sections will discuss
these types.
5.2.1 Thermal Cracking Coking Processes
Coking is an extreme form of the thermal cracking process, in which the heavy
residue is completely converted from the low-cost material to valuable products.
The common products of this process are naphtha, solid materials, gas oil, and coke.
The coking process is suitable for processing heavy oil crudes like the Canadian
heavy oil crudes. The delayed coking and fluid coking process are different types of
Table 1.1 Comparing between different thermal cracking processes and their conditions
Thermal cracking
process Process conditions
Delayed coking Operates in semi-batch mode
Moderate (482–515 C) heating at 6 bar
Soak drums (452–482) coke walls
Coked until drum solid
Coke 25–40% on feed, yield 221 C, 30% on feed
Fluid coking Operating conditions: 510–530 C and 0.7 bar
Oil contact refractory coke
Fluidized bed with steam-even heating
Higher yield of light ends (<C5), less coke yield
Flexi-coking Licensed and commercialized by Exxon Research and Engineering
Company
Different fluidized beds are utilized to produce a lighter more valuable
product from the heavy residue
A large portion of the coke is converted to a low Btu gas
The reactor temperature is maintained around (530 C)
Visbreaking Mild operating conditions
Mild (470–500 C) heating at 3.5–14 bar
Reducing the fuel oil viscosity
Low conversion (10%) to 221 C
Two types: soaker and coil visbreaking process
Heated coil or drum
Fig. 1.8 Classification of the thermal cracking process
the coking process including (1) the delayed coking process and (2) flexi-coking;
which are discussed in the following two sections. Figure 1.8 depicts the general
classification of the thermal cracking process.
Delayed Coking Process
The delayed coking processing is a thermal cracking process, where the heavy
residuum from the ACDU and VCDU is heated and converted into coke gas oil and
petroleum coke in a batch-continuous process, Fig. 1.9. Like the ACDU and
VCDU, a fired heater is used to increase the feed temperature up to (480–505 C),
resulting in a mild cracking of the heavy residuum. The output stream of the furnace
is routed to one of the coking drums with a temperature of around 500 C and a
pressure of (2–3.5 bar). The coking drum usually takes (11–20 h) to be filled with
oil residuum. The liquid/vapor mixture of the oil residuum is exposed to successive
cracking until the total destruction of the heavy fractions is achieved. As a result of
a long residence period, the coke is generated as a by-product from the rich carbon
solid materials, and it is removed from the bottom part of the drum using high-
pressure jets. The coke which is produced in the delayed coking process is called
green coke and is classified as a sponge coke.
The feed stream is regularly switched between drums with one drum operating
under the decoking process which is performed using high-pressure water jets. A
cycle of events occurs at regular intervals depending on the delayed coking unit
feed rate, drum size, and throughput capacity. Typically, delayed cokers run drum
cycle times of about 12–16 h, with one drum filling online while its counterpart is
off-line for stripping, cooling, and the decoking cycle.
Fig. 1.9 A simplified diagram of the delayed coking process

The cracked vapor leaves from the top of the drum and is then directed to the
fractionator column, where it is distilled and separated into the desirable distillate
products (e.g., naphtha, kerosene, gas oil). The bottom of the fractionator column
contains a reservoir where a combination between the fresh feed and condensed
product vapor occurs in order to compensate for the feed of the coker heater.
Flexi-Coking Process
Flexi-coking is an improved version of the conventional fluid coking process,

where the heavy residuum of oil from the atmospheric crude distillation unit
(ACDU), vacuum crude distillation unit (VCDU), or fluid catalytic cracker (FCC)
units is converted thermally to lighter and more valuable products using a contin-
uous fluidized bed reactor, Fig. 1.10. This technology is licensed and commercial-
ized by the Exxon Research and Engineering Company.
In conventional fluid coking, the oil residue is coked by being sprayed into a
fluidized bed of hot, fine coke particles. For example, a shorter contact time with
higher temperature coking might result in increased light and medium hydrocar-
bons with less cake generation. However, the product would have a lower value
from economic point view (Rana et al. 2007).
Unlike the delayed coking process, a substantial portion of the coke is converted
to a low Btu gas in the flexi-coking gasification process. The flexi-coking config-
uration has the capability of handling a wide range of feed types, particularly, feeds
Fig. 1.10 A simplified flow diagram of the flexi-coking process

with high metals, sulfur, and Conradson Carbon Residue (CCR or Concarbon)
content.
The heavy hydrocarbons are sprayed into the fluidized bed reactor, where they
are cracked thermally, by a hot coke fluidized bed. This hot coke is circulating
between the reactor and the heater vessel to maintain the reactor temperature at
around (530 C) and to supply the sensible level of vaporization heat required for
thermal cracking. The cracked vapor products leave the reactor section and enter
the scrubber zone, where a portion of the vapor (usually fine coke and heavy oil
particles) is condensed and recycled to the reactor zone. The reactor output flows to
a conventional fractionator column for separation purposes.
A steam is injected into a baffled section at the reactor bottom to strip the coke is
free from other reaction products. The coke is routed to the heater vessel, where its
temperature is increased to about 600 C. The heating process is achieved using a
coke fluidized bed, and its main goal is to transfer the heat to the reactor for the
cracking process. The coke leaves the heater vessel and enters a gasifier, where it is
converted to a low Btu gas which contains N2, H2, CO2, and CO by a reaction with
air and steam. The coke contains sulfur which is usually converted to H2S and COS
in the gasifier unit while the nitrogen is converted into NH3 and N2. This gas leaves
the gasifier and enters the heater, where it is used to fluidize the coke bed and supply
the reactor with the required heat energy. A coke purge stream is withdrawn from
the heater and is usually about 0.5–0.9 wt % of the fresh feed. Most of the metals
contained in the process feedstock are separated with this purged coke.
After leaving the heater, the coke gas is cooled using a steam generator and then
enters a tertiary cyclone and venture scrubber, where the coke fines are collected.
Finally, H2S is removed from the coke gas in the sulfur removal unit (Stretford
unit). As a result of the flexi-coking process, an upgrade in the low-quality fuel is
achieved and a fuel gas with a lower heating value compared to natural gas is
generated.
5.2.2 Visbreaking Thermal Cracking Process
The visbreaking process is a thermal cracking process under mild operating condi-
tions, where the viscosity of the VCDU residuum is reduced by breaking the long
chain molecules of the feedstock into shorter ones to obtain more valuable products
and to meet the fuel oil specifications, Fig. 1.11. In the visbreaking process, the
operating conditions of the thermal cracking are optimized in a way that breaks off
the long paraffinic side chain attached to the aromatic rings into smaller molecules.
As a result of this optimized process, the thermal cracking is not complete, the
viscosity of the product is largely reduced, and the resulting fuel exhibits good
stability. Under extreme operating conditions, the product has less stability and can
be polymerized during storage which causes filter plugging and sludge formation.
Fig. 1.11 A flow diagram of the Soaker Visbreaker unit
The principle reactions which occur during the visbreaking operation are:
• Cracking of the side chains attached to the cycloparaffin and the aromatic rings
at the ring so the chains are removed or shortened into methyl or ethyl groups.
• Cracking of resins into light hydrocarbons (primarily olefins) and compounds
which convert to asphaltenes.
• At temperatures above 480 C, there is some cracking of the naphthene rings.
There is little cracking of the naphthenic rings below 480 C .
Thus, there are two types of visbreaking process: the soaker visbreaking process
(Fig. 1.11) and the coil visbreaking process (Fig. 1.12). In the soaker visbreaker
unit, thermal cracking is achieved at a relatively low temperature of about
(427–443 C) and with a long residence time. However, the cracking is achieved
at a high temperature of around (470–500 C) and a short residence time of about
(1–3 min) in the coil visbreaker unit. Despite the similarity between the two units in
the yield and properties of the product, the soaker visbreaker unit consumes less
energy due to the relatively low temperature, and it can be operated for a long
period of time (6–18 months) before being shut down for coal removal purposes
compared to 3–6 months in the coil visbreaker unit. However, cleaning the coil
Fig. 1.12 A flow diagram of the Coil Visbreaker unit
visbreaker unit is much easier than the soaker visbreaker unit. Currently, the
majority of the new refineries use the soaker visbreaker unit instead of the coil
visbreaker unit (Sieli 1998).
5.3 Fluid Catalytic Cracking Unit
The fluid catalytic cracking unit is one of the most dynamic and complex processes
in a refinery. In the fluid catalytic cracking unit, the high-boiling, high-molecular
weight hydrocarbon fractions of petroleum crude oils are converted into valuable
products, such as gasoline and olefinic gasses, Fig. 1.13.
Cracking of petroleum hydrocarbons can be performed by (1) thermal cracking
and (2) catalytic cracking. Using catalytic cracking, more gasoline with a higher
octane rating is produced with a by-product of olefinic-valuable gasses.
The common feedstock of an FCC unit contains atmosphere gas oil, vacuum gas
oil, and a heavy stream, such as reduced crude oil.
Fig. 1.13 A flow diagram of the fluid catalytic cracking unit (FCCU)
The feed usually contains major contaminants, such as carbon residue and
metals. The fluid catalytic cracking process has two main steps: (1) the reaction
and regeneration process and (2) the fractionation process.
5.3.1 Reaction and Regeneration Process
The fluid catalytic cracking unit (FCCU) is a circulating fluidized bed system which
includes a reactor, regenerator, and a heterogeneous catalyst system. The reactor
and regenerator vessels are connected to each other by transfer lines to enable the
catalyst particles to flow between the two vessels for a continuous reaction and
regeneration process. The feed to the unit along with the recycle streams is
preheated to a temperature of 365–370 C. Then, the feed is allowed to flow to the
riser, where it encounters hot regenerated catalyst at a temperature of 640–660 C.
In the inlet of the reactor vessel, cracking occurs owing to the contact of oil with
the powder catalyst. To obtain a high surface contact area, the catalyst and oil are
dispersed inside the reactor column. This provides complete cracking in the catalyst
fluid bed in the reactor vessel. The catalyst fluidity can be maintained using a steam
injection at the bottom part of the riser.
The cracked vapor effluent flows from the top section of the riser column to enter
the recovery part of the plant. In this plant, the distillate products of cracking are
separated by fractionation and forwarded to either storage or for further treatment.

The oil slurry stream from the recovery plant is returned back to the reactor as it is
recycled. On a continuous basis, the catalytic materials from the reactor flow to the
regenerator vessel where there is contact between the catalyst particles and an air
stream that maintains the catalyst particles in a fluidized condition. The carbon that
covers the catalyst particles is burned off by a reaction with the air which leads to a
carbon conversion into gasses such as CO and CO2.
The reactions that occur in the FCC unit are extremely exothermic which pro-
duces a huge amount of energy that increases the catalyst stream temperature up to
537 C and supplies the required heat for the oil cracking reaction.
5.3.2 The Fractionation Process
In the fractionation process, the output of the reactor-regeneration system is sepa-

rated into different products. Liquefied petroleum gas and gasoline are removed
overhead as vapor. Unconverted products such as light and heavy cycle oil flow out
as a side stream. The overhead product is transferred to the stabilization section,
where stabilized gasoline is separated from the light products from which liquefied
petroleum gas is recovered.
The common products of the FCC unit contain light gasses, liquefied petroleum
gas, gasoline, heavy and light cycle oil, and coke as a by-product which is
consumed in the system regenerator to supply the reactor with the energy demand.
5.4 Hydrofluoric Acid Alkylation Process
The alkylation unit is one of the conversion units in the crude oil refinery where
isobutane and alkenes with a low molecular weight are converted into alkylate,
which is a high-octane gasoline, Fig. 1.14. The common catalysts for the alkylation
reaction are sulfuric acid or hydrofluoric acid. Alkylation is catalyzed by liquid and
solid acids, such as HF, AlCl3-HCl, H2SO4, HF-BF3, H2SO4-HSO3F, BF3—alu-
mina, trifluoromethane sulfonicacid chlorided Pt alumina, ion exchange resins, and
zeolites (Gary et al. 2007).
Based on the used catalysts, the unit may take the name of (1) sulfuric acid
alkylation unit (SAAU), (2) hydrofluoric acid alkylation unit (HFAU) or
hydrofluoric acid (HF) alkylation process (Fig. 1.15). The alkylation unit feedstocks
usually contain olefins and isobutane. The catalytic cracking and coking operations
are considered as the main source for the olefins in the alkylation process. Propene
and butenes are the main olefins that are used. However, pentenes or amylenes are
involved in some operations.
The process of hydrofluoric acid (HF) alkylation is achieved in four main steps
including (1) feed pretreatment, (2) reaction, (3) fractionation, and (4) acid regen-
eration. These steps are highlighted in the following sections.
Fig. 1.14 A simplified block diagram of the location of the alkylation unit in the refinery
configuration
Fig. 1.15 Illustration of the hydrofluoric acid alkylation flow diagram

5.4.1 Feed Pretreatment
The alkylation unit olefin feed is generated from an FCC unit and contains butene,
isobutene, and propene, in addition to amylenes, n-pentane, propane, n-butane, and
noncondensables (ethane and hydrogen). The feed may also contain contaminants
(such as water, methanol, and ethanol) which reduce the acid catalyst’s efficiency
by diluting its concentration or reacting with it. As a result, the acid consumption
and the undesirable reaction products are increased. Therefore, in the hydrofluoric
acid alkylation process, olefin feeds, which are produced from the FCC unit, are
usually deethanized. Merox (mercaptan oxidation) is treated to remove H2S and
mercaptans and then dried.
5.4.2 Reactions
After the pretreatment of the olefin feed, it is combined with a huge amount of a
recycled isobutane excess to supply a 6:14 isobutane to olefin molar ratio. Then, the
combined stream is sent to the reactor column of the alkylation unit. The extreme
exothermic heat that is generated from the reaction is removed using flowing
cooling water in the reactor tubes, and this allows the reaction to occur in a
temperature range from 27 to 38 C. The alkylation reaction occurs at a high rate
of almost complete olefin conversion. The excess amount of nonreactive hydrocar-
bons, alkylate product, and isobutane that exist in the feed stream and the acid
catalyst are transferred into the settler vessel. Using gravity, the dense acid phase
and the hydrocarbons are separated from each other rapidly. Then, the dense acid
phase is recycled to the reactor column while the hydrocarbons with the dissolved
hydrofluoric acid flow out of the settler vessel into the isostripper column.
5.4.3 Fractionation
In the fractionation sector, the distillation process is utilized to separate the alkylate
from the isobutene and acid catalyst. The unreacted isobutane is recycled and
combined with the olefin feed before entering the reaction vessel. Propane is the
main product of the distillation process and the n-butane flows off as a side product.
Generally, the fractionation sector usually has a hydrofluoric acid stripper, a
depropanizer, and an isostripper.
The isostripper is a column that has double side draws and its main function is to
recover isobutane to increase the ratio of isobutane to olefin molar of the used
reactor. The isostripper column consists of two reboilers. The goal of the upper
reboiler is to increase the use of the low-pressure steam while the lower reboiler
utilizes a heating medium which provides 200–230 C. Alkylate is withdrawn from
the lower section of the column and then cooled and transferred to the product
storage. Also, the isobutane is withdrawn from the column and recycled to the
reactor vessel while the n-butane is withdrawn from the side draw and sent to the
product storage.
The depropanizer and hydrofluoric acid stripper separate propane from the
recycled isobutene. The stream of the lower section of the depropanizer column
is isobutane which is combined with the isobutane stream of the isostripper tower
and recycled to the reactor vessel. In the upper part of the depropanizer column, the
propane product and hydrofluoric acid are separated in the overhead receiver. The
acid phase is recycled to the reactor sector and the acid which contains propane is
sent to the hydrofluoric acid (HF) stripper column, where propane is stripped free of
acid. The bottom stream of the HF stripper is a propane product treated with hot
alumina to separate the organic fluorides, and then cooled and treated with potas-
sium hydroxide pellets to remove traces of hydrofluoric acid and water.
5.4.4 Acid Regeneration
In the hydrofluoric acid alkylation process, a small stream of circulating acid is

stripped with superheated isobutane in a small monel column called the acid
regenerator. The regenerator overhead is hydrofluoric acid and isobutane that are
recycled to the reactor; the regenerator bottom is polymer and the hydrofluoric
acid–water azeotrope, which are neutralized with aqueous potassium hydroxide. In
addition to the alkylate stream, the products leaving the alkylation unit include the
propane and normal butane that enter with the saturated and unsaturated feed
streams as well as a small quantity of tar produced by the polymerization reactions.
The product streams leaving an alkylation unit usually contain grade propane
liquid, normal butane liquid, C5+, and tar.
5.5 Hydrotreating Process
In the hydrotreating process called also catalytic hydrogen treating, objectionable

materials such as sulfur, nitrogen, olefins, and aromatics are removed or reduced
from the petroleum fractions. The terms hydrotreating, hydrodesulfurization,
hydroprocessing, and hydrocracking are commonly used rather loosely in the
industry because these processes are interconnected. In the processes of
hydrodesulfurization and hydrocracking, for example, desulfurization and cracking
operations occur at the same time. The common units under the hydrotreating
process are shown in Fig. 1.16.
5.5.1 Applications of Hydrotreating
The removal of objectionable materials from crude oil fractions can be achieved by
selecting a reaction between these objectionable materials and hydrogen gas in a
Fig. 1.16 A simplified diagram of the typical hydrotreating process unit
reactor at a high temperature (on average 300–500 C) and at moderate pressures.

The lighter materials like naphtha are treated to be prepared for the next operation
in the catalytic reforming units. However, jet fuel and heavy gas oil, in addition to
other heavier distillates, are treated to meet the new stricter product quality stan-
dards regarding crude oil refinery products.
Many environmental regulations and constraints have been enforced on the oil
industry to minimize the harmful materials in the refinery products as much as
possible and to meet the new fossil fuel quality specifications.
Factors including the (1) type of feed, (2) desired cycle length, (3) and expected
the quality of the products determine the type of design of a hydrotreater. Generally,
the hydrotreating operates under the following conditions:
• Liquid hourly space velocity (LHSV) of 0.2–8.0.
• H2 circulation of 300–4000 SCFB (50–675 Nm3/m3), where SCFB stands for the
standard cubic feed hydrogen in the reactor per barrel of hydrocarbon feed.
• H2PP of (14–138 bars).
• The start of run temperatures ranges between 290 and 370 C (Chianelli et al.
2002; Topsøe et al. 1996).
The common applications of hydrotreating are for:
(i) Naphtha (as a pretreatment process for the catalytic reformer unit): the
objective is reducing or removing metals, nitrogen, and sulfur which can
poison and deactivate the catalysts of the reforming process.
(ii) Kerosene and diesel: the objective is reducing or removing sulfur, in addition
to saturating olefins and some of the aromatics, thereby improving the prop-
erties of the streams including the amount of kerosene diesel and the smoke
point. This also provides storage stability.
(iii) Lube oil: the objective is reducing or improving the viscosity index, color, and
stability while in storage.
(iv) Fluid catalytic cracker (FCC) feed: the objective is reducing or removing FCC
yields while decreasing the catalyst usage and stack emissions.
(v) Resids: the objective is reducing or removing sulfur to provide oils with low
sulfur content which can affect conversion and pretreatment for the down-
stream process of conversion.
The recycled hydrogen and hydrogen makeup are mixed with the feed before
entering the reactor vessel after the preheating process. The hydrotreating reaction
is carried out at a temperature equal to or less than 427 C to avoid cracking. The
hydrotreating process occurs in a fixed-bed reactor by a reaction between hydrogen
gas and the oil in the presence of metal oxide catalysts. The common products of
this reaction are hydrogen sulfide, saturated hydrocarbons, and ammonia. Then, the
reactor products are cooled and sent to a hydrogen separator unit to separate the
hydrogen from the oil. In the stripper column, the remaining hydrogen sulfides and
light end products are removed from the oil. The gas is treated to remove hydrogen
sulfide and recycled to the reactor (Gary et al. 2007).
5.5.2 Chemistry of the Hydrotreating Process
The chemical steps and reactions which occur during the hydrotreating process can
be summarized as:
• Sulfur removal, desulfurization or hydrodesulfurization (HDS), where the
organic sulfur compounds are converted to hydrogen sulfide (Saleh and
Danmaliki 2016a, b).
• Nitrogen removal, denitrogenation or hydro-denitrogenation, where the organic
nitrogen compounds are converted to ammonia.
• Organo-metallic, hydrodemetallation or hydrodemetallization, where the
organo-metals are converted into the respective metal sulfides which are
removed.
• Oxygen removal, where organic oxygen compounds are converted into water.
• Olefin saturation, where organic compounds containing double bonds are
converted into their saturated homologues.
• Aromatic saturation, hydro-dearomatization, where some of the aromatic com-
pounds are converted into naphthenes.
• Halides removal, where the organic halides are converted into hydrogen halides.
5.6 Hydrocracking Process
Hydrocracking processes are versatile catalytic refining processes which are

performed for crude oil feedstock upgrading by adding hydrogen and removing
impurities. In the hydrocracking process, the weight of large molecules is converted

into lower molecular weight by cracking until the desired boiling range is reached.
The feed of the hydrocracking can range from heavy vacuum gas oils to atmo-
spheric gas oils, while the products can range from heavy diesel to light naphtha.
The hydrocracking can usually be achieved by using various configuration
processes including (1) single-stage process, (2) double-stage process, and
(3) multi-stage processes, Figs. 1.17 and 1.18. These processes are highlighted in
the following paragraphs.
5.6.1 Process Description and Classifications
The hydrocracking process can be classified into two types:

(i) The hydrocracking process where the cracking and treating are combined in
one reactor is considered as a single-stage process. This single-stage process
can be used for (1) a moderate degree of conversion or (2) for full conversion
with a limited reduction in molecular weight such as the production of middle
distillates from heavy distillate oils. The disadvantages of the single-stage unit
include limitations in the conversion percentage and the deactivation and
contamination of the used catalysts by undesirable materials.
Fig. 1.17 A simplified diagram of the hydrocracking single-stage process

Fig. 1.18 A simplified diagram of the hydrocracking two-stage process
(ii) The hydrocracking process where the cracking reaction occurs in an additional
reactor or reactors is considered as a multi-stage process. In the first reactor, the
undesirable materials are separated from the unconverted hydrocarbons.
Denitrogenation and desulfurization take place along with a limited amount
of hydrocracking of the exothermic reactions. The catalyst is arranged in
several fixed beds while the temperature of the reaction is controlled by
injecting a portion of the recycle gas between these catalyst beds. The products
of the first and second reactor are transferred into the hydrogen separation unit,
where the hydrogen is separated and recycled. Then, they are sent to the
fractionation column, where unconverted materials are removed and with-
drawn from the lower section of the fractionation column.
5.6.2 Chemistry of the Hydrocracking Process
In the hydrocracking process, the heavy feedstock containing large molecular

weight molecules can be converted into smaller molecular weight compounds.
The reactions which occur in the hydrocracking units include (1) treating, called
pretreating, and (2) cracking, or hydrocracking reactions which require a bifunc-
tional catalyst, possessing the dual function of both cracking and hydrogenation.
The reactions in hydrocracking can be classified into two categories:
(i) Desirable reactions include the treating, saturation, and cracking reactions
(ii) Undesirable reactions include contaminant poisoning and coking of the catalyst
5.6.3 Advantages of Hydrocracking
Hydrocracking processes have several advantages including:

(a) Flexibility in terms of the production of gasoline and the middle distillates.
(b) The products are of a high standard.
(c) Relatively easy processes with the ability to handle a wider range of feedstock,
like the cycle oils from other cracking units.
(d) Easy to control with the capability of handling various feedstock compositions.
(e) Limited by-product yield.
(f) Good conversion rate of the gas oil and residues into useful products.
5.7 Catalytic Reforming
In the catalytic reforming process, light crude oil distillates react with the hydrogen
stream at a pressure of 3.5–34.5 bars and at an elevated temperature. In addition,
there is the presence of platinum-based catalysts to increase the octane number of
the hydrocarbon feed streams, Fig. 1.19. The paraffin-rich naphtha feed with low
octane is converted into a liquid product which is rich in aromatic compounds with
a high-octane number. In addition, hydrogen and light hydrocarbons are obtained as
reaction by-products. Reformate can be used as a blending material for motor fuels,
and as the main source of aromatics that are heavily used in the petrochemical
industry (Pujadó and Moser 2006). The common feedstocks of the catalytic
reforming unit are heavy straight-run gasolines, naphthas (82–190 C), and heavy
hydrocracker naphthas.
Fig. 1.19 General catalytic reforming flow diagram

5.7.1 Process Description
The first step generally is the naphtha feed preparation which involves removing the
impurities and reducing catalyst degradation. Then, the actual reforming process
step starts. A typical flow diagram is presented here. The reforming process
includes the following steps:
– The reaction section comprising heat recovery, furnace, and rectors
– Hydrogen separation and recirculation
– The product recovery section or distillation
The naphtha feedstock is combined with the hydrogen generated by the reaction
process itself, vaporized, and passed through a heat recovery train from the outgo-
ing reaction products. Then, it enters a succession of the alternating furnace and
fixed-bed reactors. The common catalysts that are used in these reactors are a
platinum catalyst or a bimetallic (Pt- Rh) catalyst.
The product of the least fixed-bed reactor is cooled and transferred to a separator
unit to remove the hydrogen stream which is recycled and mixed with the naphtha
feedstock. Also, the excess of the hydrogen product is transferred to other units in
the refinery plant. The liquid products from the bottom of the separator are sent to a
stabilizer called a butanizer. This makes the bottom product which is called
reformate, while the butanes and lighter paraffins pass overhead and are then sent
to the other users.
The catalysts require regeneration after a certain time. Depending on the catalyst
type and the severity of the reaction, the cycle time and method of regeneration
varies. Some catalytic reforming systems continuously regenerate the catalysts.
5.7.2 Reactions
In catalytic reforming, reaction conditions should be selected to favor the desired

reactions and inhibit the undesired reactions. Desirable reactions in a catalytic
reformer form aromatics and iso-paraffins:
• Paraffins are isomerized and converted to naphthenes which are subsequently
converted to aromatics.
• Olefins are saturated to form paraffins.
• Naphthenes are converted to aromatics.
• Aromatics are left essentially unchanged.
It should be noticed that the reactions which form undesirable products include:
• Dealkylation of side chains on naphthenes and aromatics to form butane and
lighter paraffins.
• Cracking of paraffins and naphthenes to form butane and lighter paraffin.
Major reactions that take place during reforming include:

• Dehydrogenation of naphthenes to aromatics.
• Dehydrocyclization of paraffins to aromatics.
• Isomerization.
• Hydrocracking.
5.8 Isomerization Process
The isomerization process is mainly used to transform n-paraffins to iso-paraffins.

The n-paraffins usually have a low-octane number whereas iso-paraffins have a
high-octane number, Fig. 1.20. Hence, the main applications of the process are in
producing high-octane blending components for gasoline in refineries. To obtain
high-octane stock, the common process includes:
• Isomerization of butane to isobutane
• Isomerization of pentanes and hexanes into higher branched isomers
For a general description of the isomerization process, the common feed of the
isomerization unit is a light straight-run gasoline stream high in C5 and C6+ normal
paraffins. The feed is sent to the deisopentanizer column which removes (1) iC5
Fig. 1.20 Flow diagram of a typical isomerization unit

which exists in the streams and (2) iC5 generated in the reactors which are recycled
back to the feed stream as a portion of the nC5 recycles. When the iC5 enters the
overhead of the deisopentanizer column, the balance of the feed stream is trans-
ferred to the isomerization unit. In this unit, hydrogen gas is introduced into the
stream to drive the reaction to produce the desirable products and decrease the coke
formation on the particles of catalysts. As with the previous units in the oil refinery,
the stream is sent to the hydrogen separation unit to separate and return the
hydrogen back to the feed stream of the reactor. In the stabilizer column, the light
hydrocarbons that may be generated during the reactions are removed. The sepa-
rated hydrocarbons flow from the upper part of the stabilizer column, then they are
blended into the refinery fuel gas unit. The product stream leaves the lower part of
the stabilizer column and enters a C5/C6 splitter column, where C5s are sent out of
the top of the column and recycled back. The nC5 in the C5s is reprocessed and the
iC5 can be sent out of the top of the deisopentanizer as a product. The C6 and
heavier components leave the bottom of the splitter and either go to gasoline
blending or to the catalytic reforming unit.
5.9 Nanotechnology in Refining Processes
Nanotechnology is making a significant contribution to the oil refining and petro-

chemical industry, with potential solutions for the related challenges. For example,
several forms and types of nanomaterials are being used as catalysts for several
types of refinery and developing industry in various units.
One example is the development of mesoporous catalyst materials such as
zeolite and alumina loaded with diverse types of nanoparticles as catalysts. Another
example is the use of nanotechnology in removing harmful toxic substances such as
nitrogen oxides, sulfur oxides, and related acids and acid anhydrides from vapor by
using distinct types of nanofilters and nanoparticles. The removal of mercury from
oil and gas is considered to be another challenge, where nanomaterials can play a
key role in solving these types of the problem by using, for example, nanoparticles
of metal oxides such as copper oxide. Nanotechnology further provides solutions
for carbon capture and long-term storage. The removal of sulfur compounds from
oil is another problem that is being investigated by scientists and engineers. Various
nanomaterials are being developed and evaluated for such applications.
In the following chapters, the role of nanotechnology in solving different oil and
gas-related problems is discussed along with several types of nanomaterials that are
used for such applications.
Acknowledgement The authors acknowledge the support of the chemistry department, and King
Fahd University of Petroleum and Minerals, (KFUPM) Dhahran, Saudi Arabia.
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Chapter 2
Nanotechnology Applications in Petroleum
Refining
Ubong J. Etim, Peng Bai, and Zifeng Yan
Abstract Nanotechnology has successfully gained applications in many areas of

life, thereby seen as the modern way of creating products, which results in high
efficiency of use. In the petroleum processing industries, this revolution is no
exception. The efficiency of a number of conversion processes improves upon
application of materials with the nanometer scale dimension, which is caused by
improvements and developments of better material properties as the particle size
decreases. In this chapter, the applications of nanotechnology through nanocatalysis
in petro-refining processes are highlighted. This is exemplified by discussing the
applications of nanotechnology in several typical petroleum refining processes,
including catalytic cracking, oxidative dehydrogenation of alkanes, and desulfuri-
zation. Other processes for the production of clean fuels are also briefly reviewed.
The key benefits of “nano-tech” application in catalysis are based on the exposure
of a large surface area for reaction, thereby reducing the tendencies to adverse and
side reactions. The desire for an improved catalyst with high activity, low deacti-
vation, and low coke formation to meet the growing demand for chemicals and fuels
necessitates the increasing exploitation of nanoparticles as catalysts.
Keywords Nanotechnology • Nanomaterial • Nanocatalysis • Petroleum

processing
1 Introduction
The quest for exploring and improving the properties of materials at atomic scales
has driven scientists to a broad field of research known as nanotechnology. Funda-
mentally, at the nanoscale, the properties of materials between 1 and 100 nm
provide new insights into improvements of the existing materials and ways to
U.J. Etim • P. Bai (*) • Z. Yan (*)

State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao
266580, China
PetroChina Key Laboratory of Catalysis, China University of Petroleum, Qingdao 266580,
China
e-mail: [email protected]; [email protected]

38 U.J. Etim et al.
designing novel ones with striking features can be successfully and effectively
explored. Nanotechnology has successfully gained applications in many areas of
life, resulting in improved efficiency of product creation and utilization. In the
scientific world, the term “nano” is used as a prefix that means “billionth” or a
factor of 10–9 or 1/109. A nanometer, therefore, refers to a unit which indicates an
order of spatial measurement that is one “billionth” of a meter.
Nanotechnology could be defined as the science, engineering, and application of
materials at the nanoscale (i.e., at least one dimension measured in nanometer)
(Zhou 2007). The nanoscale means dimensions in the order of 100 nm or less. With
the increased sensitivity of analytical tools at the nanometer levels, nanoscience has
thus brought one of the most incredible and remarkable revolutions into the world
of material science, enabling diverse applications. The first mention of the idea and
concept of nanoscience and nanotechnology is credited to a physicist, Richard
Feynman, in 1959 during a talk to the American Physical Society, where he
described the process in which scientist could be able to manipulate and control
materials at the nanoscale. The talk titled “There is plenty of room at the bottom”
allows humanity to benefit from the implication of materials to obtain miniaturiza-
tion for applications of the previous technologies.
The impacts of nanotechnology in the society have been unambiguously and
overwhelmingly felt in many areas through improved efficiency and high-quality
products developed at reduced overhead cost, which increases demand. Thus,
nanotechnology can be considered fundamental to the modern ways of life.
Improved and efficient products which span all sectors of the society are immediate
consequences of the intimate integration of the so-called nano-tech. Presently,
nanotechnology is applied to all areas of life, and its applications are exploited in
a number of industries, including electronics, materials and manufacturing, aero-
space, photography, construction, chemicals as well as petroleum refineries. The oil
and gas industries, from upstream through the midstream to downstream have gone
through stages where chemical processes are facilitated because of the relevancy of
employing materials with unique size-dependent properties.
1.1 Nanosize
Just how small is the nanosize? “Nano” is about as small as it gets in the world of
regular physical, materials, and biological sciences (Lindsay 2009). Based on the
units, things are measured in our everyday life, for instance, the diameter of a
hydrogen atom is about one-tenth of a nanometer, so the nanometer scale is the
smallest scale on which one might consider building blocks on a scale. Generally,
atoms are smaller than a nanometer, one atom measures in the range of
~0.1–0.3 nm, depending on the type of the element. As could be seen in Fig. 2.1,
several other objects exist at the nanometer scale. Examples include viruses
(30–50 nm), DNA (2 nm), buckyballs (1 nm in diameter), carbon nanotubes
(~1 nm in diameter), and many catalysts used in the production of fuels and
petrochemicals are based on nanoparticles. The thickness of a sheet of paper is
2 Nanotechnology Applications in Petroleum Refining 39
Fig. 2.1 Some nanometer-sized materials. Adapted from Grunes et al. (2003), with permission of
the Royal Society of Chemistry
about 100,000 nm and the human hair is about 50,000–100,000 nm in diameter

(Grunes et al. 2003). Objects and dimensions that are this small are difficult to
measure with the conventional instruments and require special tools for analysis.
So, the sensitivity of measurement is enhanced using powerful microscopic tools
that permit the use of unique methods to allow for the visualization of surface
features on the atomic scale, such as atomic force microscopy (AFM), scanning
electron microscopy (SEM), transmission electron microscopy (TEM), and scan-
ning tunneling microscopy (STM). These characterization tools have been fre-
quently used to examine the nanostructure of model catalyst systems. Using
STM, for example, it becomes possible to explain why doping Ni catalysts used
for the steam reforming of methane with a small amount of gold reduces the
tendency of such catalysts to deactivate because of carbon deposition (Besenbacher
et al. 1998).
1.2 Nanomaterials
Nanomaterials possess unique properties derived from features present in them that
are measurable on the nanometer scale. Examples of nanomaterials in use in
modern industrial applications include carbon materials, metal oxides, and zeolites.
40 U.J. Etim et al.
The preparation of materials at the nanoscale is feasible through careful design and
controlled synthesis procedures. Generally, nanomaterials can be synthesized by
two widely known methods, either by bottom-up or top-down approach. The
bottom-up approach involves the formation of nanomaterials by reaction and
assembly of the reactants in the presence or absence of structure directing agents
(SDA). In the top-down approach, the bulk materials are broken down to smaller
particle size by mechanical, thermal, or chemical methods. The former has the
advantage of precise control of the particle size; however, the use of expensive
precursors and surfactant increases cost. The latter has the disadvantage of
nonuniform particle size. Faujasite zeolite nanosheets, for example, are synthesized
by controlling the pore structure using SDA and crystallization temperature that
allow for the formation of zeolite particles with interstitial pores between the
nanosheet assemblies (Inayat et al. 2012; Mehlhorn et al. 2014; Yutthalekha et al.
2016). The most important property to optimize during the synthesis of
nanomaterials is the surface area. The shape, size, and composition of the surface
need to be controlled as well. These properties are of basic importance in applica-
tions involving catalysis because they are the determinants of catalyst activity and
stability. Often, the surface area increases with a decrease in the dimension of a
material. Thus, as the material size decreases, a greater portion of the atoms are
found at the surface compared to the bulk material. Because growth and catalytic
chemical reactions occur at materials surfaces, a given mass of nanomaterial reacts
more compared to the same mass of bulk material. Additionally, materials that are
inert in their bulk form are reactive when existing in nanoscale. Nanomaterials are
expected to have a much greater surface area per unit volume compared with larger
particles. This property makes them more chemically reactive because atoms at the
surface of some materials do not have covalent bonds as they are in an energetically
unstable state. Since more atoms located at the surface are in energetically unstable
states, nanomaterials are more reactive compared to the bulk materials.
1.3 Nanoparticles
Nanoparticles in principle have sizes ranging between 1 and 100 nm (Rao et al.
2002). Their physical and chemical properties are intermediate those of the atom of
an element and the bulk material. The beneficial aspect of this class of materials as
compared with their bulk (microparticles greater than 1 μm) is often size-
dependency of functions. As the size decreases and approaches the nanoscale,
new and fascinating functional properties develop and become significant, such
as color change and phase transformation. For example, the unique physical
properties of nanoparticles allow high absorption of radiation in photovoltaic
cells that are composed of nanoparticles than does in thin films of continuous
sheets. Other examples of size-dependent property changes could be seen in
quantum confinement in semiconductor particles, surface plasmon resonance in
some metal particles, and in chemical reactivity that is utilized for image formation
Fig. 2.2 Schematic

illustration of the ways to
increase the surface area of
dense solids. Adapted with
permission from Valtchev
and Tosheva (2013).
Copyright (2013) American
Chemical Society
in photography (Lindsay 2009). Increasing the number of surface atoms in a

material often increases surface-to-volume ratio and chemical potentials in the
material (Zhou et al. 2009). The number of surface atoms in solid materials can
be increased by (1) decreasing the size of bulk particles or (2) creating open pore
network within the bulk of the material as illustrated in Fig. 2.2 (Valtchev and
Tosheva 2013). Another unique method is to synthesize nanosized particles
containing accessible and uniform nanopores. The size of nanoparticles is very
instrumental in determining chemical properties. In catalysis, nanoparticles or
nanomaterials play a vital role in improving chemical transformations.
1.4 Nanocomposites
A nanocomposite is a multiphase solid material in which at least one of the phases

has one, two, or three dimensions of less than 100 nm. In other words, a
nanocomposite material is composed of a bulk matrix and at least one nano-
dimensional phase with properties different from those of the matrix. The properties
of a nanocomposite differ considerably from those of the constituent and/or con-
ventional composite materials due to dissimilarities in structure and chemistry, the
exceptionally high surface-to-volume ratio of the reinforcing phase and/or its
exceptionally high aspect ratio. A reinforcement surface area indicates that a
small amount of nanoscale reinforcement has an observable effect on the macro-
scale properties of the nanocomposite. As an example, loading carbon nanotubes
enhances the electrical and thermal conductivity of a conductor bulk material. Also,
some nanomaterials result in enhancing optical, dielectric, and mechanical
42 U.J. Etim et al.
characters and heat resistance. Examples of nanocomposites include porous media,

colloids, gels, and copolymers. The mechanical, electrical, thermal, optical, elec-
trochemical, and/or catalytic properties of a nanocomposite differ markedly from
those of the individual component materials. Size limits for these effects have been
proposed: size <5 nm finds applications in catalysis, <20 nm for making a hard
magnetic nanomaterials soft, <50 nm for refractive index changes, as well as
<100 nm to achieve super magnetism, mechanical strengthening or restricting
matrix dislocation movement (Kamigaito 1991).
2 Nanocatalysis
The application of nanotechnology in petroleum refining is mainly driven by the

creation of nanocatalysts that have led to improvement in the fields of both
homogeneous and heterogeneous catalysis. Nanoparticles are important catalysts
for petroleum processing and energy conversion. The performance of a catalyst is
sensitive to particle size because the surface structure and electronic properties can
change greatly with size (Zhou et al. 2009; Bell 2003). For example, the heat of
adsorption for CO and the activation energy for CO dissociation both change with
increasing the size of Ni particles, consequently, affecting the performance of Ni
nanoparticles in the Fischer–Tropsch synthesis of hydrocarbons from synthesis gas
(Bell 2003). Reducing the particle size of porous materials to nano-dimensions
allows for the optimization of their applications in catalysis. Nanoporous materials
show improved catalytic activity in diffusion-limited reactions, and manipulation of
nanocrystalline suspensions using colloidal chemistry approach results in the prep-
aration of 2D and 3D microporous materials with adjusted characteristics for
catalytic reactions (Valtchev and Tosheva 2013).
Nanocatalysis involves the synthesis and characterization of supramolecular
materials at the nanometer level and their controlled applications (Schl€ogl and
Abd Hamid 2004). It differs from conventional catalysis since the materials are
explicitly designed to a length scale much larger than that of a single active site. It
has been demonstrated in various reactions that the use of nanocatalyst can decrease
the energy requirements in chemical processes, resulting in a greener chemical
industry. The contribution of nanoscience and nanotechnology may have been seen
as a springing science in catalysis; however, it will be of beneficial interest to clarify
that the selectivity principles by which heterogeneous catalytic reactions proceed
rely exclusively on nanocatalysis, and the use of small particles in technical
catalysis has been operated for ages (Schl€ogl and Abd Hamid 2004).
Nanoporous materials are fundamental to the modern petroleum refining and the
petrochemical industry. Zeolites, for instance, are employed as key catalysts in
petroleum refining. Zeolites are crystalline aluminosilicate materials with well-
defined pore connection dependent on the particular topology. There are about
230 zeolite framework types (“Database of Zeolite Structures, http://www.iza-
structure.org/databases/”) of which the commonest ones employed in large
Fig. 2.3 Structure of zeolite Y (FAU). Constructed from (“Database of Zeolite Structures, http://
www.iza-structure.org/databases/”)
quantities in the petroleum refining and the petrochemical industry are zeolite Y
and ZSM-5 of FAU and MFI topologies as in Figs. 2.3 and 2.4, respectively. Of
special note is that these zeolites consist in nano-pores that allow for molecular
sieving functionalities in them as shown in Fig. 2.5. So far, their excellent shape
selective properties position them as one of the most important heterogeneous
catalysts practically in use.
The relevant nano-pore sizes (0.74–1.2 nm in zeolite Y and 0.54–1.0 nm in
ZSM-5) afford these zeolites the ability to screen heavier hydrocarbon molecules,
allowing only those with a diameter less than or equal to their pore size to pass
through. For more than five decades, zeolites have contributed immensely to the
growth of the petroleum industry, being a catalyst for the transformation of less
valued crude oil fractions to more valued and desirable products by a process
known as fluid catalytic cracking (FCC). Although zeolites contain inherent
nanosized pores that classify them as nanomaterials, they are usually of micrometer
particle size. Controlling the synthesis conditions of the conventional micrometer-
44 U.J. Etim et al.
Fig. 2.4 Structure of zeolite ZSM-5 (MFI). Constructed from (“Database of Zeolite Structures,
http://www.iza-structure.org/databases/”)
Fig. 2.5 Molecules diffusion through the zeolite Y pore (7.4 Å). Adapted from (“Database of
Zeolite Structures, http://www.iza-structure.org/databases/”)
sized zeolite could result in entirely nanosized zeolites such as nanosheets. For
practical applications in catalytic reactions, it is important to understand the
differences between the nanocrystals and microcrystal zeolites. The nanocrystal
zeolites exhibit high external surface area, which is advantageous for processing
bulky molecule that cannot penetrate through the small pores and channels of
zeolites. In addition, they have shorter diffusion path lengths than the conventional
micrometer-sized zeolite (Farcasiu and Degnan 1988; Weisz 1995).
2.1 Supported Metal Catalysis
2.1.1 Catalyst Support
The advances in the synthesis of materials for improved catalytic performance of

various reactions have led to exciting strategies for creating catalyst particles that
are of very small size. In most of the applications, these catalysts are sat on porous
metal oxide supports, which have diameters in orders of a nanometer. This strategy
contributes to the production of nanometer length scale catalysts that are very active
and stable under various high reaction severities. Among the widely used support
materials for catalyst fabrication, alumina and silica have received considerably
most applications for reasons pertaining to cost-effectiveness and excellent phys-
icochemical properties as catalyst supports. Aluminas are widely employed as
standard supports for many metal and sulfide catalysts at the industrial scale. For
catalysts requiring relatively low reaction temperature (less than 500 C), such as for
hydrogenation using platinum, palladium, or metal sulfides as active phase, high
surface area alumina can be used. For low-temperature reactions, such as partial
oxidation reactions, transition aluminas are preferable. Stabilized aluminas with
silica or alkali, alkali-earth, or rare earth cations (K+, Ca2+, La3+, etc.) are exten-
sively used for reactions requiring medium to high temperatures. An example is the
case of some endothermic reactions such as steam reforming or partial oxidation
reactions using platinum or rhodium catalysts. Silicas possess excellent mechanical
and thermal stabilities and are also widely used as supports for industrial applica-
tions. Nickel and copper catalysts supported on silica are frequently used for
hydrogenation reactions. In some other cases, silicas are used as stabilizers as a
very little amount is required.
2.1.2 Particle Size Effect of Metal Oxide Supports
The influence of crystalline structure or particle size on the solid-state chemistry of

materials, including metal oxides used as catalyst supports has received great
attention recently. It has long been conceived but came to limelight at the birth of
nanoscience and nanotechnology. Practically, nanostructured catalysts are more
stable materials in comparison to its bulk counterparts for the reason that the
surface-free energy predominates in the bulk. This was first reported for γ-Al2O3
with respect to corundum α-Al2O3 (McHale et al. 1997) and for other polymorphic
systems such as anatase-TiO2 with respect to rutile (Zhang et al. 2009) as well as
tetragonal ZrO2 in comparison to monoclinic zirconia (Zhang et al. 2006).
46 U.J. Etim et al.
Therefore, the easy formation and stabilities of γ-Al2O3, anatase TiO2, and tetrag-
onal ZrO2 at room temperature are because of their existence in the form of
nanoparticles (Busca 2014). An unpromoted, size-selected Ag3 clusters and
~3.5 nm Ag nanoparticles on alumina supports can catalyze direct propylene
epoxidation with only a negligible amount of carbon dioxide formation and with
high activity at low temperatures (Lei et al. 2010), whereas bulk Ag catalyst
produces substantial amount of carbon dioxide. Density functional calculations
show that, relative to extended silver surfaces, oxidized silver trimers nanoclusters
are more active and selective for epoxidation reaction because of the open-shell
nature of their electronic structure (Lei et al. 2010). Valence electrons in bulk
metals form continuous bands, and upon reduction of the bulk material in a certain
direction down to the nanometer scale, the motion of electrons in this direction is
subject to confinement (Yang et al. 2015; Valden et al. 1998). In this regard,
compared to bulk metals, nanoparticles exhibit much larger total exposed surface
areas and various combinations of surface structures, and the electronic confine-
ment effects within nanoparticles lead to major changes in the electronic structure
(Valden et al. 1998; Haruta and Daté 2001). This raises the possibility of tuning the
catalytic process. In this way, nanotechnology could provide an effective means
through which the surface structure and electronic properties of supported
nanocatalysts can be effectively controlled without changing their composition. A
very small crystal size of the nanocrystalline zeolite contributes favorably to both
the formation of a high external surface area, with no steric constraints, and to a
faster diffusion of reactant molecules to the acid sites located within the zeolite
micropores (Serrano et al. 2010). This feature leads to catalytic performance
improvement. It is therefore clear that the activity and selectivity of catalyst
nanoparticles are strongly dependent on their size and shape as well as surface
and electronic structures.
Particle size reduction of the active metal offers an invaluable benefit to energy
cost reduction. Au nanoparticles having dimensions less than 10 nm are often used
for various applications including catalysis. In catalysis, selective oxidation of
ethanol in oxygen catalyzed by SiO2 supported Au shows an improved activity at
a lower temperature than does the bulk Au catalyst (Zheng and Stucky 2006). This
behavior, besides improved catalytic activity, demonstrates energy conservation
that comes with smaller particle size catalyst. The size of Co particles plays a key
role in determining its selectivity performance. Co nanoparticles with a mean
diameter of 6–10 nm can improve the selectivity of C5+ hydrocarbons than the
bulk Co (Bezemer et al. 2006). In the following sections, selected examples of
petro-refining/chemical processes where nanotechnology finds immense applica-
tions are discussed.
3 Petroleum Refining Processes
3.1 Catalytic Cracking
Catalytic cracking occurs on solid acids catalysts. Its development in the late 1930s
brought a revolution into the petroleum industry that was previously relied entirely
on thermal cracking. The cracking catalysts are usually crystalline aluminosilicate
solids with acid sites strong enough to cause the scission of carbon–carbon bond in
hydrocarbon molecules. Unlike thermal cracking, the use of powder catalysts pro-
vides alternative routes for cracking by lowering the activation energy for the
reaction. One of the areas where the application of nanoscience has a success
story is the petroleum refining. As mentioned earlier, the use of zeolite catalyst in
the FCC for the conversion of heavy crude oil fractions has been an important
revolution in the petroleum industries since the 1960s, and its significant contribu-
tions are continuously felt hitherto. As of today, over seven million barrel of
petroleum products and chemical are annually produced using the zeolite catalyst
(Zhou 2007).
3.1.1 Nanozeolite
Crystalline zeolites have 3D networks of well-defined micropores (<1.2 nm). With

these pore constraints, only molecules of comparable or size less than the pore
aperture can access the active sites. Catalytic reactions are therefore restricted to the
molecules having a diameter below the pore constraints. Thus, larger feed mole-
cules are then crack on the external surface of the zeolite. The use of nanosized
zeolite could overcome this limitation because as the ratio of external to internal
number of atoms increases when the particle size decreases, the zeolite nanocrystals
present a large external surface area and high surface activity (Vuong et al. 2010).
The improved surface area exposes move acidic sites for catalytic reactions. This
increases catalytic performance due to higher accessibility to active sites. Decreas-
ing the zeolite crystallite size has been demonstrated to increase the conversion and
the selectivity of gas oil (Rajagopalan et al. 1986). Compared with micron-sized,
nanosized zeolites exhibit a higher activity, lower coking activity and longer life in
many reactions. One of the pioneer studies that demonstrate the influence of zeolite
crystal size on catalytic cracking was published in 1986 (Rajagopalan et al. 1986).
NaY zeolite crystals size ranging from 60 nm to 0.65 μm was employed for catalytic
conversion of gas oil in the FCC reaction. The catalyst containing the smallest
particles exhibited improved activity and selectivity to gasoline and light cycle oil
(LCO) as in Fig. 2.6a, b. These improved selectivities were attributed to the
decreased diffusion resistance to the gas oil and produced gasoline in the nanosized
zeolite. With nanozeolite, the conversion of hydrocarbons can be greatly improved.
Vuong et al. (2010) synthesized a series of zeolite Y nanocrystals and compared
their catalytic activity in a standard gas oil cracking test. It was found that small
48 U.J. Etim et al.
Fig. 2.6 Selectivity of heat-treated zeolite particles (2 h at 538 C) to (a) gasoline and (b) light
cycle oil, LCO catalysts on west Texas heavy oil feed. Adapted from Rajagopalan et al. (1986)
with permission from Elsevier. Copyright 1986 Elsevier publishers
nanosized zeolite (25, 40, and 100 nm)-based FCC catalysts exhibited higher
catalytic activities compared to larger ones as illustrated in Fig. 2.7. A correlation
is between gasoline selectivity in FCC feedstock conversion and zeolite particle
size. This performance of zeolite catalysts followed the trend as: FCC-100 < FCC-
40 < FCC-25, which can be explained by the cracking of FCC feed on the external
surface of zeolite crystals.
The intrinsic properties of a catalyst can be modified by reducing the crystallite
size. Nanosized ZSM-2 (~100 nm) has been recently prepared (Covarrubias et al.
2009). This type of zeolite possesses improved acidity, high surface area and
maintains the structural stability that makes it highly attractive for catalytic appli-
cations. The nanosized ZSM-2 zeolite offers as an excellent catalyst support for
Fig. 2.7 MAT conversion curve for nanozeolites-based FCC catalyst. Adapted from Vuong et al.
(2010) with permission from Elsevier. Copyright 2010 Elsevier publishers
metallocene polymerization. A nanoporous aluminosilicate (MMZUSY) obtained

from USY zeolite exhibits high thermal stability and accessibility for oil molecules
in the conversion of bio-oil. When compared with MCM-41, the MMZUSY showed
excellent catalytic activity and selectivity due to improved surface acidity (Park
et al. 2008). Catalytic cracking activity on the external surface of nanozeolites of
FAU (zeolite Y) and MFI-type (ZSM-5) was evaluated in 1,3,5-triisopropylbenzene
conversion and compared with conventional micron-sized zeolite Y and ZSM-5
crystals used as reference samples. Smaller crystal catalysts showed higher activ-
ities and an increase in conversion with the time of reaction. The conversion was
high for zeolite Y, as it is related to high amounts of surface acid sites with respect
to ZSM-5 (Morales-Pacheco et al. 2011). Nanosized zeolite Y crystals are
employed in the selective catalytic reduction of NO2 with urea (Li et al. 2005).
The reaction rate is significantly higher than that of commercial FAU-type zeolite.
The performance of nanosized crystallites when compared with that of commercial
micrometer-sized zeolite Y is attributed to the larger external surface of zeolite
nanocrystals rich in silanols, and extra-framework Al is found to be responsible for
the higher reaction rate. Additionally, a decrease in the formation of undesired
products like biuret and cyanuric acid is observed on the nanosized catalyst.
Light olefins, usually produced by the thermal cracking of naphtha, are an
invaluable product of the petroleum industry and an important raw material for
the petrochemical industry. Presently, an alternative method for producing light
olefins in large quantities is by catalytic processes. An example is the use of
methane as a source of methanol followed by methanol-to-olefin (MTO) reaction.
The most often used catalysts for this reaction are ZSM-5 and SAPO-34. SAPO-34
shows higher selectivity to light olefins; however, it is rapidly deactivated due to
coke deposition. A decrease in the crystal size of SAPO-34 is expected to reduce the
50 U.J. Etim et al.
coke formation and thus increase the effectiveness factor (Valtchev and Tosheva
2013). Comparing the catalytic properties of nano- and micrometer-sized SAPO-34
crystals in the MTO reaction, the nanosized catalysts exhibit a longer catalyst
lifetime, which is related to the enhanced diffusion and desorption of produced
hydrocarbons, leaving the micropore space unblocked and thus limiting side reac-
tions and coke formation (Hirota et al. 2010).
3.1.2 Synthesis of Nanozeolites
The synthesis of zeolite nanocrystals was somewhat challenging until recently

when practical approaches have become feasible. Like the conventional micron-
sized zeolites which yield particles with dimension of about 1 μm, nanocrystal
zeolites are also synthesized from clear solutions under hydrothermal conditions
(Persson et al. 1994; Mintova et al. 2016; Schoeman et al. 1994). Special attention is
required during preparation of the initial precursor gel to favor the nucleation and
crystallization processes. The number of nuclei in the homogeneous precursor
solution determines the crystal size. Therefore, a system with sufficient nucleation
results in very small crystals (Mintova et al. 2016). Different methods can be
adopted for the synthesis of zeolite nanocrystals, namely, hydrothermal crystalli-
zation, microwave, ultrasonic, confined space, seeding and use of microreactor
(Askari et al. 2013; Jo et al. 2013; Pan et al. 2009; Jacobsen et al. 2000a, b; Schmidt
et al. 2000; Sun et al. 2015, Lv et al. 2013, Hu et al. 2009, Kore et al. 2014; Gao
et al. 2016). Hydrothermal crystallization is the most widely employed method
because of the ease to control the crystallization process. The precursor gel solution
is prepared in such a way to favor the nucleation over the growth of the crystals and
to limit the aggregation between the growing crystals. Furthermore, a number of
other factors have to be controlled to achieve the desirable nucleation. Such factors
include polymerization process during preparation of the initial precursor gel,
hydrothermal treatment temperature, the amount of the metal cation in the colloidal
precursor solution, and the type and concentration of SDA. In addition, alkalinity of
the gel solution, crystallization time, precursor gel molar composition, and zeolite
particle source affect the particle size of the synthesized zeolites and direct the
growth of the crystals to the desired zeolite structure (Covarrubias et al. 2009; Sun
et al. 2015; Davis et al. 2015). High supersaturation and steric stabilization of the
proto-nuclei in the presence of quaternary ammonium cations play crucial roles in
the formation of non-aggregated zeolite nanocrystals (Covarrubias et al. 2009).
In zeolites formation mechanism, generally, amorphous particles are initially
formed and then converted into crystals with changing size. Zeolite nuclei form in
the center and grow outwards until the whole amorphous particles are transformed
into crystalline ones. After heating at a high temperature, larger cubic crystals are
obtained (Mintova et al. 1999). However, other mechanisms of nanozeolite crystals
formation have been reported in the literature. Recently, it has been shown that very
small sized EMT-typed zeolite can be synthesized from template-free Na-rich
precursor system (Ng et al. 2012a, b). The resulting nanosized zeolite which
exhibited a size of 15 4 nm along the a and c directions, respectively, was
possible due to the control of the polymerization process during the preparation of
the initial suspension (Ng et al. 2012a, b) and the low-temperature hydrothermal
treatment that limited the growth of the crystals and inhibited competitive zeolite
structures. Hierarchical beta nanozeolites were synthesized from protozeolite seeds
in the presence of an organosilane as a precursor. It was found that zeolite
crystallization proceeded through a condensed step mechanism, gradually growing
from the evolved nuclei. The organosilane played important roles as a mesoporogen
and a growth inhibitor. The crystal size and mesopore properties of the prepared
hierarchical beta nanozeolites strongly depended on the properties of seeds (Sun
et al. 2015).
3.2 Oxidative Dehydrogenation of Alkanes
Oxidative dehydrogenation (ODH) of propane is an attractive option for propene

production. In the presence of oxygen, the thermodynamic restrictions of dehydro-
genation are overcome and the exothermic character of the reaction renders it an
energetically efficient process (Karakoulia et al. 2009). Vanadia nanoparticles
supported on various oxides ZrO2, Al2O3, MgO, SiO2, TiO2, CeO2, and Nb2O5
are active catalysts for the ODH of alkanes to olefins (Khodakov et al. 1998; Corma
et al. 1992; Wachs and Weckhuysen 1997; Khodakov et al. 1999). A recent study
shows that the ODH activity per atom of exposed V decreases with increasing size
of the vanadia clusters (Khodakov et al. 1999). Support surfaces that covered with
small V2O5 clusters containing V–O–V or V¼¼O linkages lead to high dehydro-
genation rates and selectivities. The composition of the support influences the
speciation of different VOx species and V2O5 clusters, and thus the catalytic
behavior of supported vanadia in ODH reactions (Khodakov et al. 1999). Also,
the sizes of preselecting platinum clusters were demonstrated to greatly enhance
ODH of propane to propylene (Vajda et al. 2009). Platinum nanoclusters stabilized
on high surface area supports are 40–100 times more active for ODH of propane
than previously reported for bulk platinum, in addition to exhibiting high selectivity
to propylene over undesirable products. The superior performance of the nano-
platinum catalyst as revealed by quantum calculations indicates that under-
coordination of the platinum atoms is responsible for the high reactivity with
extended surfaces (Vajda et al. 2009). The calculated transition states and interme-
diates in the reaction of C3H8 leading to the formation of propylene on the Pt4
cluster are shown in Fig. 2.8. The “true” barrier to breaking the first C–H bond is
only 0.42 eV. The corresponding barrier referenced to gas-phase propane (the
“apparent” barrier) is slightly smaller (0.18 eV); this barrier is found to be smaller
(0.05 eV) when recalculated on a Pt8 cluster. In spite of the small magnitude of the
energetic barrier, this step will probably be rate-limiting because of the very large
entropic loss, and consequently, lower pre-exponential factor, associated with
propane adsorption at high temperatures on the clusters. The other pathways are
thermodynamically downhill to the formation of propylene, which binds to Pt4 by
its π bond (Vajda et al. 2009).
52 U.J. Etim et al.
Fig. 2.8 Conversion of propane to propylene from DFT calculations for the dehydrogenation of
propane on a Pt4 cluster leading to the formation of propylene adsorbed on the cluster. Energies
(in eV) of the equilibrium structures are relative to the reactants. Energy barriers for the transition
state structures are relative to the preceding equilibrium structure (“true” barriers). The first barrier
corresponds to breaking of the first C–H bond (on the CH2 group) and the second barrier
corresponds to breaking of the second C–H bond (on a CH3 group). The dotted lines in the
structures indicate partial bonds. Reprinted with permission from Macmillan Publishers Ltd.
Nature Chemistry (Vajda et al. 2009), copyright 2009
3.3 Desulfurization of Petroleum
Due to stringent regulations by various environmental protection agencies across

the world on the release of poisonous gases to the environment from petroleum
exploitation, desulfurization of commercial fuels is widely practiced in order to
reduce the sulfur content to less than 10 ppm in the refined petroleum products. In
the upgrading of heavy oil via desulfurization, unsupported metal sulfide catalysts
in its natural state are gaining serious attention. To increase the desulfurization
capacity of these catalysts, the particles size need to reduce as much as possible to
eliminate the introduction of toxic sulfur compounds to pre-sulfurize the hydroge-
nation catalysts. This simplifies the application process and improves the efficiency
of the catalysts (Li and Zhu 2012). Several types of sulfur removal are carried out
using metal catalysts. Catalysts based on molybdenum, cobalt, and nickel dispersed
on different supports are effective catalysts for the removal of sulfur from petro-
leum and petroleum products (Li and Zhu 2012; Sudhakar 1998; Mohajeri et al.
2010). The composition, as well as particle size, can play an important role in the
performance of the catalysts. A US patent 20100167915A1 (Mohajeri et al. 2010)
discloses that hydrodesulfurization (HDS) catalysts on nanostructured porous car-

bon supports are excellent for desulfurization of hydrocarbon feedstocks. A
nanocomposite based on anatase-vanadium-polyphosphomolybdate ((TiO2)/
(Bu4N)4H[PMo10V2O40]) shows a good capacity to oxidatively desulfurize a sim-
ulated gas oil. The nano layer of the anatase phase with a particle size of 20 nm
shows a high S conversion (more than 98%) (Rezvani et al. 2014). The high
oxidative desulfurization (ODS) of gas oil proves an efficient, convenient, and a
practical method for scavenging sulfur compounds with this nanocomposite mate-
rial. Fe@Si–PMo10V2 nanostructured support as a catalyst for the ODS process
selectively oxidizes sulfides to the corresponding sulfoxides and sulfones under
mild reaction conditions. The catalyst also exhibits excellent activity to remove
sulfur contents in model oil and shows a high potential as an effective catalyst for
deep desulfurization of diesel. The presence of other compounds such as nitrogen
and aromatic compounds can affect ODS conversion. An important characteristic of
this nanocatalyst is its reusability after at least three ODS cycles with a good
catalytic activity (Rafiee and Rezaei 2016). Reusability of the catalyst is an
important consideration in the design of a catalyst for industrial applications. Silver
supported on mesoporous silica nanoparticles exhibits excellent regeneration sta-
bility and maintains high activity up to six cycles (Hauser et al. 2016). This is due to
the reduction of silver ions to silver nanoparticles within the mesochannels of the
extra-framework aluminum. The good behavior of hematite (Fe2O3) nanoparticles
for thiophene decomposition in desulfurization reaction is a result of the unique
properties of the catalyst (Khalil et al. 2015). Among other factors, the size of the
hematite nanocatalyst influences the ability of the catalyst to decompose thiophene.
The catalytic performance increases with an increase in reaction temperature and
the amount of the catalyst but decreases with the particle size and the presence of
hydrogen donor. Hydrogen donor covers the surface of the catalyst and blocks the
active sites. In this reaction, the catalytic process involves a cyclic phase transfor-
mation of some of the hematite to magnetite (Fe3O4) as thiophene is oxidatively
decomposed into its products and reoxidation of magnetite to hematite in the
presence of water as the source of active oxygen (Khalil et al. 2015). Recently,
carbon materials have become excellent supports for various catalysts in different
desulfurization reactions (Mohammed et al. 2017; Guo et al. 2017). Nanocatalyst
composite structure was prepared on various carbon nanotube supports and the
formation of network structure between metal catalysts and CNTs was observed
(Mohammed et al. 2017). These supports enable the homogeneous spreading of the
active CoMo particles within the bulk of CNTs. Experiments using these
nanocatalysts reveal better results than the conventional catalyst (CoMo/Al2O3)
in the removal of sulfur from gas oil. An improvement of about 10% in HDS over
conventional catalyst was obtained after 10 h under conditions: 280 C of reactor
temperature, 10 bar of system pressure, and 2 h1 of space velocity of gas oil, which
were optimum conditions to remove sulfur from the gas oil (Mohammed et al.
2017). In an in situ experiment for upgrading heavy oil, different carbon
54 U.J. Etim et al.
nanomaterials were utilized as catalysts in the HDS reaction with thiophene as a

sulfur-containing model compound. The carbon nanocatalysts possessed an
ultrahigh specific surface area and a good degree of graphitization. It was found
that the graphitization degree of the carbon-based nanocatalysts is of great impor-
tance in the HDS reaction, contributing to catalytic activity. The performance of the
carbon-based nanomaterials demonstrates the potential application of carbon
nanomaterials as metal-free catalysts in in situ upgrading and recovery of heavy
crude oil, which will contribute to a more sustainable chemistry in terms of
production and refining of heavy crude oils (Guo et al. 2017).
Synergism of nanosized materials improves stability and recycling of catalysts
for reusability (Hauser et al. 2016). Zeolites as supports for desulfurization catalysts
synergistically contribute to excellent activities of the catalysts. Crystalline
mordenite nanofibers support with a bundle structure containing parallel mesopore
channels were tested for sulfur removal in HDS. Cobalt and molybdenum (CoMo)
species were introduced into the mesopores and micropores of nano-bundles
mordenite (NB-MOR). The NB-MOR supported CoMo catalyst (CoMo/NB-
MOR) exhibited an unprecedented high activity (99.1%) as well as very good
catalyst life in the HDS of 4,6-dimethyldibenzothiophene and diesel compared
with a conventional γ-Al2O3 supported CoMo catalyst (61.5%). The spillover
hydrogen formed in the micropores migrates onto nearby active CoMo sites in
the mesopores, which could be responsible for the great enhancement of the HDS
activity (Tang et al. 2013). These features are crucial for the design and preparation
of multifunctional high activity catalysts for HDS, selective cracking, and hydro-
cracking (Tang et al. 2013). The alumina-nano Y zeolite (Al2O3-nY) composites
reduce the metal-support interaction and heighten the MoS2 stacking degree,
shorten slabs, and enlarge corner Mo atoms. The addition of nanozeolite also
enhances the overall acidity, which improves the HDS activity compared with
NiMo/Al2O3 catalysts. Synergism of the hydrogenation activity and acid amounts
is responsible for the improved activity (Yin et al. 2011, 2015). The differences in
the basicity and/or acidity of support materials are important contributors to the
performance of desulfurization catalyst (Zhang et al. 2015). A large amount of the
strong basic sites can avoid the polymerization of catalyst species and form small
oxide clusters. On Co-MoS2/NS-MgO, after sulfidation, small MoS2 clusters with
shorter lengths and less stacking formed on the NS-MgO contribute to an increase
in the sites available for Co-promotion, resulting in the Co-MoS2/NS-MgO catalyst
with a high HDS activity (Zhang et al. 2015).
3.4 Fisher–Tropsch Synthesis
Fischer–Tropsch synthesis (FTS) is one of the efficient ways to convert coal,

biomass, and natural gas into hydrocarbon derivatives through the intermediacy
of synthesis gas (a mixture of H2 and CO) on supported metal catalysts (Jiao et al.
2016). The greatest challenge with this process in the production of olefins is low
conversion and selectivity to lighter olefins (C2¼ to C4¼). Towards overcoming

these limitations, supported metal nanoparticles have shown high promise as an
effective catalyst for increasing conversion of lower olefins (López and Corma
2012; Galvis et al. 2012). Conversion of syngas to C2 through C4 olefins with
selectivity up to 60 w%, using catalysts that compose of iron nanoparticles,
homogeneously dispersed on weakly interactive α-alumina or carbon nanofibers
supports is reported (Galvis et al. 2012). The use of iron nanoparticles improves
stability of the reaction performed at high temperature, which is necessary to shift
product selectivity to lighter hydrocarbons that is lacking with bulk iron catalysts.
At a high temperature, the undesirable Boudouard reaction, 2CO(g) ! C(s) +
CO2(g) (Steynberg and Dry 2004), leads to the deposition of carbon, which can
block the active sites and induce fragmentation of the particles in bulk iron catalysts
(Shroff et al. 1995). The mechanical and thermal instabilities of the bulk iron oxide
catalysts also result in the plugging of the catalyst bed in fixed-bed operation or in
the fouling of separation equipment in a fluidized-bed process (Galvis et al. 2012).
Compared with bulk Fe, the nanoparticle Fe catalysts display improved catalytic
performances under industrial relevant conditions as shown in Fig. 2.9. It is also
very clear that the support type exhibits significant effects on the performance for
nano-Fe catalyst. After an initial activation period, Fe/b-SiC, Fe/CNF, 25 wt%Fe/α-
Al2O3, and Fe/γ-Al2O3 show stable catalytic activities for up to 60 h (Galvis et al.
2012). The stability maintained during this time fully complies with the require-
ments for the application of catalysts in fluidized-bed reactors relevant in industrial
applications of the exothermic FTS to olefins process.
The supported and bulk Fe catalysts tested in the FTS reaction at 1 bar and
350 C at low CO conversion (0.5–1%) restrict secondary hydrogenation of olefins
as shown in Table 2.1 (Galvis et al. 2012). Catalytic activity is expressed as iron
time yield (i.e., the number of CO moles converted to hydrocarbons per gram of
iron per second). A high initial activity is observed for Fe/b-SiC and Fe/CNF over
15 h. In Table 2.2, the activities and product selectivities measured after 64 h of
reaction at 20 bar are displayed. The CO2 selectivity for all the samples is approx-
imately 40% on the basis of CO converted. The promoted catalysts prepared using
supports with low interaction with iron show high catalytic activities combined
with high selectivities to the desired products (Galvis et al. 2012).
Cobalt nanoparticles supported on mesoporous zeolites are effective catalysts
for FTS (Cheng et al. 2015; Peng et al. 2015; Sartipi et al. 2014). The cooperative
interplay of the Co sites and the acid sites on the zeolite forms a bifunctional
catalyst that exhibits better performance than a monofunctional catalyst. A bifunc-
tional catalyst consisting of uniform-sized Co nanoparticles and mesoporous
H-ZSM-5 has been demonstrated to be effective for CO hydrogenation and hydro-
cracking/isomerization reactions (Cheng et al. 2015). The bifunctional catalyst was
found to be promising for the direct production of gasoline-range (C5–11) hydro-
carbons from syngas. The Bronsted acidity in the zeolite results in hydrocracking/
isomerization of the heavier hydrocarbons formed on Co nanoparticles, while the
mesoporosity contributes to suppressing the formation of lighter (C1–4) hydrocar-
bons. The selectivity for C5–11 hydrocarbons could reach about 70% with a ratio of
56 U.J. Etim et al.
Fig. 2.9 (a–d) Catalytic performance of iron catalysts for the FTO process at 20 bar. Catalytic
tests were carried out at T ¼ 340 C, P ¼ 20 bar, and a H2/CO ratio of 1. Iron time yield is plotted
above as a function of time for (a) Fe-supported catalysts and (b) bulk Fe catalysts. Methane and
lower olefins yields are plotted below as a function of time for (c) Fe-supported catalysts and (d)
bulk Fe catalysts. The product yields were obtained at CO conversion levels between 70 and 80%.
Adapted from Galvis et al. (2012). Reprinted with permission from The American Association for
the Advancement of Science
isoparaffins to n-paraffins of approximately 2.3 over this catalyst, and the former is
markedly higher than the maximum value (ca. 45%) expected from the Anderson–
Schulz–Flory distribution (Cheng et al. 2015).
3.5 Other Reactions
Nanozeolite clinoptilolite supported rhodium nanoparticles (Rh/NZ-CP) were

tested in the hydrogenation of arenes, nitroarenes, and alkenes under moderate
reaction conditions. The nanocatalyst contains 2 wt% Rh of particle sizes in the
range of 5–20 nm distributed on the zeolite. The catalytic performance of Rh/NZ-
CP improves significantly, and the catalysts could be regenerated by a simple
process and reused for many times without significant decrease in activity and
selectivity. The high catalytic activity, thermal stability, and reusability present the
Table 2.1 Product selectivity and catalytic activity at 1 bar

Selectivity (%C)
C2–C4 C2–C4
Samplea FTY (10–6 molco/gFe.S) CH4 Olefins Paraffins C5+
Fe/CNF 1.41 23 61 4 12
Fe/α-Al2O3 (12 wt%Fe) 0.65 22 61 4 13
Fe/β-SiC 6.52 31 58 4 7
Fe/SiO2 0.14 38 56 5 1
Fe/γ-Al2O3 0.07 54 44 2 0
Fe-Ti-Zn-K 0.13 83 16 1 0
Fe-Cu-K-SiO2 0.20 43 46 2 9
Bulk Fe 0.08 76 21 2 1
From Galvis et al. (2012). Reprinted with permission from The American Association for the
Advancement of Science
a
Catalytic tests were performed at 350 C and an H2/CO ratio of 1; results after 15 h on stream are
shown (CO conversion: 0.5–1.0%). The product mixture that was analyzed consisted of C1–C16
hydrocarbons. Iron time yield (FTY) represents moles of CO converted to hydrocarbons per mol of
Fe per second; %C is defined as carbon atoms in a product with respect to the total number of C
atoms in the hydrocarbon mixture
Table 2.2 Catalytic performance at 20 bar

Selectivity (%C)
FTY C2–C4 C2–C4
Samplea (10–5 molco/gFe.S) CH4 olefins paraffins C5+ Oxygenates
Fe/CNF 2.98 13 52 12 18 5
Fe/α-Al2O3 (6 wt%Fe) 8.48 24 35 21 10 10
Fe/α-Al2O3 (12 wt%Fe) 2.66 17 39 19 14 11
Fe/α-Al2O3 (25 wt%Fe) 1.35 11 53 6 21 9
Fe/β-SiC 6.38 35 19 39 4 3
Fe/γ-Al2O3 0.25 49 33 11 1 6
Fe-Ti-Zn-K 0.49 24 28 29 10 9
Fe-Cu-K-SiO2 1.12 26 36 12 18 8
Bulk Fe 0.57 30 32 18 14 6
From Galvis et al. (2012). Reprinted with permission from The American Association for the
Advancement of Science
a
Catalytic tests were performed at 340 C and a H2/CO ratio of 1; results after 64 h on stream are
shown. The product mixture that was analyzed consisted of C1 to C10 hydrocarbons
catalyst as an attractive option when compared with the conventional (Baghbanian

et al. 2015).
The catalytic cracking of n-hexane over nano-ZSM-5 zeolite (MFI-type zeolite,
Si/Al ¼ 150 and 240) catalysts was tested at reaction temperatures ranging from
823 to 923 K under atmospheric pressure (Konno et al. 2012). The catalysts,
compared with the micron-sized zeolite, exhibited a higher n-hexane conversion
58 U.J. Etim et al.
with stable activity up to 50 h (Table 2.3). The Thiele modulus and the effectiveness
factors for the reaction using ZSM-5 zeolites with different crystal sizes are
presented in Fig. 2.10 and Table 2.4. It can be clearly seen from Table 2.4 that
the effectiveness factor for MFI (S)150, that is, small crystallite size MFI with Si/Al
of 150 is 1.0, indicating that the catalytic reaction in MFI(S)150 proceeded under
reaction-controlled conditions (Konno et al. 2012). The large external surface area
and low diffusion resistance of the nanozeolites reduce the effect of pore plugging
due to coke deposition (Yin et al. 2014). For this reason, the application of
nanozeolite in the catalytic cracking of n-hexane is effective in stabilizing the
catalytic activity. Similarly, in the cracking of n-hexane and naphthenes, (cyclo-
hexane and methyl-cyclohexane), coke was readily formed from the beginning of
the reaction leading to significant deactivation of the catalyst for micron-sized
ZSM-5 (Konno et al. 2013). For ZSM-5 catalysts, regardless of the reactant, the
nanoscale ZSM-5 exhibited a high conversion and a high light olefins yield with a
stable activity. As a result, the application of nanoscale ZSM-5 zeolites to the
catalytic cracking of naphtha is effective and gives light olefins with high yield and
excellent stable activity. Nanosized β-zeolites for the isomerization of hexane are
also active with good selectivity to branched isomers because of the high external
surface area of the small particles of the nanosized β-zeolites and the rapid diffusion
of the reactants and products (Sakthivel et al. 2009).
In another report, methanol conversion to light olefins was investigated over
SAPO-34 nanocatalyst with a crystal size of about 50 nm, and its catalytic proper-
ties were compared with those of 600 nm SAPO-34 catalyst (Askari et al. 2012).
The product distribution over the two catalysts was almost the same, but their
deactivation behaviors differ considerably. SAPO-34 catalyst with large crystal
deactivates faster than SAPO-34 nanocatalyst. This variation in the deactivation of
the different SAPO-34 crystallites is attributed to the number of accessible cavities
near their external surface and the diffusion limitation of the reactant and product
molecules. Due to a shorter diffusion length, the residence time of the produced
hydrocarbons is short, resulting in the long catalyst lifetime of the SAPO-34
nanocrystals. Incorporation of a stabilizer into active catalysts could influence
their performance. Boron incorporation into H-ZSM-5 nanocatalyst results in the
isomorphic substitution of B into the framework of H-ZSM-5 (Yaripour et al.
2015). The interaction between B species and H-ZSM-5 reduces the strong acid
sites and generates new weak acid sites which modify the densities and distributions
of acid sites on the [B]-HZSM-5. This raises the lifetime of the modified zeolite in
MTO reaction up to 1300 h compared to that of the conventional reference sample
340 h (Yaripour et al. 2015). However, propylene selectivity does not change
significantly with the substitution of B in H-ZSM-5. The deactivated catalysts
reveal that incorporation of boron improves coke resistance of the ZSM-5
nanocatalyst. The considerable enhancements of the lifetime and catalytic stability
are attributed to the reduction of strong/mild acid sites ratio as well as small crystal
size of the [B]-H-ZSM-5 nanocatalyst. In summary, the boron-modified ZSM-5
nanocatalyst exhibits more stable catalytic performance and longer catalytic life-
time for the MTO reaction.
Table 2.3 n-Hexane conversion, product yields, and coke amounts over the catalyst with different crystallite sizes
Light olefins yield BTX yield Others yield Coke amount of
Catalyst Time (h) Conversion (C-mol%) (C-mol%) (C-mol%) (C-mol%) after 50 h (wt.%)
C2¼ C3¼ C4¼ Total olefin
MFI(S)150 0.5 94.1 20.8 32.7 3.8 57.3 4.2 32.6
7 93.5 19.1 32.8 4 55.9 4.1 33.5 –
50 82 13.2 29 4.7 46.9 4.5 30.6 59.6 59.1
MFI(M)150 0.33 92.2 22.8 30.3 6.6 59.7 4.3 28.2
7.5 93.1 20.8 32.4 7.3 60.5 3.9 28.7 –
2 Nanotechnology Applications in Petroleum Refining
50 81 13.6 31.3 8.4 53.3 2.6 25.1 21 21.0

MFI(L)150 0.33 94.7 23.9 28.6 5.9 58.4 6.2 30.1
8.5 81 13.6 30.8 8.1 52.5 3.1 25.4 –
50 48.3 6.2 19.5 6.3 32 1.5 14.8 7.5 7.5
Reprinted from Konno et al. (2012) with permission from Elsevier. Copyright 2012, Elsevier publishers
59
60 U.J. Etim et al.
100 Mild
deactivation
Rapid
deactivation
Effectiveness factor, η [–]
Reaction Diffusion
controlling transition controlling
condition condition condition
10–1
MFI(S)150
MFI(M)150
MFI(L)150
tanh(φ )
Coked MFI(S)150 η=
φ
Coked MFI(L)150
10–2
10–3 10–2 10–1 100 101 102
Thiele modulus,φ [–]
Fig. 2.10 Relationship between the Thiele modulus and the effectiveness factor in n-hexane
cracking at 923 K over ZSM-5 zeolites (Si/Al ¼ 150) with different crystal sizes. Adapted from
Konno et al. (2012) with permission from Elsevier. Copyright 2012 Elsevier publishers
Table 2.4 Effectiveness factors of ZSM-5 zeolites (Si/Al ¼ 150) with different crystal sizes in
n-hexane cracking at 923 K
Reaction rate constant Thiele modulus Effectiveness factor
Sample k (m3 kg1 s1) ϕg (mc) ηg (mc)
MFI(S)150 (1.04) 1502 (5.38) 1502 1
MFI(M)150 – (8.97) 1502a 1
MFI(L)150 – 1.38a 0.65
Coked MFI(S) 150 8.27 MFI3 9.03 MFI1 0.8
Coked MFI(L) 150 4.24 MFI3 2.41 0.41
Reprinted from Konno et al. (2012) with permission from Elsevier. Copyright 2012, Elsevier
publishers
a
Theoretical value calculated from reaction rate constant of MFI(S)150
4 Concluding Notes and Future Perspectives
The relationship between nanoscience/nanotechnology and catalysis offers huge

opportunities for improvements in petroleum processing. The utilization of
nanoporous materials as supports and as active catalysts and metal nanoparticles
for catalysis traverses various petroleum refining processes. The tremendous ben-
efits the nanoscale materials possess over their micron-sized counterparts are due to
their intrinsic size-dependent properties. The formulation of ideal nanoparticles to
improve a process efficiency requires careful designed and controlled experiments.
The improvements of several features make them a better choice. The properties
that make them ideal candidates for petroleum processing include a greater surface
area to volume ratio due to tiny particle size, and thermal and catalytic stability.
Although the physiochemical characteristics of nanoparticles, such as phase, struc-
ture, or behavior, may be influenced by the method of preparation and the nature of
the environment in which the nanoparticles are subjected to, the extent of these
factors on the particle properties can also be size dependent and therefore can be
controlled. Phase transformation in a metal nanoparticle catalyst could lead to the
catalyst deactivation. However, it is not true in the case of nanoporous materials
such as zeolites. The large external surface area to volume ratio decreases the
tendencies of coke formation, which causes catalyst deactivation. Metal catalysts or
solid acidic catalysts (such as zeolite) are utilized extensively in the petroleum
industry, for example, in catalytic cracking hydrocracking, hydrodesulfurization,
isomerization, reforming, and dehydrogenation.
The desire for improved catalysts with high activity, low deactivation, and low
coke formation to increase production to meet the growing demand for chemicals
and fuels are increasingly necessitating the exploitation of nanoparticles as cata-
lysts, and there are even more opportunities lying to be explored using the potentials
of nanotechnology. The inherent stability of nanoparticle catalysts and their bifunc-
tional catalysis potentials provide even more future opportunities for many appli-
cations, such as the catalytic application to renewable fuels. Nanotechnology will
continue to improve the future of petroleum refining explorations and exploitations.
It is expected that lower energy consumption, extended lifetime of catalyst system
and reduced amount of materials and reuse of nanomaterials will offer more
environmentally friendly catalysts in the future.
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Chapter 3
Advances in Nanocatalyzed
Hydrodesulfurization of Gasoline and Diesel
Fuels
Tawfik Abdo Saleh and Ibrahim Munkaila Abdullahi
Abstract This chapter is aimed toward providing a general overview of the signif-
icant progress that desulfurization technology has brought to the oil and gas indus-
tries. Organosulfur compounds are known to release various environmentally
harmful sulfur products into the atmosphere from the combustion engines of vehicles,
leading to a serious environmental threat. Efficient removal of these sulfur com-
pounds from diesel and gasoline fuels that we inevitably use in various capacities
every day is therefore paramount. Various desulfurization technologies have been
developed over the years to address this issue, and one of the most efficient and cost-
effective approaches is transition metal-catalyzed hydrodesulfurization (HDS). Sev-
eral nanocatalysts have been designed for this purpose. The chapter encapsulates
some of the various ways in which these catalysts are being prepared, including
doped nanocatalysts which are relatively unexplored for this application. It also
includes a discussion and examples of their activities in the desulfurization reactions.
The limitations are discussed, as well as possible ways to improve their sulfur
removal efficiency. Furthermore, some of the commercially employed HDS catalysts,
including feedstock, the reaction conditions they work best under, the type of reactor,
and various factors affecting the hydrodesulfurization reactions are discussed, along
with illustrations. The HDS mechanism is another important aspect of desulfurization
that was thoroughly reviewed, including a discussion of the suggested pathways for
the hydrodesulfurization of dibenzothiophenes (DBTs) and their derivatives, in
addition to the toxic processes of HDS catalysts. Finally, the ongoing research on
improved desulfurization processes, specifically the deep HDS of diesel and gasoline
fuels in order to comply with the current standard for sulfur removal specifications, is
also briefly addressed in this chapter.
Keywords Diesel and gasoline fuels • Nanocatalysts design • Mechanisms of

hydrodesulfurization
T.A. Saleh (*) • I.M. Abdullahi

Chemistry Department, and Center of Excellence in Nanotechnology (CENT), King Fahd
University of Petroleum and Minerals, Dhahran 31261, Saudi Arabia
e-mail: [email protected]; [email protected]; http://faculty.kfupm.edu.sa/CHEM/
tawfik/

68 T.A. Saleh and I.M. Abdullahi
1 Introduction
Crude oil has been known to be one of the most substantial energy sources, serving
as the most wide reaching of all sources. It comprises a mixture numerous organic
compounds. The use of fuel for transportation is the key area where crude oils are
primarily used substantially, e.g., gasoline in automobiles, diesel for some cars and
trucks, and jet fuel for aircraft. Crude oils may have different forms of impurities
present in them, but the most common of all are the sulfur compounds. Liquid (oil)
fuels among other fuel types contain sulfur which ultimately resorts to direct sulfur
(IV) oxide (SO2) emission, in addition to other sulfate particulate matter (SPM) that
endangers lives and property in public communities and promotes corrosion,
reduces the life span of refinery engines. In addition, the emission control technol-
ogy developed to meet NOx and SPM emission specifications may be significantly
affected by the presence of sulfur compounds in the diesel engines exhaust gases
(Srivastava 2012). Various industrial catalysts such as sulfur-based transition metal
catalysts have been widely employed in hydrotreatment refining applications of
petroleum, e.g., hydrodesulfurization and hydrodenitrogenation, hence, these cata-
lysts are considered industrially vital in the oil industry. These industrial catalysts
are in general formed from Group VIII (Co or Ni) mixed with sulfides of an element
in Group VIB (Mo or W). Commercial molybdenum catalysts promoted with Co- or
Ni- commonly supported on alumina are employed in petroleum hydrotreatment
applications. Some important characteristics of alumina support that makes it to be
widely employed include high active metal phase dispersion (Vasudeven and Fierro
1996) and its excellent mechanical properties. Intensive researches since the last
few decades have pointed out that its promising physical properties are owing to the
rather strong chemical bonding interactions present between the transition metal
oxides of precursor states and amorphous alumina (Topsøe and Clausen 1986).
Ultra-trace removal of sulfur has become highly attractive as a result of sulfur
amount excessively increasingly in the crude oils as well as decline in the allowable
limit of the amount of sulfur in diesel and gasoline fuels by specifications regulatory
bodies. Diesel and oil of low-sulfur content is highly desirable for a safe and
friendly environment. The challenge of removing sulfur from FCC naphtha has
predominated the recent gasoline desulfurization problem, contributing at least
one-third of gasoline pool but over 90% of sulfur in gasoline; this sulfur results in
the release of SOx in air from combustion engines of vehicle leading to air pollution.
It is essential that deep gasoline sulfur removal or diesel sulfur must be made,
without any decrease in octane number nor loss in the yield of gasoline.
Hydrodesulfurization (HDS) is no doubt among the most regarded processes
necessitated to produce diesel fuel of low-sulfur content to as low as below 0.05 wt.
% which is in accordance with the reported raising challenge for the environmen-
tally accepted clean fuel with the least increment in production cost. It has been
previously reported that alkyl-dibenzothiophenes derivatives with 4- and/or 6-alkyl,
for example, 4,6-dimethyl-dibenzothiophene (4,6-DMDBT), exhibited far lower
3 Advances in Nanocatalyzed Hydrodesulfurization of Gasoline and Diesel Fuels 69
reactivity in HDS than the unsubstituted dibenzothiophene counterpart (Ma et al.

1995). Generally, the desulfurization of light fractions; constituting high proportion
of reactive sulfur-based compounds, e.g., alkyl-benzothiophenes much easier and
faster (less reaction time; first few minutes) than heavy fractions; constituting
relatively less reactive sulfur-based compounds. For example, alkyl-
dibenzothiophenes are difficult to desulfurize under regular HDS techniques
(Ma et al. 1995).
2 Processes of Desulfurization Technology

in Oil and Gas Industries
Modern refineries are highly integrated industrial plants, with primary assignment
of efficiently converting various complex crude oil mixtures feed into high yields of
desired valuable products. For this reason, more research efforts are considered to
improve conventional hydrodesulfurization and develop substitutes for desulfuri-
zation technologies like oxidation-extraction called also oxidative desulfurization
are always on the rise. Others are biodesulfurization and selective adsorption, for
adequate removal of refractory sulfur compounds present in petroleum products
(Srivastava 2012). Cracking, hydrogenation, reforming, blending, extraction, and
distillation are some of the crucial physical and chemical processes employed in
refineries to convert crude oil to higher value desirable products (Babich and
Moulijn 2003). At present, in order for refineries to meet dynamic societal needs
with regard to quality of products and other specifications, there is a need to
upgrade the existing refining technologies, while researching for innovatively
more advanced technologies. Co- and Ni-promoted MoS2 have shown promising
catalytic activity in HDS, and thus, a catalytic system of MoS2 promoted with Co or
Ni have widely been used in HDS catalytic processes. (Moses et al. 2009). The
refinery streams of sulfur containing gasoline becomes an environmental threat
when gasoline of S 30 ppm is produced, and the need to treat such gasoline
becomes necessary. Advanced and conventional Co–Mo and Ni–Mo catalysts have
demonstrated high degree of usefulness in their ability to remove sulfur reasonably
at high level. On the other side, hydrogenation of unsaturated compounds (olefins)
should be minimized as it leads to simultaneous fall in octane number of gasolines.
Product yield and specifications are used to rate the efficiency of process applica-
bility. Catalysis based on conventionally employed HDS technologies have been on
the rise for better improvement, while in recent years, more sophisticated desulfur-
ization techniques providing efficient ways of removing sulfur as well as increasing
the octane number are highly desirable (Babich and Moulijn 2003; Saleh and
Danmaliki 2016a).
The basic classifications of desulfurization could be grouped based on the
following classes:
1. Nature of employed process; whether physical, chemical, or both
2. Organosulfur compounds fate during desulfurization
Fig. 3.1 Organosulfur compound-based classification of desulfurization process
3. The role played by hydrogen in the process

Starting with the organosulfur compounds transformation, the process can be
subdivided into three main categories, depending on whether decomposition of the
sulfur compounds takes place or not, refinery stream separation without sulfur
elimination, or both processes (Fig. 3.1). In the first category, the organosulfur
compounds decompose into solid sulfur or gaseous products, while the hydrocar-
bon, on the other hand, remains in the refinery streams and is recovered. The most
common illustration of this specific process type is the conventional HDS.
The second category simply separates the organosulfur compounds from the
refinery streams. Many processes like this usually transform the organosulfur
compounds first into easily separable components from the refinery streams. How-
ever, the two challenges associated with desulfurization of streams by separation
are that it may lead to the loss of some desired product as well as the disposal of the
retained organosulfur molecules. In the third process type, decomposition in a
single reactor, as well as separation of organosulfur compounds from streams in
separation vessels are carried out simultaneously. The joint processes from the root
for several technologies which may be very reliable for producing fuels of ultra-low
sulfur contents at industrial scale. An interesting example of this special category of
the process is the catalytic distillation desulfurization.
Another form of desulfurization processes which depends on the role hydrogen
plays in sulfur removal, this classification is the one based on:
1. HDS processes
2. Non-HDS processes
HDS processes employ hydrogen for the decomposition of organosulfur com-
pounds and sulfur elimination from refinery streams; this may involve several pre-
or post-distillation treatments of refinery streams with hydrotreatment to enable the
specifications of desired fuel maintained. On the other hand, hydrogen is not
involved in the non-HDS processes.
Fig. 3.2 Nature of a key process classification of desulfurization technologies for sulfur removal
The last but not the least form of the desulfurization processes classification is
based on the nature of employed processes; physico-chemical processes (Fig. 3.2).
Catalytic conversion of organosulfur compounds involving the elimination of sulfur
is the most advanced and commercialized technologies. Examples of such technol-
ogies to maintain good fuel specifications are conventional hydrotreatment,
hydrotreatment in reactor design in the presence of high active catalysts, and
hydrotreatment combined with some chemical processes. One major characteristic
of the technologies of the last-mentioned example is the employment of physico-
chemical processes involving major step such as adsorption, extraction, distillation,
alkylation, oxidation, or the combination of one or all of these processes, which has
an entire different approach from the separation and/or to transformation of
organosulfur compounds from refinery streams by catalytic HDS. For example,
the adsorption process requires adsorbents which take up the sulfur molecules
selectively from the crude oil sample. A nonreactive, porous substrate that permits
the greatest surface area for adsorption is used to hold the active adsorbent.
Adsorption is said to take place when there is attachment of sulfur molecules to
the adsorbent on the substrate; this remains adsorbed and hence separated from the
fuel. Although the method requires low temperature and pressure and may be
relatively cheaper, it is not as promising as the catalytic transformation methods
(Srivastava 2012).
HDS is a refining process that has a well-established commercialization protocol

that involves heating the mixture of a feedstock and hydrogen, in the presence of a
catalysts for the essence of sulfur removal. Both the streams from conversion units,
e.g., fluid catalytic cracking (FCC) and hydrocracker units and distillate streams
obtained during direct distillation of crude oil are desulfurized by the refineries.
Depending on the nature and the design of the refinery, HDS can be carried out
either before or after FCC. Although due to the poisoning effect of sulfur on Pt,
HDS must be carried out before feedstock reforming. H2S liberation occurs as a
result of sulfur reduction occurring in the HDS reactor; this is gradually removed
from the flue gas by amine scrubbing. Today, HDS is the most employed desulfur-
ization technology employed although processes like caustic washing is performed
as well, basically to remove low molecular weight thiols. Majority of HDS oper-
ations in addition to removing sulfur, also help to get rid of nitrogen compounds as
well as some metal impurities. In order to meet up with the specifications of ultra-
low sulfur on fuels that are produced from straight-run streams, refineries system-
atically control the appropriate catalysts selection as well as the hydrogenating
conditions. The challenge, however, comes up when dealing with the desulfuriza-
tion of other steams originating from the conversion units, which usually include
the refracted sulfur compounds. The currently practiced HDS processes was
improved for the removal of sulfur from the derivatives of DBT using a zeolite
catalyst supported by nickel (Isoda et al. 2000). In this technology, mainly two steps
are involved.
1. Passing hydrogen gas at a pressure of 250 Pa, at 270 C for 1 h and is the
optimum reaction condition for the first step.
2. Further desulfurization of the products is carried out by passing hydrogen gas at
a pressure of 250 Pa, over a CoMo/Al2O3 catalyst at 300 C for 2 h, for the
removal of 4,6-DMDBT.
The need for a relatively elevated temperature, high pressure as well as several
steps associated with this desulfurization process adds to the overall cost of running
the refineries and hence are the major disadvantages of the process.
3 Hydrodesulfurization of Diesel and Gasoline Fuels
In refining process, sulfur compounds are generally unwanted, this is because aside
having pollution and health effects from the sulfur oxide gases they produce, they
usually turn some catalysts employed inactive in processing crude oil, as well as
causing problems of pipeline corrosion in refining and pumping equipment. For
these, desulfurization is highly necessary to have a safe fuel for various applica-
tions. Diesel fuel oil deep hydrodesulfurization (HDS) principally targeting alkyl-
dibenzothiophenes such as 4-methyl- and 4,6-dimethyldibenzothiophenes for deep
HDS was designed through various stages and fractional HDS to obtain a satisfac-
tory sulfur level as well as the fluorescent color of desulfurization oil product was
reported by I. Machida et al. The multi-stage hydrodesulfurization process of diesel
Fig. 3.3 Advantages of

microwave heating
technique
fuel is carried out at a 2.9 MPa pressure, initially over Co–Mo at 360 C for a
duration of 30 min, reducing the sulfur level to 0.092 wt.%. This is followed by
carrying out the process over Ni–Mo at a temperature of 360 C for a duration of
20 min, further decreasing the sulfur level to 0.035 wt.%, and finally, performing
the process once again over the same Ni–Mo catalyst but this time, at a relatively
lower temperature of 260 C makes it possible to achieve an overall sulfur level of
about 0.016 wt.% low and reaction time of 60 min. The results obtained satisfy the
acceptable sulfur level as well as the reaction time (Mochida et al. 1996).
There are some important parameters that affect the deep HDS of diesel fuels. To
start with, inorganic reactants and products including hydrogen, ammonia, and
hydrogen sulfide if present could remarkably influence the hydrodesulfurization
reaction rate as shown by numerous works that adopt model feed. However, for
commercial units deep HDS, the partial pressures of these gasses encountered
deviate considerably from those usually employed in model feed studies. Further-
more, unlike the data for many pure compounds, obtained in gas-phase or vapor-
phase study, the hydrodesulfurization of gas oil is a liquid-phase reaction. And it is
often not an easy task to correlate the data obtained at the interface gas-solid and
liquid-solid, although, interestingly, another work finding illustrates that many
similarities are exhibited with the hydrodenitrogenation of quinoline carried out
in the liquid phase and vapor phase (Satterfield et al. 1975).
Several techniques can be used for upgrading heavy crude oil into lighter one.
Although high temperatures are required for the methods usually in use, other
setbacks include health-threatening environmental pollution as well as long reac-
tion time. The use of carbon-based nanocatalysts in heavy crude oil upgrade was
reported to have significant impact in the oil upgrading process by efficiently
upgrading the heavy oil into lighter ones at a considerably lower temperature of
about 150 C. Microwave-assisted heating is used to elevate the temperature of
crude oil. This proposed technique was found to have the advantages, shown in
Fig. 3.3. Thus, upgrade transformation of heavy crude oil to lighter ones could be
more environment-friendly and cost-effective (Li et al. 2014).
4 Nanocatalysts Design
The catalytic activities of most sulfides of transition metals have been tested
towards HDS (Pecoraro and Chianelli 1981). When their activity was investigated
individually towards HDS, they were found to vary across the periodic table over
three orders of magnitude. Most of the metals of the second and the third rows were
literally found to be the most active catalysts. This varying activity among the
metals could be attributed to the structural nature as well as electronic properties.
The employed catalysts in the refractory sulfur species desulfurization are designed
in two possible approaches:
1. The first method relays on finding a catalyst that could selectively hydrogenate
the refractory sulfur species among the major presence of polyaromatic hydro-
carbons. In the presence of H2S, Ru is one of the most promising noble metals
reported to be highly active (Hirschon et al. 1987).
2. The second approach involves the elimination of the steric hindrance in DBT
skeleton to the desulfurization by the isomerization of their methyl groups. A
Co–Mo/Al2O3 catalyst-containing zeolite is more preferred as it exhibits slightly
more promising activity than commonly employed Ni–Mo/Al2O3 and Co–Mo/
Al2O3; this was justified from the higher conversion of 4,6-DMDBT it showed,
confirmed from the analytical data of the product, which indicates the methyl
groups disproportionation and isomerization (Mochida et al. 1996).
Trickle-flow experiments were carried out in accordance with the guidelines
reported by van Looij et al. (van Looij et al. 1998; Sie 1995), using the catalysts:
CoMo/Al2O3 and a NiMoP/Al2O3 (Criterion Catalyst Company). A stainless-steel
reactor of an internal diameter of 15 mm was loaded with 20 mg catalyst, diluted
with SiC, after which the drying of the catalyst takes place at 450 C for a period of
2 h. The influence of internal mass transport on the reaction rate was minimized by
adopting catalyst bodies of a sieve fraction of 180–600 μm: according to the
reported study, an efficiency factor of >0.95 was obtained under the conditions
employed (Gosselink and Stork 1987). Additionally, experiments have verified that
the use of viz. 180–250 mm which are even much smaller catalyst bodies, virtually
the same HDS activity observed, confirming that according to the reported inves-
tigations, the limitation associated with internal diffusion was negligible. Several
catalytic systems have been designed for various HDS processes, most of which are
Co-, Mo-, and Ni-based catalysts supported on alumina with one metal serving as
promoter, commonly Mo. The reaction is carried out in specialized types of reactors
with reactions optimized for each specific catalyst adopted. Table 3.1 below shows
the summary of catalyzed that have been designed and applied in various capacities,
the reaction system used and its optimum conditions.
The resistance of sulfur to noble metal catalysts has been an area of emphasis for
several studies due to its significance in desulfurization processes (Cooper and
Donnis 1996). In recent times, a novel strategy for the design of sulfur-resistant
noble metal catalysts was proposed for the production of clean distillate fuels, by
Table 3.1 Optimal conditions for the removal of sulfur by HDS
Sulfur compound Reactor S Conc. Co Temp. Pressure %S
Process feedstock Catalyst system (ppm) ( C) (MPa) Removal References
Deep HDS Alkyl DBTs light oil Co–Mo/An Al2O3 Packed bed 4000 300 – 67% Kabe et al.
(1993)
Three stage Alkyl DBTs diesel CoMo + NiMo Packed bed 7060 250 2.9 69% Ma et al. (1994)
HDS
HDS Alkyl DBTs heavy Co–Mo–Al Trickle bed 1800 360 5.5 20% Yitzhaki et al.
gas oil (1995)
Deep HDS Alkyl DBTs gas oil Co–Mo/γ–Al2O3 Fixed bed 13200 350 3 96% Andari et al.
(1996)
HDS Alkyl DBTs heavy Co, Ni, Mo, W supported on Trickle bed 13300 320 5.4 80% Vradman et al.
gas oil Al2O3/SiO (1999)
In situ H2 BT water/toluene Mo Batch 350 340 20 99.5% Ng and Milad
generation emulsion autoclave (2000)
Staged HDS Alkyl DBTs NiMoS/Al2O3 Packed Bed 4900 340 5 97% Shin et al.
medium cycle oil (2001)
Deep HDS Alkyl DBTs light Co–Mo supported on Packed Bed 21900 350 4.5 57% Turaga and
cycle oil MCM-41 Song (2003)
Lab Scale HDS Alkyl DBTs middle NiMo/γ–Al2O3 Trickle bed 16740 350 4 90% Pedernera et al.
distillates (2003)
Deep HDS Alkyl DBTs gas oil CoMo/Al2O3 + NiMo/Al2O3 Packed Bed 14350 340 3 98% Choi et al.
(2003)
HDS Alkyl DBTs gas oil NiMo sulfide on Al2O3–Si Packed Bed 11780 340 4.9 94% Kunisada et al.
support (2004b)
3 Advances in Nanocatalyzed Hydrodesulfurization of Gasoline and Diesel Fuels
Deep HDS Alkyl DBTs gas oil CoMoS and NiMoS Batch 340 – 4.9 97% Kunisada et al.
autoclave (2004a)
Oil presaturated Alkyl DBTs diesel CoMo Two phase 1200 400 7 99% Schmitz et al.
with H2 reactor (2004)
(continued)
75
Table 3.1 (continued)
76
Sulfur compound Reactor S Conc. Co Temp. Pressure %S

Process feedstock Catalyst system (ppm) ( C) (MPa) Removal References
Lab Scale Deep Alkyl DBTs diesel P and Ni–Al2O3 supported 520 340 4 50% Costa et al.
HDS Mo oxycarbides (2005)
HDS Thiophene FeS–MoS supported on 1000 280 0.1 30% Hubaut et al.
n-Heptane Al2O3 and carbon (2007)
T.A. Saleh and I.M. Abdullahi
Fig. 3.4 Proposed novel concept for catalyst design based on shape-selective exclusion, hydrogen
spillover, and two sulfur resistance types. The scheme represents internal surface metal particles as
black dots
employing low-temperature hydrotreating of sulfur-containing distillates (Song

1999), diesel fuels, and jet fuels are examples. Special zeolites-supported noble
metals were invoked in the proposed design concept, which utilizes the following
(Song 1999):
• Selective exclusion based on shape
• Spillover of hydrogen
• Two sulfur resistance types
Noble metal particles bimodal distributions could be prepared from special
zeolite supports. The pore sizes of the metals vary from small (pore opening of
about 5 Å or less) to large (6 Å pore opening or larger).
Note: according to IUPAC recommendation, pores are classified as:
1. macropores: pores with widths exceeding about 50 nm
2. mesopores: pores of widths between 2 nm and 50 nm
3. micropores: pores with widths not exceeding about 2 nm
Some materials are categorized by small pores whereas others will be contained
in large pores. It is of interest that distribution of the two pores is uniform or their
systems interconnect, so that they are as close as possible. Size inhibition may occur
when some relatively bigger organosulfur compounds, e.g., thiophenic molecules
try to diffuse into the small pores leading to “selective exclusion based on shape.”
On the other hand, the larger pores (micropore or mesopore size range) would
permit fast diffusion preferentially as well as allowing bulky polycyclic aromatic to
reaction with sulfur compounds. The thiophenic molecules are small enough to
penetrate the large pores but big enough to be blocked by the small pores. H2
molecules, on the other hand, are very special in that, they are small enough to enter
both pore types quite readily, get dissociatively adsorbed on the available metal
around, and be conveyed between pore systems by means of spillover. This
spillover hydrogen plays a vital role in recovering poisoned metal sites via the
elimination of R-S-R and R-S-H; this poisoning occurs when adsorbed sulfur
deactivates the metal in the large pores. The classification of sulfur resistance
based on types; type I implying resistance to organic sulfur compounds and type
II implying resistance to inorganic H2S is of paramount importance. A higher type
II sulfur resistance is an expected property exhibited specifically by small pores
metal species. Figure 3.4 shows an elegant scheme of the proposed novel concept
(Song 1999).
5 Doped Nanocatalysts Preparations
Preparation approach for catalyst synthesis generally has a significant effect on the
catalyst activity for any specific type of transformation or reaction. There are very
limited reports in documented literature illustrating the effect of the method of
catalyst preparation has on HDS. Although, it is yet to be well understood, the
reasons why catalyst developed by one have better activity than that developed by
another method. The effect CoMo/silica catalysts on thiophene HDS has been
studied and reported (Venezia et al. 2002). Two possible methods can be used to
prepare the catalysts, namely, incipient wetness impregnation/co-impregnation
route and the complete sol-gel method; a control catalytic system was prepared
by supporting the catalysts on a commercial silica, and the results were compared.
The highest activity was found to be exhibited by the sol-gel silica supported
catalyst with the two co-impregnatedly loaded metals in the presence of
nitrilotriacetic acid. Equilibrium deposition filtration (EDF) technique was
employed for the preparation of CoMo/Al2O3 catalyst by Mo precursor deposition,
and the subsequent dry impregnation deposition of Co precursor; these gave rise to
the catalysts with higher activity as compared to those prepared by the regular
co-EDF and those by the technique of conventional impregnation (Papadopoulou
et al. 2003).
The preparation of HDS catalysts can be done by the technique of incipient
wetness impregnation of Ni–Mo(W) and Co–Mo(W) species over zirconium-doped
siliceous MCM-41 (Rodriguez-Castellon et al. 2008). These catalysts were found to
exhibit a very satisfactory activity within the temperature range of 300–340 C,
with conversion yields of 92.6% and 49.0%, respectively, for Ni–Mo(W) and Co–
Mo(W). The catalysts promoted with Ni were found to exhibit better performance
as compared to those catalysts promoted with Co in the DBT HDS reactions. Other
catalysts prepared were Ti-loaded hexagonal mesoporous SBA-15 supported
Co/Mo and Ni/Mo catalysts. The use of Ti-loaded SBA-15 material as catalysts
support leads to the enhancement of the DDS route in this reaction, thus, more
active than those of their Ti-free counterpart (Nava et al. 2007).
Other prepared catalysts reported are the unsupported types, example of such
catalysts are the unsupported MoS2 catalyst reported to have been prepared in situ,
under moist condition, through the decomposition of ammonium thiomolybdate.
Various characterization techniques were employed to fully characterize this
catalyst, these include; scanning electron microscopy (SEM), XRD, measurements

of specific surface area were carried out using BET and BJH etc. The catalytic
performance of the catalyst was studied on diesel oils HDS; such oils include LCO,
SRGO, light cycle, and straight-run gas oil. Also, further investigation on some
refractory sulfur compounds selected in oils was carried out on
4,6-dimethyldibenzothiophene (4,6-DMDBT), dibenzothiophene (DBT), and
benzothiophene (BT). The preparation of MoS2 catalysts was carried out via the
decomposition of ammonium thiomolybdate precursor under moist condition in
situ, in decalin (Trakarnpruk et al. 2008) as:
ðNH4 Þ2 MoS4 ! 2NH3 þ H2 S þ MoS2 þ S
The occurrence of MoS2 was confirmed by the XRD technique; the XRD pattern
shows MoS2 Phase (JCPDS-ICDD 3701492, 2 θ (Å) ¼ 14 (002), 33 (100),
40 (103), and 58 (110) (Song et al. 2000a, b). The XRD pattern of the catalyst
after the HDS reaction shows less crystallinity. Specific surface areas, total pore
volume of the in situ prepared MoS2 are determined using BET. The catalyst
prepared in the presence of water shows high surface area of 544 m2 g1 and
pore volume of 1.16 cm3 g1. It was proposed that water helps dispersion of the
precursor droplets in decalin under agitation (Trakarnpruk and Seentrakoon 2007).
Specific surface area, total pore volume as well as elemental analysis (EDX) of
the MoS2 catalyst before and after HDS reactions are reported. The surface area
and pore volume of the catalyst after HDS reaction decreased considerably to
332 m2 g1 and 0.63 cm3 g1, respectively. This might be attributed to sintering of
MoS2 crystallites. From EDX analysis, it shows the slight decrease of S/Mo ratio
from 1.7 to 1.6. However, C/Mo ratio was increased from 5.9 to 7.1, the carbon
detected in the catalyst before the HDS comes from decomposition of decalin
which was used as solvent. This reveals contribution of decalin in the preparation
of MoS2 catalyst by in situ decomposition of ammonium thiomolybdate. The
carbon increased in the catalyst after the HDS is derived from oil. Scanning
electron microscopy (SEM) of the MoS2 catalyst reveals a highly porous and
rough surface. The water addition increases dispersion of MoS2 generated from
ammonium thiomolybdate precursor since it is insoluble in oil. The surface of the
catalyst after the reaction is less porous.
6 Hydrodesulfurization Reactions
The HDS model compounds’ reactions, Fig. 3.5, were carried using CoMo/carbon-
supported catalyst and commercial CoMo/alumina support. Two independent reac-
tion routes are possible, the first route start with desulfurization of DBT, and then
hydrogenation, and the second requires the hydrogenation of DBT, followed by
desulfurization. For all the catalysts studied, the selectivity was close at the same
temperature. However, a dramatic change was reported in the preferred mechanistic
Fig. 3.5 HDS of dibenzothiophenes (DBT and derivatives) (R ¼ H, CH3, or any other alkyl
group)
route for desulfurization of 4,6-DMDBT with temperature. At low temperature, the

hydrogenative pathway is preferred, while at high temperature direct desulfuriza-
tion predominates. The catalytic activity of carbon-supported CoMo catalyst was
found to be more than that of the analogous alumina-supported catalysts for DBT.
The most active preparation method was over three times more active for DBT
HDS than a comparable commercial HDS catalyst. The major reason for its higher
activity is the higher number of active sites the carbon-supported catalyst is
suggested to be on it. Thus, the substrate/catalyst ratio may influence the activity
difference of the two catalysts as described above with 4,6-DMDBT. In addition,
the narrow pores of the present active carbon (12.5 Å) may have some hindrance on
the diffusion of bulky 4,6-DMDBT. Mesoporus carbon of large surface area is an
interesting support for heavier feedstocks (Farag et al. 2000).
7 Factors Affecting the Reactions
The influence of changes in the concentrations of polycyclic aromatic compounds,

e.g., pyrenes, chrysenes, napthalenes, etc. on the rate of reaction kinetics of deep
HDS in a trickle-flow system is negligible within the operating window of existing
once. One of the key parameters of reaction rate inhibition in deep HDS is the use of
trace amounts viz. within the range of ca. 0–30 ppm of organo-nitrogen compounds.
It could be inferred from the reported literature that there is a strong resemblance
between the behavior of trace amounts and high concentrations effect of basic
organo-nitrogen compounds. An order of 0.15 with respect to basic organo-
nitrogen compounds was calculated in commercial gas oil. In the presence of at
least 10,000 ppm polycyclic aromatics, trace amounts (viz. ca. 0 30 ppm) of basic
organo-nitrogen compounds affects the kinetic rate of the overall HDS reaction in a
significant way. It could be deduced from reported literature that the principal role
of the basic organo-nitrogen compounds of relatively high concentrations in model
feeds resemble closely the key role of trace amounts currently pinpointed in deep
HDS of a highly complex mixture, e.g., gas oil. The influence of variations in the
concentration is negligible in bulky polycyclic aromatics, e.g., pyrenes, chrysenes,

and naphthalenes (van Looij et al. 1998; Danmaliki and Saleh 2017).
Hydrogen sulfide is another factor that has been reported to have an effect on
hydrodesulfurization reactions. Although it is important, it is of secondary impor-
tance even in the treatment of raw distillates in HDS. It is well known that
hydrogenolysis reactions are more prone to H2S poisoning as compared to hydro-
genation. The HDS of β-DBTs requires hydrogenation which is a crucial step in
HDS, while H2S could assist in the enhancement of the hydrogenation process; this
has been an under-acknowledged point in the past. An example of this was seen in
the HDS of DBT on CoMo/Al2O3 catalyst. The HDS of 4,6-DMDBT over NiMo/C
was observed to give a similar result (Sakanishi et al. 2000). This could be
attributed to an increment in surface SH groups as a result of the dissociation of
H2S (Topsøe et al. 1996). H2S modestly inhibits hydrogenation in the HDN of
six-membered nitrogen heterocycles, which could improve the scission of C–N
bond. The point of emphasis here is that there is less pronounced H2S inhibiting
effect in β-DBTs HDS than in that observed in DBT HDS. This is consistent with
the known fact that hydrogenation is more important and hence plays a key role in
β-DBTs HDS than hydrogenolysis.
The commercial NiMo/Al2O3 was reported to exhibit around three times higher
activity than the commercially employed CoMo/Al2O3 catalyst in the HDS reaction
pathways of 4,6-DMDBT in decalin. Again, this could be attributed to the higher
hydrogenation activity of NiMo/Al2O3 catalyst as compared to CoMo/Al2O3. The
low reactivity of 4,6-DMDBT, on the other hand, could be ascribed to steric
hindrance. This (steric hindrance) is relieved by aromatic ring hydrogenation and
therefore, catalysts with higher hydrogenation potential show better catalytic activ-
ity towards 4,6-DMDBT HDS.
Trickle-bed reactors are used to carry out the HDS reaction in refineries. The
operating conditions of for these reactors usually requires H2 gas pressure between
3.0 and 5.0 MPa and a temperature of range 300–450 C, commonly employing
CoMo/Al2O3 or NiMo/Al2O3 catalysts (Whitehurst et al. 1998; Saleh and
Danmaliki 2016b). These severe conditions lead to excessive consumption of
hydrogen, hydrogenating the available olefins, as well as decreasing octane rating.
Linear or branched thiols referred to as recombinant mercaptans can be formed
from the reaction of olefins with H2S in the reactor under mild HDS conditions,
forming typically a chain of 5–12 carbons long. Sulfur is maintained in the product
due to the formation of recombinant mercaptans, restricting the HDS process
effectiveness. A further extended research in catalysis and process designs of
HDS are being carried out to improve the efficiency of sulfur removal, while
maintaining the least specification of the fuel quality. For some special systems,
e.g., fuel cells, atmospheric pressure is preferably the most suitable condition to
carry out HDS reactions. Also, low H2 to fuel ratio is essentially desirable for such
systems to run the HDS reaction since hydrogen is crucial reactant in the fuel cell.
In the case of phosphoric acid fuel cell (PAFC) on the other hand, natural gas is the
crucial reactant for its operation; hence, the system also adopts HDS. HDS reaction
in systems like direct carbonate fuel cell has also been studied. HDS reaction at
atmospheric pressure condition proceeds only via the less effective route;
hydrogenolysis and not through the popular hydrogenation (HYD) route which is
believed to be the efficient desulfurization route especially for refractory sulfur
compounds, e.g., 4,6-DMDBT (Bartsch and Taniellian 1974). These HDS route
mechanisms are discussed in coming section. Under certain conditions, tempera-
tures >300 C and atmospheric pressure, thermodynamic factors tend to limit
hydrogenation of aromatic rings. There are a lot of merits, in that the catalysts
active sites are usually unoccupied during the hydrogenation of aromatic com-
pounds. Although the presence of aromatics themselves may lead to possible
inhibition, this could be possible even in their unhydrogenated form. Great interest
is laid on the studies that channels towards determining the optimal conditions,
especially the operational pressure for the HDS unit to be applied for various fuel
cell systems.
Hydrogen supply is another factor that affects this reaction. The solubility of
hydrogen in hydrocarbon solvents swiftly appreciate with temperature raise. Also,
the kinematic viscosity of hydrogen is relatively high. Hence, the order of its
solubility as a function of solvent structure has a trend which decreases in the
following order: hexadecane > bicyclohexyl > tetralin > 1-methylnaphthalene.
It has been noticed and reported that the rates HDS 4,6-DMDBT and of DBT
increases in the presence of hydrocarbon solvent, e.g., the use of cyclohexane
solvent led to better rate enhancement than decaline and much lower rate in the
absence of any solvent (Saleh et al. 2017). The HDS of 4,6-DMDBT was observed
to experience a more pronounced solvent effect as compared to that of DBT HDS.
This observed solvent effect corroborates the argument on hydrogen solubility, in
that the solubility has a strong inverse relationship to solvent’s specific gravity
function, of which diffusivity can be used to justify. The hydrogenation of toluene
studied was found to be affected by the effect of solvent. A study was conducted to
screen the catalyst in deep HDS, and the variation in the activity of this catalyst in
the study was observed to generally diminish with raise in hydrogen pressure. This
compression effect could be associated with hydrogen “starvation” since more
hydrogenative catalysts would experience more of the effect with fall in hydrogen
pressure. At low hydrogen pressure of about 0.79 MPa, desulfurization of LCO with
bulk was compared to that which takes place in the presence of a commercial HDS
catalyst at 343 C; the results showed that RuS2 gave 220 ppmw from 1.47 wt.%, in
contrast to 1680 ppmw that was obtained using the commercial catalyst (Ho 2004).
This activity of RuS2 is quite remarkable and could be linked to its structural feature;
isotropic cubic. The surface SH groups density may be increased by disulfide (S–S)2
species from the effect of hydrogen cleavage from facile heterolytic. Depending on
the structure of catalyst, steric hindrance may tend to become an issue; it appears to
be more pronounced in RuS2 catalysts than those of MoS2 based having highly
anisotropic layered structure. The key remaining question that may come up despite
this interesting result is: will hydrogen supply be a problem for 10–15 ppmw sulfur
regime at low pressures? The use of supercritical solvents attempted to put an end to
the issue potential hydrogen supply (Ackerson and Byars 2000). This approach can
best be proven when the rate limiting step is the hydrogen supply at high pressures.
Subsequently, the HDS of 4,6-DEDBT over a sulfided (catalyst A); CoMo/Al2O3-

SiO2 was employed to examine some elementary details of deep HDS (Ho 2004).
8 Mechanisms of Hydrodesulfurization in Diesel

and Gasoline Fuels
Gasoline, jet fuels, and diesel are the three principal types of transportation fuels
which may vary significantly in composition and properties, produced from various
refinery streams. The typical sulfur compound types found in liquid fuels and their
corresponding refinery streams for fuels are summarized in Table 3.2 (Song et al.
2000a, b). The reactivity ranking is obtained from well-tabulated experimental data
and a large pool of literature information. Direct HDS through hydrogenolysis
pathway occurs in compounds like disulfides, sulfides, thiols, and
tetrahydrothiophene and other sulfur compounds with no structural conjugation
between the π-electrons on the aromatic ring moiety and the lone pairs on S atom
and the lone pairs on S atom of the compound. Significantly higher HDS reactivity
has been shown by these sulfur compounds relative to those of thiophene because
the former has weaker C–S bond as well as higher electron density on the S atom.
The reactivity of 1- to 3-ring sulfur compounds increases in the order
dibenzothiophenes < benzothiophenes < thiophenes (Vasudeven and Fierro
1996). Consequently, thiophenes found in naphtha are relatively far less reactive
than the disulfides, sulfides, and thiols as such; in practical high-conversion pro-
cesses, the latter can be essentially infinitely reactive. Similarly, in gas oils, the
reactivity of (alkyl-substituted) sulfur-containing compounds such as
4-methyldibenzothiophene and 4,6-dimethyldibenzothiophene (4,6-DMDBT) are
by far low relative to the others (Gates and Topsoe 1997; Kabe et al. 1992). Hence,
Table 3.2 Typical sulfur compounds and corresponding refinery streams for fuels (Song 2003)
Refinery streams Corresponding
Types of sulfur compounds obtained fuels generated
Mercaptanes, RSH; sulfides, R2S; disulfides, SR-naphtha; FCC naph- Gasoline
RSSR; thiophene (T) and its alkylated deriva- tha; coker naphtha (BP range:
tives, benzothiophene 25–225 C)
Mercaptanes, RSH; benzothiophene (BT), Kerosene; heavy naph- Jet fuel (BP range:
alkylated benzothiophenes tha; middle distillate 130–300 C)
Alkylated benzothiophenes; dibenzothiophene Middle distillate; FCC Diesel fuel
(DBT); alkylated dibenzothiophenes LCO; coker gas oil (BP range:
160–380 C)
Greater than or equal to three-ring polycyclic Heavy gas oils; vacuum Fuel oils
sulfur compounds, including DBT, gas oil; distillation (non-road fuel and
benzonaphthothiophene (BNT), phenanthro resides heavy oils)
[4,5-b,c,d]thiophene (PT), and their alkylated
derivatives and naphthothiophenes (NT)
Mercaptanes Gasoline
R-SH, R-S-S-R Range
Thiophenes
R R = Alkyl or H
S
T with Me at C–2 /C–5 Jet
Range
R
S
Me
Relative Reaction Rate (AU)
Benzothiophenes
Diesel
R Range
S
BT with Me at C–2 /C–7
R
S
Me
Dibenzothiophenes
R
S DBT with Me at C–4
R
S
DBT w/ Me at C–4/C–6
Me
R
S
Me Me
Increase in Size & Difficulty for HDS
Fig. 3.6 The relationship between reactivity ring sizes and positions of alkyl substitutions on the
ring of various organic sulfur compounds in HDS process
in deep HDS, the required conditions are the major factors that affect the transfor-
mation of these main methyl-substituted dibenzothiophenes. In 1997, it was
reported that catalysts and reaction mechanisms are most appropriately studied
using 4-methyldibenzothiophene and 4,6-DMDBT. In general, the most acceptable
HDS mechanism for the reaction of DBT and 4,6-DMDBT takes place through two
principal pathways, Fig. 3.6 (Song et al. 2000a). The first pathway requires the
removal of sulfur in the absence of the aromatic rings abetting; this is otherwise
called the hydrogenolysis pathway, while the second pathway on the other hand
involves the preferentially hydrogenation of aromatic rings of DBT into 4H- or
6H-DBT intermediates before are finally desulfurized. This pathway is also called
the hydrogenation desulfurization (HYD) route (Srivastava 2012).
Co–Mo–S model has for long provided a key basis for strategic developments of
catalyst, shown in Fig. 3.7, specifically based in situ characterization techniques.
Alumina support, commonly employed in hydrotreatment of catalysts, has the
superiority that it allows quite easily a high Co–Mo–S structural dispersion, and
in fact, the Co–Mo–S structure may not contain MoS2 backbone as single MoS2
layers. Reports based on the previously conducted research also suggested that the
Fig. 3.7 (a) Pictorial

diagram showing alumina-
supported Co–Mo–S, Co,
and other Co sulfide
structures. (b) Ball sphere
model of a bulk-truncated,
hypothetical simulated
hexagonal MoS2
nanocluster clearly showing
the (0001) basal plane
(Lauritsen et al. 2007)
support may contain some of the promoter atoms or as separate promoter sulfide
structures. Nevertheless, these are inactive structures, and therefore to avoid their
formation, it is essential to have preparation and activation parameters control
(Topsøe et al. 1981; Wivel et al. 1981). And because employing the use of alumina
support enhances the development of small MoS2 nanoclusters of high stability,
which are usually characterized by high MoS2 edge sites concentration, this is
essential as it accommodates higher quantity of (Co) (Ni) which could be in the
active Co–Mo–S (Ni–Mo–S) structure form. The support, in addition to its ability to
stabilize small nanoclusters, could also have a direct interaction with the clusters,
thereby influencing the intrinsic activity of the Co–Mo–S structures’ active sites
(Topsøe et al. 1996).
It has been observed that elevating the temperature of the sulfiding process from
400 to 600 C brings about bond breakage yielding a modified Co–Mo–S structure
and alumina as well and were found to have significantly promising per active site
activity relative as compared to the lower temperature formed ones. These are
referred to as Type II and Type I Co–Mo–S, respectively (Candia et al. 1984).
Experimental results have been reported to show that in the structures of Type I
category, Mo–O–Al bonds uniquely exist specifically between the Co–Mo–S struc-
tures and alumina support, hence, making the Co–Mo–S structure adopt some
modified catalytic properties in many ways (Hinnemann et al. 2005). The bond to
the support in the low-active Type I may be broken by high-temperature sulfiding,
perhaps transforming into the Type II category which are high active. However,
since this method of treatment may as well lead to unplanned sintering as well as
subsequent loss of crucial edge sites, it’s an undesirable approach of producing
Type II structures. There is therefore a need to find alternative methods of prepa-
ration; this may involve the addition of some additives or chelating agents, and
alone side a weakly interacting support, e.g., carbon (Topsøe et al. 1996). Type II
sites containing catalysts may form multi-stack MoS2 structures, which could just
be a side reaction product owing to the presence the very important weak support
interactions, for example during hydrogenation reactions, the multi-stacks play an
important role as only its top most layer will reveal the special brim sites. While in
fact, single block piece of Type II Co–Mo–S structures catalysts could also be
produced even for supports like carbon, which is a weakly interacting support,
single slab structures may dominate (Carlsson et al. 2004). Other important
advances were the possible existence of the structures Ni–Mo–S and Co–Mo–S in
both low activity and high activity corresponding to Type I and Type II structures,
respectively. However, there are several other atomic level features about Co–Mo–
S that are yet to be known and understood, and consequently, for several years, it
has been challenging to advance further as more information is required for
fundamental understanding of the mechanism, for example, without atomic insight,
it’s virtually impracticable, to fully understand in great details the sites involved
and how they are involved in the HYD and DDS pathways for HDS. Fortunately,
more recent advancements in technology have changed this whole idea, and with
special techniques like scanning tunneling microscopy (STM), well-resolved
atomic images of MoS2 nanoclusters can be provided (Helveg et al. 2000), Co–
Mo–S and Ni–Mo–S (Lauritsen et al. 2007), and direct images of catalytically
active edges can be obtained as well. Coupling this technique with DFT calcula-
tions (STM-DFT) provides a good avenue to generate electronic structure informa-
tion, which demonstrate a key role in understanding catalysis and hence, more
useful information can be unveiled. The small sulfide clusters may have uncommon
sites with metallic-like feature, called “brim sites,” located adjacent to the edges
and appear bright in the STM images, which reveal a detailed insight into the Co
and Ni promoter atom positions in Co–Mo–S and Ni–Mo–S structures. The STM
results provide much more detailed insight, revealing the preferential occupation of
the promoter atoms in very specific edge sites types, referred to as S-edges. It was
also found that different modifications of Co–Mo–S and Ni–Mo–S might as well be
present (Lauritsen et al. 2007). It has been shown that a detailed insight in the
morphological of catalysts with high surface area can be obtained using high angle
annular dark field scanning transmission electron microscopy (HAADF-STEM)
(Carlsson et al. 2004). High-resolution electron tomography is another approach
that may be used and interestingly, information on the catalyst morphology can be
obtained even for the Ni–Mo–S structures consisting of single layers. The Ni–Mo–S
crystals were found to exhibit the hexagonally truncated morphology and higher
order truncations as well for this catalyst preparation (Lauritsen et al. 2007).
Dibenzothiophenes (DBT) and DBT derivatives substituted especially at the 4-
and 4,6- positions of the ring structure are considered one of the most refractory
classes of sulfur compounds in gas oil (Girgis and Gates 1991; Beens and Tijssen
1997). The identification of a novel catalytic routes mechanism for the improve-
ment of the efficiency of hydrodesulfurization of substituted dibenzothiophenes is
crucial in achieving deep HDS. Houalla et al. (1980) reported two parallel reaction
pathways they suggested for the hydrodesulfurization of DBT:
1. formation of biphenyl by C–S bonds direct hydrogenolysis
2. two steps formation of cyclohexylbenzene via hydrogenation of one of the
benzenoid rings followed by their subsequent rapid hydrogenolysis
Several other studies (Houalla et al. 1980; Nagai et al. 1986), in addition to these,
suggested that for the hydrogenation and hydrogenolysis transformations, other
possible catalytic sites do exist. According to Landau et al., they reported that a
higher desulfurization rate was obtained in the hydrogenation of
4,6-dimethyldibenzothiophene (4,6-DMDBT) (Landau et al. 1996). Accordingly,
catalysts with higher activity towards hydrogenation also show promising activity
in the hydrogenation of 4,6-DMDBT. In spite of that, the hydrogen-to-hydrogen
sulfide ratio employed at least 380 Nl/Nl, which swiftly mismatch the standard
commercial once-through trickle-flow reactors results: ca. 15–20 Nl/Nl, hence does
not suitably serve as representative of a deep HDS. And this is because hydrogen
sulfide not only heavily influences the absolute activity of HDS, but also tempers
with the relative significance of the competitive hydrogenolysis and hydrogenation
pathways, and the relative catalytic activities of the supported NiMo and CoMo
catalysts in refractory compounds the hydrodesulfurization, such as 4-MDBT and
4,6-DMDBT (Lamure-Meille et al. 1995): Ma et al. found that at high hydrogen-to-
hydrogen sulfide ratios NiMo catalyst has an advantage over a CoMo catalyst when
employed in the hydrodesulfurization of 4-MDBT and 4,6-DMDBT; however, the
catalysts activities were very much comparable at low hydrogen-to-hydrogen
sulfide ratios. Consequently, the question remains open whether the use of NiMo
catalyst in deep HDS provides any advantage over a CoMo catalyst at the low
hydrogen-to-hydrogen sulfide ratios representative of commercial once-through
trickle-flow HDS reactors.
Co-promotion of MoS2 catalysts forms the Co–Mo–S phase, where (10 10)
S-edges of MoS2 particles assist in the incorporation of Co atoms, leading to the
formation of Co–Mo–S edge and significantly varying the structural and hence
catalytic properties of the catalyst (Besenbacher et al. 2008). An essential effect of
the Co-promotion is that the produced Co–Mo–S equilibrium structure contains
inherent sulfur vacancies, which means that at the start of the catalytic cycle,
additional sulfur vacancies need not to be formed. The unpromoted S-edge, in
contrasts with, Co-promotion ones, requires the creation of vacancies as the first
step in a catalytic cycle since it has full S coordination at its equilibrium state. It is
important to emphasize that unique coordinatively unsaturated sites (CUS) are
available at equilibrium conditions in the Co–Mo–S edge, and for this reason, the
catalysis requires no vacancy formation at the initiating step. The situation is very
dissimilar in the case of the unpromoted S-edges catalysis, and research findings
have stressed the fact that it is very vital to consider that initial vacancy creation and
Fig. 3.8 Scheme showing the HDS of thiophene, reactions, and structures involved. Equilibrium
structures are shown in atomic structures format at HDS conditions of the (10 10) and the (10 10)
edge. The scheme shows an overview of the Co-promoted reactions, (10 10) edge marked with red
lines and the non-promoted (10 10) edge indicated with black lines in the upper part of the scheme
and in the lower part the reactions at the non-promoted (10 10) edge and in the middle the possible
interactions between the two coexisting edges. The dotted arrows denote slow progressing
reactions (Moses et al. 2008)
sulfur addition are two possible mechanisms both of which hydrodesulfurization

(HDS) reactions can occur. The bright brim is a feature exhibited by Co–Mo–S
active sites (Lauritsen et al. 2007) which are quite analogous to brim site of the
Mo-edge. Turning to the catalytic activity, Fig. 3.8 provides a scheme showing the
HDS of thiophene, reaction pathways, and structures involved, comparing an
unpromoted MoS2 and a promoted Co–Mo–S catalyst. The suitability of the Co–
Mo–S edge for both C–S-scission and hydrogenation steps is the main consequence
of the Co-promotion, whereas the unpromoted Mo- and S-edges are basically fitted
for one of the two. The driving force for intermediates adsorption is thermodynam-
ically controlled to transform from the (unpromoted) Mo-edge to the Co–Mo–S
edge and thus, there is a high chance of hydrogenation occurring at both the Mo-
and Co–Mo–S edges. The concluding remark here is that Co-promotion improves
the catalytic properties of the catalyst towards hydrogenation. C–S-scission barriers
are lower for Co–Mo–S than those for the non-promoted Mo-edge, but higher for
the non-promoted S-edge. Although with the increasing hydrogenation activity and
rise in adsorption energy of thiophene via the direct desulfurization (DDS) path-
way, it is expected that Co–Mo–S brim site’s activity rises higher than the
unpromoted S-edged ones.
In MoS2-based catalysts catalyzed hydrodesulfurization (HDS) reaction, various
basic nitrogen-containing compounds, e.g., pyridine are popularly known to serve
as inhibitors for this reaction. The interplay of density functional theory (DFT)
calculations together with experimental data from scanning tunneling microscopy
(STM) revealed an atomic-scale insight into the nature of pyridine adsorption on

MoS2. Previous IR-spectroscopy and DFT studies were found to be in good
agreement with the STM results obtained, which showed that the interaction of
pyridine molecule itself with the MoS2 nanoclusters is a very weak one or not even
interacting at all. However, a significant adsorption enhancement observed in the
presence of hydrogen is present at the MoS2 edges, revealed by STM at the edges
showing some adsorbed species. By analyzing the DFT energies obtained from
calculation and simulated STM images, it could be concluded that these species are
pyridinium ions located at the catalytically active brim sites. In addition to that, the
results of DFT calculations for the vibrational modes of the adsorbed pyridinium
species were found to agree quite well with those obtained from previously reported
IR experiments on alumina-supported MoS2 catalyst of high surface area. There is
high level of similarity between these adsorption sites and the brim sites involved in
hydrogenation reactions in HDS. Therefore, combining the STM results and DFT
calculations reveals a novel atomic-scale insight into the inhibition mechanism of
basic N-compounds in HDS and directly observing for the first time, the mode of
adsorption of basic nitrogen compounds on the active catalytic MoS2 edges.
Furthermore, these results were in full support of the previously reported study
correlating the affinity of the N-containing compounds for proton and their strength
inhibitions.
The detailed information of the interaction of pyridine molecules at atomic scale
with the active catalytic sites on MoS2 nanoclusters has been studied using STM
studies and DFT calculations. The pyridine molecules were found to be only
adsorbed weakly on the MoS2 edges as revealed by atom-resolved STM. In
addition, the presence of SH groups on the edges leads to the observation of other
chemisorbed species on the brim sites. These results were compared with DFT
calculations and simulated STM images and the species were assigned to the
adsorbed pyridinium ions on the brim site edges of the MoS2 nanoclusters. Conse-
quently, these results reveal the first direct observation of pyridinium ions. It was
found that pyridinium adsorbed in an inclined fashion on top of the MoS2
nanoclusters on the brim sites was the most suitable binding mode. In addition,
there was a very good agreement between frequencies observed from previous IR
studies on MoS2/Al2O3 catalysts of high surface area and the calculated ones for
pyridine and pyridinium ion. The findings that the peak at IR frequency of 1546 cm1
could be best attributed to pyridinium ion further emphasize that the principal
HDS inhibitor for the MoS2 catalyst is not actually pyridine molecule itself, but
rather the pyridinium ion. The fact that the previously reported DFT calculations
revealed a very satisfactory activation barrier for pyridinium ion formation
(Logadottir et al. 2006), in distinction to the experimental IR data gathered,
could possibly be related to the effects of catalytic support that were not taken
into consideration by the DFT calculations. A twofold effect of the adsorption of
pyridinium ion on the sites of Mo-brim edge are known in the overall poisoning
process of the HDS catalyst:
• The first adsorption effect is the assisted consumption of adsorbed hydrogen

atoms, which could potentially improve hydrogenation reaction step.
• While the second effect is believed to occur due to blockage of the hydrogena-
tion pathway sites by the strongly binded pyridinium species adsorbed on the
MoS2 brim sites.
According to some reported results in the literature, an even stronger poisoning
effect were suggested for cyclic nitrogenous compounds heavier than pyridine, due to
the more intrinsic delocalized p-character they have, van der Waals interaction with
the MoS2 nanoclusters is high promoted, and consequently, binding more strongly to
the active catalytic brim sites (Beens and Tijssen 1997; Shih et al. 1992). These
compounds also have better proton affinity, qualifying them as stronger inhibitors for
the hydrogenation mechanistic pathway. Several other reports suggested that heavier
N-cyclic compounds be further studied with Co- or Ni-promoted MoS2 nanoclusters.
In another study, active carbons supported NiMo sulfide (NiMo/C) was used in the
desulfurization of 4,6-Dimethyldibenzothiophene 4,6-DMDBT into n-decane inside
a microautoclave inserted in a sampling apparatus to essentially establish the kinetics
and mechanism of hydrodesulfurization HDS by measuring the equilibrium between
4,6-DMDBT and corresponding tetrahydro derivative assisted by a computational
curve fitting. At higher temperatures between 340 and 380 C, regardless of the
presence of carbon supports the (NiMo/C) catalysts was shown to exhibit relatively
higher activity towards the HDS of 4,6-DMDBT than the commercially established
NiMo/alumina catalyst (Sakanishi et al. 2000).
9 Deep Hydrodesulfurization of Diesel and Gasoline Fuels
The increasing rise in the standard for sulfur removal specifications has triggered
continuous research for the further improvements in the processes of deep
hydrodesulfurization (HDS) technology, of which were mostly carried out using
fixed bed reactors. One of the major issues faced in deep desulfurization of diesel
fuels is the troubles involved in removing refractory sulfur compounds, especially
4,6-dimethyldibenzothiophene, with conventional hydrodesulfurization processes.
This issue engulfing deep HDS is exacerbated by the compounds: H2S and
polyaromatics inhibiting effects and those of nitrogen compounds as well. While
on the other hand, selective HDS of thiophene compounds and derivatives with no
significant loss of octane number is, in fact, a critical issue for gasoline deep
desulfurization. The appropriate octane number can be retained by the isomeriza-
tion of the paraffinic components of naphtha, as well as by olefinic components
preservation in FCC naphtha (Song 2003). A more recent approach reported is the
use of slurry reactor hydrodesulfurization (HDS) of diesel, which has proven to be
more promising than the one conducted in a fixed bed reactor. This improvement
was attributed to the high activity of the catalyst, online catalyst introduction, and
elimination, and finally the uniform heating profile, thereby increasing the
efficiency the process. The HDS of straight-run diesel was carried out in a high-
pressure autoclave under the following operating conditions: 3–5 MPa of pressure,
at a hydrogen flow rate of 0.56–2.77 L min1, at temperature of 320–360 C, using
a NiMoS/Al2O3 catalyst, with a loading of 4.8–23.1 wt% in the reactor. The rate of
reaction was observed to be sensitive to the amount of catalyst used as well as the
hydrogen flow rate, pressure, and temperature employed (Deng et al. 2010). A set
up was designed to carry out deep desulfurization using a steady-state model as a
test plant for a catalytic trickle-bed reactor. This was developed to adequately
model the hydrodesulfurization of vacuum gas oil with high sulfur compounds
content. Kinetic study was conducted based on the experimental data of the sulfur
content of the exit reaction mixture to estimate the kinetic parameters and was
found to be in satisfactory agreement with the theoretical data obtained from the
model. According to the experiments conducted, while keeping other parameters
constant, a rise in pressure and the ratio of H2/CH, as well as a fall in LHSV,
enhance the effective removal of sulfur compounds from the gas oil. Also, an
improved quality of gas oil product was obtained as shown by the analysis of
physico-chemical characteristics of the products relative to the feedstock, such as a
decrease in density and viscosity, as well as the increase in cetane index values.
Also, the theoretical simulation study was conducted by keeping all other param-
eters constant and varying parameters such as pressure, the ratio of H2/CH, and the
LHSV. It was concluded that many design parameters offer the possibility of
accepting the best process conditions for specific feedstock (Sertic-Bionda et al.
2005).
The desulfurization of alkyl-dibenzothiophenes can be achieved in two ways.
The first takes place via the through direct extraction of sulfur, producing biphenyl-
type products (BP). It is sometimes called the hydrogenolysis path. Hydrogenation
is the second desulfurization path, in this approach, prehydrogenation of one of the
aromatic rings leads to the formation of cyclohexylbenzene-type products (CHB).
The ratio of the rate constants of these two paths is the measure of their relative
importance. However, this ratio is not easily obtainable, and for that reason, another
term is defined: hydrogenation index (γ), which may be expressed as the ratio of the
weight percent of CHB to BP in the desulfurized product, mathematically stated as:
Wt:%CHB in product
γ¼
Wt:%BP in product
This definition can be better understood using an example for illustration. When
applying the definition to the HDS of 4,6-diethyldibenzothiophene (46DEDBT), γ
is the ratio of C4CHB (diethylcyclohexylbenzenes and isomers) to C4BP
(diethylbiphenyls and isomers), even though C2CHB compounds such as
ethylcyclohexylbenzene and dimethylcyclohexylbenzenes as well as C2BP, e.g.,
ethylbiphenyl and dimethylbiphenyls are formed as side products (Ho 2004). In a
similar way, in 4,6-dimethyldibenzothiophene (46DMDBT) HDS, the ratio of
C2CHB to C2BP is simply the γ. It is important to note that it is only reasonable
to compare γ for different catalysts at constant HDS. It is only fortunate that, at
constant conditions of temperature and pressure, for highly hindered β-DBTs (e.g.,
46DEDBT) at least, γ does not change significantly with space velocity (Ho 2004).
Since in general, hydrogenolysis has a considerably higher activation energy
relative to hydrogenation (Farag et al. 2000), γ swiftly falls with temperature.
And γ on the other hand has a direct proportionality relationship with pressure,
and this is because hydrogenation is a stronger dependent on hydrogen pressure
(Bataille et al. 2000).
10 Conclusion
Despite the rigorous ongoing research on desulfurization and the considerable

attention in some areas of desulfurization like oxidative desulfurization, the use
of microbes for sulfur compounds metabolism and selective adsorption, the princi-
pal approach to sulfur removal remains the HDS method. Herein, we discussed
some important processes of desulfurization technology in oil and gas industries
and the various classifications of desulfurization and as well, the forms of
hydrodesulfurization of diesel and gasoline fuels which is the focus of the chapter.
Also, nanocatalysts design was another aspect that we try to consider, by looking at
various catalyst reported for some specific desulfurization process and the condi-
tions they work best in. In addition, doped nanocatalysts preparations was also a
topic of interest. Furthermore, an example of hydrodesulfurization reaction was
described, where a model example of dibenzothiophene was used, as HDS of
thiophene, its derivatives, and closely related compounds are still relevant. Factors
generally affecting hydrodesulfurization reactions were also considered. Most
importantly, we pointed out some essential mechanisms of hydrodesulfurization
in diesel and gasoline fuels, and some of the approaches to deep hydrogenation of
diesel and gasoline fuels which provides a cost-efficient alternative to meeting the
future specifications of world’s environmental agencies regarding sulfur contents;
however, it is important to note that more research still needs to be conducted to
check for the suitability of future approaches to meet the sulfur limit specifications
and address the problems that may hinder their feasibility.
Acknowledgement The authors acknowledge the support of the chemistry department, and King
Fahd University of Petroleum and Minerals, (KFUPM) Dhahran, Saudi Arabia.
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Chapter 4
Improvement of Hydrodesulfurization
Catalysts Based on Insight of Nano Structures
and Reaction Mechanisms
Hui Ge, Zegang Qiu, Zhenyu Ge, and Wenpeng Han
Abstract Two-dimensional (2D) layer materials have attracted surging interests

since the discovery of the super properties of graphene in 2004.
Hydrodesulfurization (HDS) catalysts which contain mainly 2D layer Mo(W)S2
active phases with Co or Ni as promoters thus obtain new development chance.
Combining characterization technologies with theory calculations, the catalytic
structure, electronic properties, and reaction mechanisms have been largely
revealed. These new insight understandings have facilitated the design and fabri-
cation of high-performance HDS catalysts for not only ultra-deep desulfurization
but also the quality improvement of different type of fuels. However, this needs the
subtle tradeoff among different catalytic properties such as HDS, selective hydro-
genation, hydrodenitrogenation, and hydrodearomatics for the achievement of the
octane value retaining of gasoline, cetane number improvement of diesel, or
polyaromatics saturation of heavy fuels, which still have a lot of technique chal-
lenges. The industrial application also requires the effective synergism between
process and HDS catalysts.
Keywords 2D MoS2 • Hydrodesulfurization • Promoters • Alumina • Support

interaction
H. Ge (*) • W. Han
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of
Sciences, Taiyuan, Shanxi 030001, PR China
e-mail: [email protected]
Z. Qiu
College of Chemistry and Chemical Engineering, Xi’an University of Petroleum, Xi’an,
Shaanxi 710065, PR China
Z. Ge
School of Material Science and Engineering, Shandong University, Jinan, Shandong 250002,
PR China

98 H. Ge et al.
1 Introduction
Hydrodesulfurization (HDS) is one of the most important processes in the refinement

of petroleum, by which the sulfur impurity is removed from hydrocarbons. Other-
wise, upon fuel combustion, sulfur oxides are emitted, causing harmful sour rain.
Although industrial Co(Ni)Mo(W) sulfide catalysts are effective to remove most
organosulfur compounds, such as thiol, thioether, thiophenes, benzothiophenes, and
dibenzothiophenes (DBT). It remains a tough challenge for HDS of
4,6-dimethyldibenzothiophene (4,6-DMDBT) analogs that have substitutions hinder-
ing the adsorption and reaction of sulfur heteroatoms. The situation becomes more
serious by the continually increased sulfur content in the crude oils and more stringent
sulfur limits for fuel products (Fujikawa et al. 2006). Meanwhile, the refining cost
needs to be carefully controlled due to the decreased interests. Thus, catalysts must be
effective to achieve ultra-deep desulfurization with affordable cost.
The last two decades have seen major advances in the characterization tech-
niques and theory calculation which have helped us to understand active sites,
elementary steps in reaction paths, and the interactions between active phases with
supports in the Mo(W)S2-based HDS catalysts. Since Novoselov (2004) discovered
monolayer graphene with super properties, there emerges a researching wave to 2D
MoS2 analog materials. The newly acquired knowledge have opened up the way to
rationally design and synthesize novel Mo(W)S2-based catalysts for ultra-deep
desulfurization of oil streams (Wang et al. 2013).
In this chapter, we review the recently obtained insights on the relation of
structures with catalytic properties of HDS sulfide catalysts. And we present how
the novel catalysts are designed and synthesized based on these understandings.
And then we show that the newly developed catalysts are effectively applied in the
ultra-deep desulfurization in petroleum refinement.
2 Relation of Structures of Mo(W)S2-Based Catalysts

with Activities
2.1 Structures of Layer Mo(W)S2
Mo(W)S2 materials have the unique “sandwich” structure composed of a metal

layer between two sulfide layers. The “sandwich” layers are interacted by the weak
Van der Waals forces and atoms in the layer are linked by the strong covalent bond.
Thus, the bulk Mo(W) sulfides can be easily exfoliated into single- or few-layered
2D materials, which can be further tuned or assembled to heterostructures (Wang
et al. 2015a).
According to the array of sulfur atoms in the layer and the stacking configura-
tions, Mo(W)S2 can form three phases (Fig. 4.1). 2H phase is thermodynamically
stable, in which each layer rotate 180o and the layer configure is recovered every
other layer. While 3R phase returns original configuration every three layers. Each
4 Improvement of Hydrodesulfurization Catalysts Based on Insight of Nano. . . 99
Fig. 4.1 Structure of MoS2. They can crystallize in 1T (tetragonal), 2H (hexagonal), or 3R

(rhombohedral) symmetry. The figure also shows the hexagonal Brillouin zone with the high
symmetry k points (Reproduced from Heine 2015)
Mo or W atom is coordinated by six sulfur atoms in a trigonal prism for 2H and 3R

phases. 1T-MoS2 phase is metastable and six S atoms form a distorted octahedron
around one metal atom (Heine 2015). Three phases can be transformed via
intralayer or interlayer atomic gliding. For example, with intercalation of Li,
2H-MoS2 can be converted to 1T-MoS2 (Wang et al. 2014), which however
gradually transforms back to 2H-MoS2 at room temperature (Jiménez Sandoval
et al. 1991).
2.2 Promoting Effect of Co or Ni to the Mo(W)S2 Active

Phase
Mo(W)S2-based catalysts usually prepared with Co or Ni as promoters to improve

the HDS activities. Topsøe (1981) suggested the so-called Co-Mo-S model where
Co is located at the edge of Mo(W)S2 slabs. Lauritsen et al. (2007) indeed observed
the Co-Mo-S and Ni-Mo-S structures by STM (Fig. 4.2a–c). And they found that
the promoter coordination leads to a morphology transformation from the triangle
of unpromoted MoS2 to the distorted hexagon.
100 H. Ge et al.
Fig. 4.2 STM images of a hexagonally truncated Co-Mo-S nanocluster (a) and Ni-Mo-S (b, c)
supported on Au (111). Morphology diagrams for the Co-Mo-S (d–f) and Ni-Mo-S (g–i)
nanocluster as a function of ΔμS and p(H2S)/p(H2) at T ¼ 525 K. The S-edge compositions are
reported above the blue line, and the Mo-edge compositions are below this line. The gray region
visualizes the range of usual HDS conditions (Adapted from Lauritsen et al. 2007; Krebs et al.
2009)
Fig. 4.2d–i shows that the equilibrium morphology of Co-Mo-S and Ni-Mo-S
nanocluster under HDS conditions is a hexagon and a deformed hexagon, respec-
tively. Ni is located in a square planar environment at both Mo and S edges. The
same is true for the mixed Ni-Mo sites. Co is predominantly located in the
tetrahedral environment at the S-edge. However, mixed Co-Mo sites are preferen-
tially located on the Mo-edge. The Co atoms on the edges of MoS2 crystallites are
4-fold coordinated with either tetrahedral, pseudo-tetrahedral, or square planar
structure depending on the sulfur coverage, type of substituted edge (S or Mo),
and promotion degree (Castillo-Villalon et al. 2012).
The thermodynamic balance between the stability of promoted sites and promoter
segregation effects is mainly driven by S-reductive conditions and can be interpreted
by Le Chatelier’s principle (Krebs et al. 2008a). Complete promoter segregation
occurs under reductive conditions and at high temperature, corresponding to condi-
tions not reached in HDS. Three sulfiding regimes characterized by the chemical
potential of sulfur (μS) can be distinguished in Fig 4.2. In the high sulfiding regime
(μS 0.25 eV), Co and Ni are stabilized on both edges. In the intermediate regime,
i.e., traditional HDS conditions (1.1 μS 0.25 eV), the selective affinity of the
promoters for one type of edge is revealed. In the highly reductive environment
(μS 1.1 eV), the mixed phase becomes unstable (Schweiger et al. 2002).
Different from the Co-Mo-S model. Delmon and Froment (1996) suggested the
remote control mechanism illustrate the interaction of promoters with MoS2 crys-
tallites in bulky HDS catalyst. They found that in unsupported Co(Ni)Mo(W)S2
system, the hydrogenation and HDS ability of MoS2 or WS2 can be significantly
enhanced by the spillover hydrogen which is produced on the NiSx or CoSx phase.
This synergetic effect is demonstrated by the experiments of stacked bed where the
formation of Co-Mo-S phase was physically prohibited (Ojeda et al. 2003).
Ramos et al. (2012) suggested that increase of the contact between MoS2 and
Co9S8 improves the HDS activity of bi-component sulfide catalyst. Wang et al.
(2016) reported the spillover hydrogen effect between the NiSx and MoS2 two
phases played an important role on the high HDS performance of unsupported
NiMo catalyst with high promoter loading. Villarroel et al. (2008) and Pimerzin
et al. (2015) also evidenced that the synergism between Co(Ni) and Mo(W) sulfide
phases leads the high catalytic activity of promoted sulfide catalysts.
2.3 Carburization of HDS Catalysts
Using dimethydisulfide (DMDS) instead of H2/H2S as sulfiding agent, Hallie

(1982) observed that the HDS activity of gas/oil was apparently improved, which
was explained by Kelty et al. (2007) as the formation of carbide-like structures at
the edge of the active phase. By the analysis of spent HDS catalyst, Breysse et al.
(2003) suggested that the “carbide” phase could present in between Co-Mo-S
structures. And the cobalt promoter can facilitate the sulfur replacement by carbon
at MoS2 edges. Wen et al. (2006) showed by DFT calculation that carbon atom
replacing sulfur atom at the edges of MoSx cluster is a thermodynamically favored
process. However, Tuxen et al. (2011) studied the carbonization of MoS2-based
catalysts by DMDS or dimethylsulfide. They could not observe the formation of
carbide type phase. DFT calculation suggested that the carburization at (Co)MoS2
edge by organic sulfiding agent is not favorable.
102 H. Ge et al.
Fig. 4.3 Simultaneous sulfidation and carburization by CH3S or CH3SSCH3 over CoMo/Al2O3
(Reproduced from Ge et al. 2014)
Recently, a combination of experiments and theory calculation, we carefully

analyzed the process of carbonization of CoMo HDS catalyst. We found that the
replacement of sulfur atoms at (Co)MoS2 edge by the carbon atoms of DMDS
molecule is indeed thermodynamic unfavored (Ge et al. 2014). However, the
simultaneous sulfidation and carbidation on the unsaturated edges of (Co)MoSx(Cy)
are possible (Fig. 4.3 and Table 4.1).
Carburization is not limited to the formation of carbide-like structures. Several
carbon species may be simultaneously presented on the catalysts in real HDS
conditions. Thus, the effect of carburization is usually an additive result of multi-
carbon species. The organic chelating agents, such as EN, coordinated with Co2+
delays the sulfidation of cobalt promoters and facilitates the formation of Co-Mo-S
active structures; on the other hand, the carbonization of chelating agent may coat
the Co2+ retarding its access to the MoS2 slabs. Ge et al. (2009) reported that the
support-like carbon weakens the interaction between active metals and support
which can improve the HDS activity. And coke-like carbon covers the active sites
and suppresses the catalytic activity. Glasson et al. (2002) observed a positive effect
of carbon bearing CoMo catalysts prepared with the addition of soybean oil for
thiophene and crude oil desulfurization. They suggested that carbon deposits
isolated the active particles resulting in a high dispersion. Similar positive results
were found in CoMo catalyst presulfided by alkylpolysulfides (Alonso et al. 2002)
and in MoS2 catalyst produced by in situ decomposition of (R4N)2MoS4 (Alvarez
et al. 2004).
Table 4.1 The relative energy (eV) of simultaneous sulfidation and carburization by CH3S or
CH3SSCH3
Process Edge From To CH3S CH3SSCH3
a to e S 50% S 75% S and 25% C 1.53 2.88
b to f S 25% S and 25% C 50% S and 50% C 0.57 0.78
c to g S 50% C 25% S and 75% C 1.65 0.30
d to h Mo 0% S 25% S and 25% C 1.02 0.32
2.4 Interaction of Support with Active Phase
In refining industry, alumina is used almost exclusively as the support of HDS

catalyst due to the excellent textural and mechanical properties and relatively low
cost. However, the strong interaction between alumina support and metal sulfide
phases can lead to the detrimental effect on the catalytic activities.
Hinnemann et al. (2005) revealed the nature and the influence of oxygen
linkages between MoS2-type nanocrystals and alumina support by DFT calcula-
tions. They show that oxygen linkages are predominantly present on the sulfur edge
with the orientation approximately perpendicular to the MoS2 sheets. Because Co
promoters also present dominantly on the S edge, the formation of linkages
compete with the incorporation of Co into the S edge (Byskov et al. 1999). Thus,
if the S edge has been saturated with Co, the linkages to the support may not be
likely formed. The DFT results also suggest that the oxygen linkages between the
MoS2-type structures and the support are not stable, but once Mo-O-Al linkages are
formed, the activation energy for the bond breakage is quite high.
Both the structure and the reactivity of S edges can be severely influenced by the
oxygen linkages. Many studies have shown that vacancy formation is a key step in
the HDS process. But if existing the Mo-O-Al linkage, the vacancy formation
becomes very endothermic. Thus Type I structures, which has a strong interaction
between active phase and support, have a lower catalytic activity than Type II
structures. And the transformation of Type I to Type II is suggested to associate
with the breaking of Mo-O-Al linkages. The adsorption of hydrogen on sulfur edge
sites above linkages is only slightly exothermic (5 kJ/mol) compared to 52 kJ/
mol on the S edge sites without linkages. Interestingly, the adsorption of hydrogen
on a site neighboring to an edge site with a linkage is significantly more exothermic
with 73 kJ/mol. Thus, the hydrogenation reactions can be influenced significantly.
Arrouvel et al. (2005) investigated how the active phase is influenced by
different supports under reaction conditions. The coordination of MoS2 with alu-
mina support depends on the size of the active phase particles. Very small size
MoS2 particles (<15 Å) on γ-Al2O3 (110) and (100) surfaces exhibit Mo-O-Al
bonds for both Mo- and S-edges. While for larger sizes (>15 Å), H bonds and van
der Waals interactions can stabilize the particles parallel to the surface. For anatase-
TiO2 (101) and (001) surfaces, an epitaxial relationship is established between the
Mo-edge and the support surfaces with the formation of Mo-O-Ti-S-Mo rings. But
this epitaxy is not possible between the S-edge and the TiO2 surface. The epitaxial
MoS2 clusters create edge-contacted particles in tilted or perpendicular orientations
104 H. Ge et al.
owing to strong the interaction between the MoS2 edge and TiO2 planes. These
perpendicularly arrayed MoS2 particles are more active. Breysse et al. (2003)
showed four times enhancement of the HDS activity of anatase-supported MoS2
catalysts than alumina-supported ones. DFT calculation of adhesion energies of
Mo5CoSn clusters on the two supports shows that Co promoters suppress the edge
anchoring of active phase due to weakened edge interaction. And smaller size
particles are stabilized on γ-alumina by the ligand effect of the promoter (Costa
et al. 2007). Raybaud (2007) investigated the interface between MoSx and support
using DFT. It was revealed that the surface species and acid-basic properties are
quantitatively correlated with the sulfo-reductive conditions (pH2, pH2S, pH2O, and
T ) and the exposed surface of support. Under HDS conditions, the (110) surface of
γ-alumina is highly hydroxylated, and the (001) surface of anatase (TiO2) is
partially hydroxylated and sulfide (Arrouvel 2004). They both present Brønsted
sites. On the contrary, neither γ-alumina (100) nor the anatase (101) surfaces are
hydrated or sulfided, thus only containing Lewis sites.
2.5 HDS Reaction Mechanism
Thiophene (C4H4S) is the main sulfur component in gasoline fuel and has been
extensively used to investigate the reactivity and kinetics of HDS reactions
(Fig. 4.6). Using the room temperature STM technique, it confirmed that interac-
tions between thiophene molecules and MoS2 clusters mainly occur at the edge
domains. It is revealed that both sulfur vacancies on the edges and the interaction of
flat-lying molecules with the “brim” sites are important for HDS reaction (Lauritsen
et al. 2004). The desulfurization and the hydrogenation of thiophene may occur at
the edge and brim, respectively.
Fig. 4.4d shows the schematic overview of the reaction pathways for thiophene
HDS over unpromoted MoS2 and Co-Mo-S catalysts. Co-promotion makes the Co-
Mo-S edge suitable for both hydrogenation and C–S-scission, meanwhile the
unpromoted Mo- and S-edges are primarily suited for one of the two. Hydrogena-
tion is suggested to occur at both the Mo-edge and the Co-Mo-S edge. And Co
promotors increase the hydrogenation properties of the catalyst. The C-S scission
barriers on Co-Mo-S sites are higher than those on the non-promoted S-edge but
lower than those on the non-promoted Mo-edge. However, due to the increased
hydrogenation activity and adsorption energy of thiophene, the overall activity of
the Co-Mo-S site is high. The equilibrium structure of Co-Mo-S has already
contained sulfur vacancies. Thus, it is not necessary to form sulfur vacancies during
the catalytic cycle. This is contrary to the unpromoted S-edge, which shows full S
coordination in an equilibrium state and requires the creation of vacancies in the
catalytic cycle.
Valencia et al. (2012) investigated the HDS reaction mechanism by DFT. The
full chemical structures in the energetic profile of hydrogenation (HYD) and direct
desulfurization (DDS) routes were shown in Fig. 4.5. The DBT-type compounds
Fig. 4.4 Thiophene adsorption and reaction on unpromoted and Co-promoted MoS2. (a) STM
images of MoS2 nanoparticle and after exposure to thiophene (b) and atomic hydrogen (c). (d)
Schematic overview of the reactions and structures involved in the HDS of thiophene at the
(-1010) S edge and the (10-10) Mo edge (Reproduced from Lauritsen and Besenbacher 2015;
Moses et al. 2009)
exhibit high stability for both aromatic cycle and C-S bond. However, the HYD
reaction route is more favored owing to lower energetic barriers compared with
DDS reaction route.
Tuxen et al. (2012) highlighted the role of interactions of DBT with MoS2 and
Co-Mo-S for HDS reactions using STM and DFT (Fig. 4.6). The corner sites on the
hexagonal CoMoS nanoparticles may play a main role in the DBT desulfurization.
Grønborg et al. (2016) recently revealed how 4,6-DMDBT is desulfurized via
the DDS pathway over CoMo catalyst (Fig. 4.7). It is found that the direct
chemisorption of the 4,6-DMDBT molecule on the CoMoS nanocluster is only
possible at a vacancy in the corner position of the S-edge. But the formation of this
vacancy is energetically unfavorable under HDS conditions and can be present only
at very low frequency. Thus, 4,6-DMDBT is hard to be desulfurized. Interestingly,
106 H. Ge et al.
Fig. 4.5 Mechanism of HDS reaction route for DBT-type compounds (Reproduced from Valencia
et al. 2012)
Fig. 4.6 STM images of Co-Mo-S nanoclusters after exposure to atomic hydrogen and subse-
quent dosing of DBT (Reproduced from Tuxen et al. 2012)
Fig. 4.7 STM image shows the transfer of 4,6-DMDBT adsorption between σ-model (a) and
π-model (b). Line scan along the cyan line shown in the inset of the figure (b) revealing structural
information (c). DFT calculations for 4,6-DMDBT adsorbed on top of a corner S-vacancy in
π-mode (d), at corner-site without a corner vacancy (e) as well as at one corner vacancy (f). Ball
model showing how the σ-mode is sterically impossible to occur in central corner vacancies (g)
(Reproduced from Grønborg et al. 2016)
it is found that the σ-adsorption can transform reversibly into a π-like adsorption.
This suggests the possibility to alternate between two configurations and between
two reaction pathways, namely, on-top brim π-adsorption for HYD and the periph-
eral σ-chemisorption in cluster corner for DDS. Thus, both hydrogenation and
direct desulfurization reactions can occur in the same adsorption process but in
different configurations.
3 Design and Synthesis of Nano HDS Catalysts
3.1 Design of HDS Catalyst
The catalytically active phase in promoted catalysts is suggested to be Co(Ni)-Mo-S

phase, where Co(Ni) atoms are located on the edges of the MoS2 particles (Topsøe
2007). Another model, which is less preferred, is the so-called remote control
theory (Delmon and Froment 1996).
Candia et al. (1984) found that there are two types of Co-Mo-S phases with
distinctly different HDS activities, Co-Mo-S type I and type II, the latter with
decreased support interaction exhibited about two times higher activity than the
former. It is thus expected that highly active HDS catalysts should compose of
highly dispersed Co-Mo-S type II phases. Conventionally, the alumina is used as
108 H. Ge et al.
the support of HDS catalysts. However, the undesirable very strong metal–support
interaction, which results in the type II structures, has urged new supports in order
to achieve more efficient HDS reactions.
The surface energies play an essential role in the shape of the catalyst particles,
the type of exposed facets, and consequently the catalytic activity. Elizabeth
Cervantes-Gaxiola et al. (2013) observed that there is a direct correlation between
the surface energies and DBT conversion for Ni-promoted catalysts. The DFT
calculation shows surface energies in the sequence of NiWS2 (0.1148 eV/Å2)
< NiMoS2 (0.1221 eV/Å2) < NiMoWS2 (0.1336 eV/Å2). The easiness of formation
of mixed Mo and W catalyst surfaces is essential to the incorporation of promoter
Ni in the active surface sites.
Hydrogenation to aromatics improves the quality of diesel with the increased
cetane number. And the hydrogenation to polycyclic aromatics facilitates the
hydrocracking of heavy fuels. However, inhibition of hydrogenation of olefins
(HYDO) is preferred for gasoline fractions, which can avoid the loss of octane
value.
It was observed that incorporating Co into Mo sulfide enhance the HDS activity
apparently but has little effect on HYDO activity. This suggests the different active
sites for these two reactions. Candia et al. (1984) reported that Type II Co–Mo–S
phase with high stacking had better HDS/HYDO selectivity than the Type I Co–
Mo–S one. Choi et al. (2004) reported HYDO occurring at the interfacial sites
between sulfide phase and alumina support and HDS at the edge vacancies MoS2
slabs. Mey et al. (2004) observed that addition of alkali reduces the HYDO activity
more than the HDS one, which enhances the HDS/HYDO selectivity of CoMo/
Al2O3. Recent results showed that the dispersion and stacking of supported NiMoS2
crystallites influence the HDS/HYDO selectivity of FCC gasoline more than other
factors, such as pore diameter or acidity (Fan et al. 2009). Li et al. (2010) found that
longer average slab length of (Co)MoS2 phases shows better HDS/OHY selectivity.
Krebs et al. (2008b) developed a kinetic model based on a Langmuir–Hinshel-
wood model with 2-methylthiophene (2-MT) and 2,3-dimetylbutyl-2-ene
(23DMB2N) competing for the same catalytic active site (Fig. 4.8). It shows that
the optimum of the selectivity volcano is shifted to the E(MS) value close to 145 kJ/
mol, higher than the optima found for HYDO activities (close to 120–125 kJ/mol,
dashed line in Fig. 4.8b). In particular, this model discovers that the CoMoS
active phase (E(MS) 143 kJ/mol) should be more selective than NiMoS
(E(MS) 128 kJ/mol).
Baubet et al. (2016) investigation of the relation of active structure of CoMoS
catalysts with HDS activity and olefin hydrogenation selectivity. They observed
that the structure of active phase was modified by the change of sulfiding condi-
tions. And the HDS/HYDO selectivity is >2 for all the CoMoS catalysts and
increases as a function of the sulfidation temperature (Table 4.2). The increasing
HDS/HYDO selectivity is mainly due to the enhancement of the TOF of HDS
reaction. And it is found that the HDS/HYDO selectivity can be influenced by the
2D shape driven by the activation-sulfidation conditions of the CoMoS catalyst.
Fig. 4.8 (a) Volcano-

curves kinetic models of
HYDO of 23DMB2N, (b)
HDS/HYDO selectivity as a
function of E
(MS) (Reproduced from
Krebs et al. 2008a)
For diesel HDS catalysts, there needs a tradeoff between HYD and DDS
functions. Although the HYD sites are preferred because of their intrinsically
high activity for desulfurizing hindered DBTs, such as 4,6-DMDBT, they are
however very vulnerable to nitrogen inhibition. On the other hand, the DDS sites,
notwithstanding their low activity for the HDS of hindered DBTs, have the advan-
tage of being more resistant to nitrogen inhibition.
As shown in Fig. 4.9, the DBT-HDS and 46DEDBT-HDS systems are nearly
orthogonal to each other because the former requires a high hydrogenolysis (HYL)
selective catalyst, while the latter requires a highly selective catalyst for hydroge-
nation of aromatics (HYA). For deep HDS, the required catalyst properties are a
sufficiently high HYA activity combined with a sufficiently high resistance to N
inhibition. Thus, an optimum industrial catalyst system should represent the best
possible compromise between the two opposing requirements, represented by the
gray area in Fig. 4.9.
Improvement of Co(Ni)Mo(W)S2 catalysts for HDS of oil streams is a compli-
cated process. Many parameters are necessary to consider (Fig. 4.10). Sufficient
formation of Co(Ni)-Mo(W)-S active phases is usually pre-required for the ultra-
deep HDS. Support properties determine the diffusion of feed and products
influencing the kinetics of reactions. And they determine the formation of type I
or II active phases. Additives modify support interaction and acid-base properties.
110
Table 4.2 HYDO and HDS rate constants (k and k0 )a and selectivity (S) of CoMoS/Al2O3 catalysts to 23DMB2N and 3-MT, as a function of the sulfidation
conditions
H2S H2S H2S H2S H2S H2S H2S H2S/H2
250 C 350 C 400 C 475 C 550 C 625 C 700 C 550 C
kHDS 1.04 1.06 0.98 2.14 2.18 1.68 0.71 1.52
kHYD 0.36 0.36 0.32 0.44 0.34 0.19 0.07 0.50
S 2.89 2.94 3.06 4.86 6.41 8.84 10.14 3.04
2D shape* nc nc
n S-edge* nc nc 0.196 0.250 0.264 0.162 0.118 0.259

n M-edge* nc nc 0.535 0.444 0.324 0.138 0.069 0.501
n edge* nc nc 0.731 0.694 0.588 0.300 0.189 0.759
k0 HDS nc nc 1.34 3.08 3.71 5.60 3.76 2.00
k0 HYD nc nc 0.44 0.63 0.58 0.63 0.37 0.66
a
Rate constant k is given in units of h–1 and rate constant k0 is given in terms of h–1 mmol–1; k0 is normalized by the number of edge sites (expressed in mmol)
H. Ge et al.
Fig. 4.9 Desired catalysts for diesel HDS lie inside the gray area that represents the optimum
compromise between two opposing requirements (Ho and Qiao 2010)
Fig. 4.10 Catalyst components and their key role to the HDS catalyst: a concept of acid-base
supported catalyst (Reproduced from Stanislaus et al. 2010)
Preparation method and preparing parameters in the large extent determined the
active structures and the final catalytic performance of HDS catalysts.
3.2 Synthesis of HDS catalysts
In the conventional impregnation method, the Mo(W)S2-based active phases are

generally yielded by sulfiding oxidic precursors which have been in advance
prepared through three steps, e.g., impregnation on an alumina support, drying,
112 H. Ge et al.
and calcination. The addition of chelating agents in the catalyst preparation is an

effective way to improve catalytic activity. Many chelating ligands such as citric
acid, nitrilotriacetic acid, glycol, 1,2-cyclohexanediamine-tetraaceticacid, ethylene
diamine tetraacetic acid, and ethylene diamine have been used in preparation of
HDS catalysts and evidenced to have a positive effect with proper contents (Lélias
et al. 2010; Rana et al. 2007; Sun et al. 2003). To avoid the decomposition of a
chelating agent, the obtained catalyst is usually free from calcination (Pashigreva
et al. 2010).
It reveals that the usage of chelating agents increases the sulfidation temperature
of promoters by the formation of thermally stabilized complexes. This facilitates
the selective location of Co or Ni atoms on the edge sites of preformed MoS2
particles to form the Co(Ni)-Mo-S structure and thus decrease the formation of
separate Co or Ni sulfide particles, part of which may block the active sites of the
catalyst.
The addition of P, B, and F change the acidity and support interaction of HDS
catalysts. Phosphorus and boron increase the support acidity, weaken the interac-
tion between Mo and Al, and enhance the Co decoration on the edge sites of MoS2
particles. They can also increase the Mo and Co dispersion so as to improve the
HDS activity (Rashidi et al. 2013). CO adsorption shows that the electron defi-
ciency of the CoMoS sites increases with boron content. The hydrodenitrogenation
(HDN) activity is strongly improved owing to the acidity enhancement. Meanwhile,
for HDS, the extent of the beneficial effect of boron is smaller and limited to the
boron addition smaller than 0.6 wt%. Increasing the support acidity enhances
mainly the catalytic performances for the hydrogenation routes (Chen et al. 2013a).
Cosmo Oil Co., Ltd. developed highly active CoMo HDS catalyst, C-606A, for
the production of ultra-low sulfur diesel fuels. The preparation method involves
impregnation of the support with a solution containing CoCO3, MoO3, citric acid,
and phosphoric acid, and air-drying without calcination. The commercial operation
has demonstrated the excellent activity and stability of C-606A under industrial
operating conditions (Fujikawa 2009).
Now alumina is still the most widely used support in preparation of HDS
catalysts. Various nano-porous alumina has been synthesized with novel preparing
methods. Wang et al. (2015b) synthesized hierarchy porous Al2O3 support by the
“pH swinging” method. Pseudo-boehmite is synthesized with the pH value swing-
ing between 10 and 2 with the alternative addition of sodium aluminate and
aluminum nitrate at 45 C. The prepared pseudo-boehmite was dried and calcined
to obtain the alumina support. The pore sizes and pore distributions can be modified
with pH swinging frequencies. CoMo catalyst using this alumina support with
tri-modal pore distribution improved the HDS of FCC gasoline.
A hard-template method using polystyrene (PS) microbeads is a prospective
technique for the preparation of hierarchical macro/mesoporous materials. The
alumina support synthesized by this approach exhibited a bimodal pore size distri-
bution of 9 nm mesopores and 250 nm macropores (Fig. 4.11). Compared with
template-free method, the PS template increased the pore volume by 2.5 times and
the specific surface area by 20%. The strong macroporous texture reduced the
Fig. 4.11 A pair of mesoporous and hierarchical macro/mesoporous alumina-supported catalysts

having distinct textural parameters have been chosen to elucidate the effect of texture on activity in
HDS and hydride metal (HDM) of heavy tar oil possessing extremely high viscosity and sulfur
content (Semeykina et al. 2016)
catalyst plugging during HDS of heavy tar. And the templated catalyst resulted in
56% higher HDS conversion that could be accounted for reducing diffusion limi-
tations and increasing the availability of active sites (Semeykina et al. 2016).
Rashidi et al. (2010) prepared nanorod-like mesoporous γ-alumina by a
surfactant-templating free sol-gel technique where aluminum isopropoxide was
used as a precursor with ethanol, 2-propanol, or 2-butanol as solvents and sulfuric
or hydrochloric acid as peptizing agents. The mesoporous alumina is a high surface
area, large size, cylindrical pore shape, and high pore volume possessing an acidic
texture and surface defects. These properties facilitate the Mo and Co dispersion
and formation of the Type II Co–Mo–S phase, thus greatly enhancing the HDS
activity.
Many other supports based on mixed oxides and zeolites have also been devel-
oped. La Parola et al. (2004) investigated CoMo catalysts supported on sol-gel
prepared SiO2-Al2O3 oxides with different Al/Si ratio. They reported that a max-
imum of activity was achieved for the mixed support in correspondence of Al/Si 2.
The different strength and polarizability of Mo-O-Al or Mo-O-Si links are
suggested responsible for the improved dispersion and reducibility of the Mo. For
the mechanically mixed support of Al2O3 and SiO2, the amount of SiO2 modifies
textural, acidity, and electronic properties of active phases. Increasing the SiO2
content in the support decreased the interaction of the Mo and Ni phases with the
support significantly influencing their dispersion. High SiO2 content produced
larger crystallites of MoS2 (Leyva et al. 2012).
Sintarako et al. (2015) investigated the effect of ZrO2 as a secondary support on
DBT HDS activity over CoMo/Al2O3 catalysts. They found that ZrO2 suppressed
the inhibition of pyridine on the HDS activity of CoMo/Al2O3-based catalyst.
CoMo/Al2O3-ZrO2 catalyst with 10 wt% of ZrO2 shown the best HDS performance
which is ascribed to the decrease of the total amount of acid sites on CoMo/Al2O3-
ZrO2.
114 H. Ge et al.
Mohanty et al. (2012) synthesized meso-structured alumina-silicate materials

from ZSM-5 nanoclusters and used as catalysts support. The alumino-silicate
materials exhibited different acid strength and textural properties depending on
the time of hydrothermal treatment of the zeolite seeds. Synthesis with short
treating time (4 h) showed properties similar to Al-SBA-15, whereas resembled
ZSM-5 with 24 h long seeding time. The EXAFS study revealed that the highest
sulfidation was achieved for the NiMo catalyst supported on mesoporous alumino-
silicate synthesized from ZSM-5 seeds with 16 h of hydrothermal treatment, which
gave higher HDS and hydrodenitrogenation (HDN) of light gas oil than NiMo/γ
Al2O3.
Wan et al. (2010) prepared NiW catalysts supported on γ-Al2O3-MB-TiO2
(denoted as AMBT) composites in which zeolite MB was synthesized from kaolin
mineral. The characterization results showed that the additions of MB and TiO2
reduced the interaction between the metal components and the composite support.
And the overall acidity of the NiW catalysts was tuned by the incorporation of MB
into the support. The high HDS activity of NiW/AMBT catalyst was attributed to
the enhanced hydrogenation activity.
Gao et al. (2015) synthesized a series of ultra-small EMT and nano-sized EMT
zeolites by a template-free system, and the micrometer-sized EMT, EMT/FAU, and
FAU zeolites using 18-crown-6 as structure directing agent. CoMo catalysts using
zeolite-incorporated alumina support exhibited high specific surface areas and pore
volumes. Among the EMT zeolites involved catalysts, the micrometer-sized
EMT-incorporated CoMo catalyst showed the highest HDS efficiency, but with
the greatest loss of octane number due to the excessive olefin saturation. The EMT/
FAU-incorporated CoMo catalysts possessed the suitable B and L acidity sites and
excellent pore structures which made a good balance among HDS,
hydroisomerization, and aromatization activities.
Heteropolyanions (HPA) have been used as precursors for preparing Mo or W
HDS catalysts. The current attention was mainly focused on Keggin (Romero-
Galarza et al. 2011) and Anderson (Palcheva et al. 2010) types HPA. These HPA
were comprising edge-sharing octahedral Mo(W)Ox surrounding a heteroatom.
Waugh-type is another HPA, in which the Ni and the Mo atoms can be included
in a single molecular entity. It features three triplets of Mo3O13 edge-sharing
molybdenum octahedra condensation surrounding a central nickel atom. Cationic
exchange of the ammonium cation in Waugh-type NiMo HPA with Ni2+ can give a
Ni/Mo ratio of 0.45, which was very close to the optimal Ni/Mo ¼ 0.5 reported for
conventionally prepared HDS catalysts (Liang et al. 2014).
Ben Tayeb et al. (2010) deposited the W and Ni in the same entity of HPA on an
amorphous silica–alumina support by incipient wetness impregnation. The best
catalytic result was obtained over the catalyst based on the Ni4SiW11O39 precursor,
which was 30% more hydrogenating. This catalyst with the high Ni/W ratio
allowed by the HPA salt stoichiometry has the better Ni promoting effect. And a
good dispersion was also obtained.
Use of the cobalt salt of the HPA [Co2Mo10O38H4]6 for the preparation of
CoMo HDS catalysts supported on Al2O3, TiO2, and ZrO2 shows that this cobalt
salt HPA leads to higher dispersion and higher promoting effect (Mazurelle et al.
2008). A close interaction between Co and Mo in the final catalyst can be achieved
by impregnating Co-Mo HPA precursors (Martin et al. 2005).
Alsalme et al. (2016) prepared NiMo/SiO2 HDS catalyst through the HPA route
using Keggin type phosphomolybdates. The pre-catalyst retains intact Keggin
structure of phosphomolybdic polyoxometalate possessing Brønsted and Lewis
acidity. During in situ sufidation, the oxidic pre-catalysts transform into an active
sulfidic phase with the loss of Keggin structure and catalyst acidity. And it shows
higher thiophene conversion and higher butene selectivity than conventional indus-
trial NiMo/Al2O3 catalyst with similar Mo loading.
North et al. (2015) fabricated bulk and supported Mo- and W-based catalysts
containing Co or Ni as promoters and phosphorus as a modifier through the PHA
route using Keggin type phosphomolybdates and phosphotungstates. Catalyst activ-
ity of thiophene HDS increases in the order of supports: SiO2 < TiO2 < γ-Al2O3.
And CoMoP/γ-Al2O3 catalyst shows higher HDS activity and butene selectivity
than the industrial catalyst of comparable composition.
Coelho et al. (2015) synthesized unsupported CoMgMoAl catalysts from
CoMgAl-terephthalate layered double hydroxides which were prepared by ion
exchange with ammonium heptamolybdate, followed by calcination at
723 K. The catalysts were sulfided in situ and subsequently tested in simultaneous
thiophene HDS and cyclohexene hydrogenation (OHYD). Both the HDS and the
OHYD activities of the catalysts increased with increasing Mg content, possibly
due to improved Co/Mo ratio. And the HDS selectivity of the most active catalysts
was higher than that of a commercial alumina-supported CoMo catalyst.
Højholt et al. (2011) developed a new approach for preparing bifunctional HDS
catalysts by ion-exchanging CoMo6 HPA onto the functionalized mesopore surface
of a ZSM-5 zeolite. The obtained bifunctional catalyst displayed a significantly
higher activity compared to the impregnated counterpart. The difference in HDS
activity is attributed to an improved dispersion of the metals throughout the zeolite
support, as illustrated in Fig. 4.12. Combining the intrinsic properties of the
zeolites, such as acidity and size-selectivity, with the possibility to anchor catalyt-
ically active metal clusters in the close vicinity of these acid sites creates the novel
type of bifunctional zeolite catalyst.
Hydrothermal synthesis using water or organic solvents can produce highly
active nano-sized Mo-based sulfide particles. Yoosuk et al. (2010) prepared
unsupported NiMo sulfide catalysts from ammonium tetrathiomolybdate and nickel
nitrate by a hydrothermal synthesis method. The activity of these catalysts in the
simultaneous HDS of DBT and 4,6-DMDBT is higher compared to that of the
commercial NiMo/Al2O3 sulfide catalysts. Meanwhile, the unsupported NiMo
sulfide catalysts showed higher activity for HYD pathway than the DDS pathway
in the HDS of both DBT and 4,6-DMDBT. Higher temperature and higher H2
pressure and addition of organic solvent increased the HDS activity. Higher prep-
aration temperature increased HYD selectivity. The optimal Ni/(Mo+Ni) ratio for
the NiMo sulfide catalyst was 0.5, higher than that for the conventional Al2O3-
116 H. Ge et al.
Fig. 4.12 Schematic illustration of the functionalization and anchoring of CoMo on hierarchical
ZSM-5 with (a) SEM image of the parent hierarchical ZSM-5, (b) and (c) TEM images of the spent
anchored catalyst, (d) TEM image of spent impregnated catalyst. The insets in a, c, and d part show
the pore size distributions (Reproduced from Højholt et al. 2011)
supported NiMo sulfide catalysts. This was attributed to the high dispersion of the
active species and more active NiMoS generated.
Lai et al. (2016a) synthesized uniform 3D NiMoS nanoflowers with self-
assembled nanosheets via a simple hydrothermal growth method using elemental
sulfur as sulfur sources. The HRTEM results indicate that the curve/short MoS2
slabs on the nanosheets possess dislocations, distortions, and discontinuity, produc-
ing more Ni-Mo-S edge sites. The NiMoS nanoflower catalysts exhibited an
excellent HDS activity for thiophene and 4,6-DMDBT. Liu et al. (2016) used a
facile one-pot evaporation-induced self-assembly method to synthesize ordered
mesoporous NiMo-Al2O3 catalysts with P123 as a structure-directing agent and
anhydrous ethanol as solvent, which presented high HDS activities of DBT. By the
hydrothermal method, Li et al. (2016) obtained a higher stacking layer number of
MoS2x, where the S/Mo atomic ratio was controlled by adjusting the concentration
of S and Mo precursors. It was observed that the catalysts with lower S/Mo ratio
show a higher HDS/HYDO selectivity of gasoline due to larger sulfide crystallites
exposed lower corner sites.
Hadj-Aissa et al. (2016) prepared Co9S8@MoS2 unsupported catalysts by a
solution reaction in ethylene glycol using cobalt sulfide seeds. The core-shell hybrid
catalysts show high activity in HDS with an exceptionally high thermal stability.
The catalytic sites takes place at the interface between the cobalt sulfide crystallites
and the stacks of MoS2 slabs. It is consistent with the NiWS system with nickel
sulfide covered with bent WS2 slabs, where the active centers are located at the
interface between nickel sulfide and WS2 slabs (Le et al. 2008).
Shan et al. (2015) reported W-based hybrid nanocrystals as a precursor to
prepare NiW/Al2O3 catalysts showing highly selective HDS performance of FCC
naphtha. Singh et al. (2016a) synthesized ultra-small NiMo oxide nanoclusters
(2 nm) by colloidal synthesis using oleic acid and oleylamine as ligands, followed
by incorporation of nanoclusters into the pores of γ-Al2O3 and calcination. Com-
pared to the catalyst using wet impregnation method, the nanoclusters prepared
sulfide catalyst showed enhanced catalytic activity for the DBT HDS. Using the
same procedure, Co-promoted MoO3 nanoclusters supported over γ-Al2O3
possessing increased Mo edge atoms presented improved HDS performance
(Singh et al. 2016b).
Scott et al. (2015) prepared NiMoS nanoparticles of 100 nm with crystallite sizes
3–5 nm by precipitation from micro emulsions. These particles show good HDS
conversion (50%) of a vacuum as oil, as well as an enhanced HDN activity
compared to the NiMo/Al2O3 catalyst.
Gonzalez-Cortes et al. (2014) synthesized γ-alumina-supported NiMoW catalyst
via the impregnation solution-based combustion method using urea as fuel for deep
hydrotreating. This preparing method avoids the formation of Al2(MoO4)3,
NiMoO4 or NiWO4, instead of that it facilitates a strong interaction of NiO with
MeOx species that could enhance the promoter effect of Ni on the edges of Mo
(and/or W) sulfide. The presence of tungsten in the NiMo catalyst selectively
enhances the HDS reaction rates through the hydrogenation pathway. This is
attributed to the type II Ni-(Mo/W)-S structures and a combination of Ni, Mo,
and W.
Recent years, ordered mesoporous materials have been extensively investigated
as the support of HDS catalysts (Garg et al. 2008). The mesoporous supports can be
coarsely classified as 2D channels, such as MCM-41, SBA-15, and HMS, and 3D
channels, such as MCM-48, SBA-16, KIT-6, and FDU-12 (Fan et al. 2009). When
the active phases are incorporated into the pores of the meso-porous support, their
structural and electronic properties will be tuned by the confining effect of the pore
size, as well as support interaction.
Zepeda et al. (2014) investigated the effect of Al and P additives in NiMo/HMS
catalysts on HDS activity of thiophene and 4,6-DMDBT. It was found that NiMo/
Al-HMS-P catalysts containing 1.0 wt% of P exhibited the best performance in both
HDS reactions as a consequence of the proper balance between the active phase
dispersion and hydrogenation ability.
Tang et al. (2013) introduced the Co and Mo into the mesopores and micropores
of mordenite nanofibers. This CoMo catalyst exhibited an unprecedented high
activity (99.1%) as well as very good catalyst stability in the HDS of
4,6-DMDBT compared with a conventional γ-alumina-supported CoMo catalyst
(61.5%). This is due to that the spillover hydrogen formed in the micropores
migrates onto nearby active CoMo sites in the mesopores.
Hao et al. (2016) used micro-mesoporous ZK-1 molecular sieves with different
Si/Al ratios as supports for preparing Co-Mo catalysts. The CoMo/ZK-1 catalysts
118 H. Ge et al.
show high surface areas (700 m2/g), large pore volumes, and hierarchical porous
structures, which promote the dispersion of Co and Mo oxide phases on the ZK-1
supports. The TPR results show that the interactions between the Co and Mo oxide
phases and the ZK-1 support are weaker than those in the CoMo/γ-Al2O3 catalyst.
Under mild reaction conditions, the DBT HDS activity of CoMo/ZK-1 was higher
than those of Co and Mo supported on ZSM-5, AlKIT-1, and γ-Al2O3.
4 Characterization of Synthesized Mo(W)S2-Based

Catalysts
Characterizations can reveal the relation of structures with the catalytic properties
and assist the development of catalysts. Okamoto et al. (2004) developed an
efficient technique to identify the maximum potential activity of HDS catalysts.
They used Co(CO)3NO as a probe molecule to coordinate on the edges of MoS2
particles forming the Co-Mo-S active phases by CVD method (Fig. 4.13). The Co
K-edge XANES results confirmed a selective formation of Co-Mo-S phase. Using
this special “characterization,” some important information can be obtained, such
as maximum potential HDS activity, the extent of blocking of the active phase, the
coverage of Co(Ni) atoms, and the dispersion of the MoS2 particles in Co(Ni)Mo
(W)S2 catalysts.
It was found that Co(CO)3NO molecules selectively adsorb on the vacant edge
sites of MoS2 particles if the contents of Ni or Co promotors are below the
Fig. 4.13 Schematic surface models of Co–MoS2/Al2O3 and CVD-Co/Co-MoS2/Al2O

(Reproduced from Okamoto et al. 2004)
saturation threshold. The tested HDS activity of CVD-Co/MoS2/Al2O3 is the

maximum potential activity of CoMoS2/Al2O3 at the situation that the edges of
MoS2 particles are fully occupied by Co atoms without any blocking by Co sulfide
clusters (Okamoto 2003). If the MoS2 edge has already been occupied by promoter
Co(Ni) atoms, the Co(CO)3NO molecules are converted to less active, separate Co
sulfide clusters, resulting in a decreased HDS activity.
Lai et al. (2016b) studied the effect of non-stoichiometric sulfur on the NiMoS
structure of NiMo/Al2O3 and unsupported NiMo catalysts. Their results indicated
the presence of reducible nonstoichiometric sulfur species (composed of S2, S22,
and S0) on the NiMoS surface and a sulfur dynamic equilibrium between the
NiMoS edge and the gas phase. The S-S bonds on the NiMoS edge can be cleaved
by hydrogen to form SH groups releasing H2S. This leads to a significant increase of
coordinatively unsaturated sites (CUS) on the NiMoS edge, beneficial for HDS
activity. It was found that nonstoichiometric sulfur over the NiMoS/Al2O3 catalyst
shows a higher H2S partial pressure sensitivity than that over the unsupported
NiMoS catalyst.
The sulfidation of supported NiW catalysts at different temperatures was shown
in Fig 4.14. Conversion of tungsten oxides to WS2 is more difficult than molybde-
num oxides to MoS2; therefore, typical sulfidation procedures result in mixed
WOxSy and WS2 phases. The former phase stabilizes Ni sulfide particles to form
NiS-WOxSy, which is the precursor of the Ni-W-S phase. M€ossbauer spectroscopy
demonstrated that the NiS particles redisperse over the WS2 edges when partly
oxidic tungsten phases transform to WS2. Owing to very slow W sulfidation, the Ni
promoters end up in two phases, i.e., Ni-W-S and NiS–WOxSy phases, this in
contrast to Co(Ni)Mo catalysts that mainly contain Co(Ni)–Mo–S phases after
sulfidation. The NiS–WOxSy phase is deemed to perform well in liquid-phase
HDS reactions whereas the Ni-W-S phase is most active for gas-phase HDS. The
relative speciation of these two phases for alumina-supported NiW can be con-
trolled by parameters as the calcination temperature and the sulfidation temperature
and pressure. Chelating agents improve the edge occupation in NiW catalysts
significantly by retarding Ni sulfidation. This is a more efficient formation of the
Ni-W-S phase.
van Haande et al. (2015) studied morphology and structures of Ni-promoted
mixed MoxW(1x)S2/Al2O3 catalysts under different sulfidation and reaction con-
ditions, as shown in Fig. 4.15. XPS and EXAFS showed that the slower sulfidation
kinetics of W in activation process lead to the two-dimensional core-shell structure
of NiMoxW(1x) sulfides with Mo located in the core and W in the shell. Increasing
the H2S/H2 pressure during sulfidation distributed Mo and W more homogeneously,
which was attributed to the favorable sulfidation of W under these conditions. And
support interactions in the oxidic precursor plays a key role in the formation of these
structures. Catalytic testing demonstrated that a core-shell structure is more active
for thiophene HDS, whereas homogeneously mixed MoxW(1x)S2 phase catalyzes
the HDS of DBT.
120 H. Ge et al.
Fig. 4.14 W and Ni EXAFS k3-weighted FT functions of NiW/Al2O3 after sulfidation at indicated
temperatures, showing that W sulfidation starts at 573 K. Intervals I and II indicate the W–W
contributions of WO3 and WS3, respectively. Ni is already completely sulfided at 573 K (Adapted
from Hensen et al. 2007)
Nikulshin et al. (2014) investigated the effect of carbon on active phase mor-
phology. Carbon varies the ratio of stacking number/linear size of active phase
particles. As a result, the HYD/DDS selectivity of DBT is changed (Fig. 4.16). And
the hydrogen uptake by the C-coated support could be a source of hydrogen for
HDS reactions.
Fig. 4.15 Possible structures of the active phase in Ni-promoted MoxW(1x) catalysts (x 1) at
different HDS environment. For the sake of clarity, Ni has been omitted from the drawings
(Adapted from van Haande 2015)
5 Application of Mo(W)S2-Based Catalysts for Deep

Desulfurization
The synergy coordination of process technology with catalyst property is of critical

importance for the industrial application of HDS catalysts. To tradeoff between
ultra-deep HDS and octane containing in clean gasoline production, a two-stage
fluid catalytic cracking (FCC) gasoline hydro-upgrading process is proposed with
the selective HDS catalyst in the first reactor and the complemental HDS and octane
recovery catalyst in the second reactor (Fig. 4.17). The full-range FCC gasoline is
firstly separated into light and heavy cracked naphtha fractions (LCN and HCN)
through distillation at 60 C. LCN contains thiols as major sulfur-containing and
most of the olefins with high-octane, and HCN contains mainly refractory sulfur-
containing compounds (such as thiophenes, alkylthiophenes, and benzothiophenes)
and low concentration of olefins. The LCN is treated with a 10% NaOH solution to
remove the predominant C2 and C3 thiols. And the HCN is selectively desulfurized
over a K and P modified Co-Mo/Al2O3 catalyst, followed by octane recovery over a
Ni-Mo/HZSM-5 catalyst achieving hydroisomerization and aromatization of resid-
ual olefins as well as the compensating HDS. Finally, the hydro-upgraded HCN and
caustic-treated LCN is blended again to obtain high-quality gasoline. The process
endowed superior octane recovery ability while remarkably reducing the olefin
content of FCC gasoline.
Control of the coordination patterns and the ratio of promoters/Mo(W), to a large
extent, dominates the final performance of HDS catalysts, Zuo et al. (2004) studied
the influence of Ni promoter amounts on thiophene HDS reaction of NiW catalysts.
Compared with no-promoting catalysts they observed about 30 times drastic
increase of activity for the catalyst with optimized Ni contents. It mainly correlates
to the concentration of Ni-W-S phase. Meanwhile, the Ni promoters lead to a slight
increase of stacking and length of WS2 crystallites, as well as sulfidation of WOx
precursors.
Figure 4.18 shows the effect on additional amount of Ni promoters on the HDS
of different sulfur compounds over the NiMoS2/γ-Al2O3 catalysts. It can be seen
122 H. Ge et al.
Fig. 4.16 3D dependences of TOF number (a) and HYD/DDS selectivity (b) in DBT HDS on
average length and average stacking number of Co(Ni)MoS2 particles in the catalysts (Reproduced
from Nikulshin et al. 2014)
Fig. 4.17 Schematic diagram of the two-stage process for upgrade of FCC gasoline (Reproduced
from Fan et al. 2013)
that the rate constant shows a volcano type with a maximum at Ni/(Ni + Mo) 0.33
where the NiMo catalyst is about 20 times higher active for DBT HDS than the Mo
one. The rate constants of 4-methyldibenzothiophene (4-MDBT) and 4,6-DMDBT
are dropped by roughly a factor of 2–3 and 4–6, respectively, owing to the steric
hindering effect of substituents. Meanwhile, the DDS pathway of HDS of all three
DBT derivatives is significantly enhanced by the addition of Ni, as shown in
Fig. 4.18 (b), which is attributed to the formation of Ni-Mo-S phase.
Yin et al. (2016) studied the deep HDS of FCC and coking gas oils over highly
loaded NiMoW catalysts compared with a commercial NiMo/γ-Al2O3 catalyst and
a highly loaded NiMo catalyst. The observed that the FCC gas oil was relatively
easier to process than coking gas oil. 4-MDBT had been totally removed when the
coking gas oil was desulfurized to a level of 50 μg/g S. And only 4,6-DMDBT and
2,4,6-trimethyldibenzothiophene were detected in the deep HDS to a level less than
10 μg/g S. The highly loaded NiMoW catalyst had a higher activity than highly
loaded NiMo and commercial NiMo/γ-Al2O3 catalyst, more suitable for the pro-
duction of ultra-low-sulfur gas oils.
Peng et al. (2016) evaluated the deep desulfurization efficiency of stacking
schemes for processing diesel feeds (Fig. 4.19). Results showed that the
W-Mo-Ni/Mo-Co catalyst stacking is the most effective because of the following
two reasons: (1) loading W-Mo-Ni catalyst on the upper bed of reactor not only
facilitates the saturation of polyaromatics even but also provides low nitrogen feed
for the bottom bed; (2) loading Mo-Co catalyst with alkyl transfer performance in
the bottom bed favors the alkyl transfer reaction at high temperature, consequently
improving the HDS efficiency.
124 H. Ge et al.
Fig. 4.18 Catalytic activities (a) and DDS selectivities (b) for HDS of DBTs over
Ni-MoS2/γ-Al2O3 catalysts. Reaction conditions: 2000 ppm sulfur, 3 MPa, 310 C,
LHSV ¼ 300–3600 h1, H2 flow rate ¼ 200 cm3 min1 (Reproduced from Gao et al. 2011)
Fig. 4.19 Schematic deep HDS process in two-stage stacking bed (Reproduced from Peng et al.
2016)
To be confronted with the inhibition of nitrogen containing a compound to HDS,

ExxonMobil Research and Engineering Co. developed a catalyst-zoning strategy
that plays the strength of two catalysts with very different selectivity (Ho and Qiao
2010). For example, to treat light catalytic cycle oil (LCO), one catalyst used is a
bulky Ni0.5Mn0.5Mo sulfide that has a very high HYA selectivity (Ho 2004). The
other is sulfided CoMo/Al2O3 catalyst, which is HYL selective. The HDS activity
of the bulky catalyst is more sensitive to N inhibition than that of the supported
CoMo catalyst. A profitable way of using these two catalysts is to place
Ni0.5Mn0.5Mo sulfide downstream of CoMo/Al2O3 in a stacked-bed reactor. Even
a modest HDN by CoMo/Al2O3 catalyst can significantly dampen the N inhibition
impacts on the downstream bulky catalyst. And the bulk catalyst is relatively
insensitive to the H2S generated from the CoMo/Al2O3 catalyst. It noted that the
50/50 stacked bed outperforms a uniform mixed bed. This is because an effective
ultra-deep HDS process requires a delicate balance between the hydrogenation
function and tolerance of organonitrogen inhibition among catalysts. Cobalt as a
promoter plays an important role in helping MoS2-based catalysts combating
organonitrogen inhibition.
A potential valorization of pyrolysis oils from lignocellulosic biomass is their
co-hydrotreatment with petroleum cuts to produce transportation fuels (Pinheiro
et al. 2009). Bui et al. (2009) investigated the impact of co-processing guaiacol, a
representative oxygenated molecule of pyrolitic bio oils, with a straight run gas oil
in an HDS process over the CoMo/Al2O3 catalyst. A decrease of HDS performance
was observed at low temperature and high contact time. It was assigned to the
formation of intermediate phenols competing with sulfur containing molecules for
adsorbing on hydrogenation/hydrogenolysis sites. However, complete
hydrodeoxygenation (HDO) of guaiacol was observed above 320 C and HDS
could proceed without any further inhibition.
Co-hydroprocessing of fossil fractions with lipids is an alternative pathway for
integrating biomass in the transportation sector (Mercader et al. 2011). Bezergianni
et al. (2014) evaluated CoMo/Al2O3 and NiMo/Al2O3 catalysts for
hydroconversion of heavy atmospheric gas oil (HAGO) and waste cooking oil
(WCO) mixtures. The results showed that the HDS efficiency depends primarily
upon the reaction temperature and HAGO to WCO ratio. The HDS of NiMo
catalyst is not affected by WCO, even in the 330 C low temperature. However,
the addition of WCO leads to strong deactivation of the CoMo catalyst. It was
evident that NiMo type catalysts are more suitable for co-hydroprocessing of
petroleum fractions with lipid-containing feedstocks.
Chen et al. (2013b) study the co-hydroprocessing of canola oil–heavy vacuum
gas oil (HVGO) with different blending ratios under typical hydrotreating condi-
tions over a commercial NiMo/Al2O3 catalyst. It was found that the HVGO–canola
oil blend feeds had a higher conversion to the light product than the pure HVGO
feed at similar operating conditions. However, the HDS and HDN were not affected
by the addition of canola oil. Under similar conversion or light product yield,
co-processing of HVGO–canola oil blends required lower temperature and/or
pressure than the pure HVGO hydroprocessing, an implication of potential energy
saving. It was also found that at the same conversion, the HVGO–canola oil blends
generated more diesel but less gasoline than pure HVGO, an effective way to meet
the fast increasing diesel demand. Vonortas et al. (2014) studied the effect of the
refined and acidic vegetable oil content (0–30 wt%) on the co-hydroprocessing of
their mixtures with gas oil over a NiMo/Al2O3 catalyst. It was found that 49–55% of
the ester bonds are removed by the decarboxylation/decarbonylation pathway for
both the refined and acidic vegetable oil. And the influence of the vegetable oil
concentration on gas oil HDS of NiMo catalyst was negligible.
126 H. Ge et al.
6 Conclusion
The advanced characterization techniques and DFT calculations have provided a

fundamental understanding of surface reactions and highlighted the role of struc-
tures such as edge, corners, or single atom defects/vacancies as potential active sites
in HDS catalysis. In particular, the atomic-scale insight into the Co-Mo-S active
sites and “brim” edge has led to developing the better industrial HDS catalysts.
To supported CoMo, NiMo, and NiW catalysts, improvement can be achieved
by increasing loading level of active metal (Mo, W, etc.); by adding one more
transient metal (e.g., Ni to CoMo or Co to NiMo); and by incorporating a noble
metal (Pt, Pd, Ru, etc.), but these methods may lead to the increase of cost and
become unacceptable from economic perspective. Thus, enhancement of atomic
efficiency of metals is more favored, such as the formation of as many as active
centers with a limited amount of metals, control of active structures granting higher
catalytic activity and synergy of different catalytic functions.
Apart from deep desulfurization, other catalytic properties are also important.
Catalysts used for gasoline fraction HDS should suppress the hydrogenation to
olefins avoiding the octane loss. But catalysts for diesel oil streams needs to have
enough hydrogenation ability so as to achieve the desulfurization of refractory
sulfur-containing compounds by HYD route and saturation of aromatics improving
the cetane number. For the HDS of heavy fuels, a bi- or multi-functional catalyst is
necessary to balance the hydrogenation of metal sites with cracking of acidic sites
on support. Thus, the HDS catalysts require the fitful compromise among catalytic
properties for specific type fuels.
Design and fabrication of HDS catalysts based on the rich understandings of
active structures, the reaction mechanism, and kinetics as well as reaction engi-
neering have become a trend with the fast advances in fundamental research and
industrial application. To satisfy the demand of petroleum industry, it is also
important to improve the synergism between HDS catalysts and the processes.
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Chapter 5
Selective Sulfur Removal from Liquid Fuels
Using Nanostructured Adsorbents
Diana Iruretagoyena and Raul Montesano
Abstract In recent years, there has been an increasing pressure to develop strate-
gies to reduce the level of sulfur in transportation fuels due to stringent environ-
mental regulations. Currently, hydrodesulfurization (HDS) is the most mature (pre-
FCC) technology to remove sulfur from gasoline and diesel. However, conven-
tional HDS can hardly produce ultra-low sulfur fuels while maintaining important
fuel requirements (i.e., oxygen content, overall aromatic content, olefin content for
gasoline, and cetane number for diesel). As a consequence, improvement of
existing HDS processes and development of new desulfurization technologies is
needed. In this regard, selective adsorption removal of sulfur (SARS) is a promising
emerging approach for ultra-deep desulfurization of refinery streams by means of
solid adsorbents. Contrary to HDS, SARS is usually carried out at low temperatures
and pressures with minimal hydrogen consumption, preventing olefin hydrogena-
tion and thus maintaining the properties of the fuels. This chapter presents a general
overview of SARS. Emphasis is given to the use of nanostructured materials as
sulfur adsorbents. Section 5.1 introduces the chapter presenting a general descrip-
tion of HDS, SARS and other emerging desulfurization technologies. Section 5.2
describes the two main groups of SARS (adsorption desulfurization and reactive
adsorption desulfurization). Subsequently, the three main mechanisms for sulfur
adsorption (π-complexation, direct sulfur–adsorption site interactions, and bulk
incorporation in reactive adsorption desulfurization) are reviewed. Section 5.3
gives an overview of relevant literature concerning the use of promising groups
of nanostructured adsorbents for SARS including zeolites, MOFs, mesoporous
silicas, and carbon-nanostructured adsorbents. Finally, Sect. 5.4 gives some con-
cluding remarks.
D. Iruretagoyena (*)
Department of Chemical Engineering, Imperial College London, South Kensington Campus,
London SW7 2AZ, UK
R. Montesano
Department of Chemical Engineering, Imperial College London, South Kensington Campus,
London SW7 2AZ, UK
Haldor Topsoe A/S, Haldor Topsoe Allé 1, 2800 Kongens Lyngby, Denmark

134 D. Iruretagoyena and R. Montesano
Keywords Nanostructured-adsorbents • Sulfur removal from liquid fuels • SARS •

Zeolites • MOFs • Mesoporous silicas • Carbon-nanostructured adsorbents
1 Introduction
In recent years, there has been an increasing pressure to develop strategies to reduce
the level of sulfur in transportation fuels due to stringent environmental regulations.
The European Parliament has set a limit of 10 ppm of sulfur in gasoline and diesel
since 2009 while the Environmental Protection Agency (EPA) has adopted the
same limit in the Clean Air Act (Tier 3) effective from January 2017. In most
refineries, gasoline and diesel are formed by blending the corresponding straight-
run distillates with additional naphtha and diesel coming from cracking processes
(fluid catalytic cracking FCC, hydrocracking and thermal cracking of the vacuum
residue). The product from the cracking units contributes with ca. 48% of the
gasoline and 39% of the diesel pools, but amounts to 97% and 63% of the sulfur
content, respectively. Evidently, treatment of cracking streams is essential to meet
the low sulfur limits in current regulations and therefore emphasis has been given to
pre- and post-FCC desulfurization in recent years.
Hydrodesulfurization (HDS) is the most mature (pre-FCC) technology to
remove sulfur from gasoline and diesel. In this process, hydrogen reacts with the
organosulfur compounds to produce sulfur-free hydrocarbons and
H2S. Conventional HDS is carried out at high temperatures (300–400 C) and
hydrogen partial pressures over sulfided CoMo/Al2O3 and NiMo/Al2O3 catalysts.
The reactivity of the sulfur-containing compounds depends on the steric hindrance
and the electron density of the sulfur atom and decreases in the following order:
mercaptans, sulfides, disulfides, thiophenes, and benzothiophenes (and their
alkylated derivatives), and polynuclear sulfur compounds. It is possible to meet
the ultra-low sulfur levels imposed on gasoline by current regulations under severe
HDS conditions and using improved catalyst formulations (Topsøe et al. 1999;
Gutierrez et al. 2015) but higher temperatures lead to an increased catalyst deacti-
vation by coke deposition while higher H2 partial pressures enhance the undesired
hydrogenation of unsaturated hydrocarbons, lowering the octane number. The
gasoline can be upgraded in a subsequent stage (isomerization + alkylation) but
to the detriment of the process economics. In the case of diesel, the competitive
adsorption between sterically hindered sulfur compounds and polyaromatics
decreases the desulfurization rate at low sulfur contents, and therefore, extremely
large catalyst volumes are required for deep HDS.
From the discussion above it is evident that conventional HDS can hardly
produce ultra-low sulfur fuels while maintaining important fuel requirements
(i.e., oxygen content, overall aromatic content, olefin content for gasoline, and
cetane number for diesel). As a consequence, improvement of existing HDS
processes and development of new desulfurization technologies is needed. Prom-
ising approaches for industry have been reviewed by Babich and Moulijn (2003)
5 Selective Sulfur Removal from Liquid Fuels Using Nanostructured Adsorbents 135
and Song (2003) and include HDS with fuel specification recovery (Javadli and de
Klerk 2012) and catalytic distillation (Ju et al. 2015), shifting the boiling point by
alkylation (Arias et al. 2008), desulfurization via extraction (Farzin and Miran
2015), selective oxidation (Seeberger and Jess 2010), and selective adsorptive
desulfurization (Menzel et al. 2016). This chapter presents a general overview of
selective adsorption for removal of sulfur compounds (SARS). Emphasis is given to
the use of nanostructured materials as sulfur adsorbents. Section 5.2 describes the
two main groups of SARS (adsorption desulfurization and reactive adsorption
desulfurization). Subsequently, the three main mechanisms for sulfur adsorption
(π-complexation, direct sulfur–adsorption site interactions, and bulk incorporation
in reactive adsorption desulfurization) are reviewed. Section 5.3 gives an overview
of relevant literature concerning the use of promising groups of nanostructured
adsorbents for SARS including zeolites, MOFs, mesoporous silicas, and carbon-
nanostructured adsorbents. Finally, Sect. 5.4 gives some concluding remarks.
2 Selective Adsorption Removal of Sulfur Compounds
Selective adsorption removal of sulfur (SARS) is an emerging approach for ultra-

deep desulfurization of refinery streams by means of solid adsorbents. SARS is
most often regarded as a complementary step to conventional HDS for FCC
naphtha and diesel, or as a final treatment to the blended pools. Contrary to ultra-
deep HDS, SARS is usually carried out at low temperatures and pressures with
minimal hydrogen consumption, preventing olefin hydrogenation and thus
maintaining the properties of the fuels (e.g., octane and cetane numbers). In
addition, the milder operating conditions of SARS potentially decrease the cost of
the process, particularly considering the lower H2 consumption, which is one of the
most expensive items in ultra-deep HDS. Selective adsorption removal is conceived
as a cost-effective strategy to reach ultra-clean fuel levels, removing the less
reactive species that remain after conventional HDS. The main challenge of
SARS is to find suitable solid adsorbents for the process, with high adsorption
capacity, fast kinetics, adequate stability and renewability, and high selectivity for
organosulfur compounds in the presence of competing species such as olefins and
aromatics. SARS can be classified into two groups depending on the type of
interaction between the organosulfur compound and the adsorbent: adsorption
desulfurization and reactive adsorption desulfurization.
2.1 Adsorption Desulfurization
Adsorption desulfurization involves a weak interaction between the organosulfur

molecules and the adsorbent (parallel adsorption via π-electrons of the aromatic
rings) at low temperature (below 300 C), low pressure (near atmospheric), and in
Fig. 5.1 Schematic representation of (a) IRVAD (adapted from Irvine 1998), (b) PSU-SARS
processes (adapted from Velu et al. 2005)
the absence of hydrogen. The low heats of adsorption involved allow the adsorbed
molecules to be easily desorbed by moderate changes in the process conditions, for
instance, flushing the spent adsorbent, increasing temperature or decreasing pressure.
In adsorptive desulfurization processes, the sulfur molecules are recovered during
regeneration in a concentrated stream which can be treated easily downstream.
Research in adsorptive desulfurization has focused on the use of pure and modified
activated carbons (Thaligari et al. 2016), CoMo-catalysts (Kim et al. 2016), alumina
(Ullah et al. 2016), silica (Rodrigues et al. 2014), and zeolites (Lee and Valla 2017).
Two main processes have been developed but have not been implemented in the
industry yet. The IRVAD process consists of a moving bed of alumina-based adsor-
bent which is counter-currently brought into contact with FCC and coker naphta,
Fig. 5.1a (Irvine 1998). The process operates at 240 C and pilot tests have shown
90% reduction in the sulfur content. The spent adsorbent is regenerated at a slightly
higher temperature and recirculated back to the adsorber. The alumina composition is
optimized to improve hydrocarbon recovery during desorption. The PSU-SARS
process operates between ambient temperature and 250 C using an undisclosed
adsorbent, most likely a transition metal complex supported on a zeolite, Fig. 5.1b
(Velu et al. 2005). Experiments in laboratory scale showed that less than 20 ppmw
remained in gasoline, jet fuel, and diesel treated with the developed adsorbents.
2.2 Reactive Adsorption Desulfurization
In reactive adsorption desulfurization, the sulfur atom from the organosulfur com-
pound interacts strongly with the adsorption sites, remaining bounded to the
surface. The organic molecule is hydrogenated and desorbed to the fuel stream
without further structural changes. A schematic representation of this desulfuriza-
tion process is given in Fig. 5.2. The operating conditions for reactive adsorption
Fig. 5.2 Schematic representation of reactive adsorption desulfurization of thiophene using

Ni/ZnO (adapted from Babich and Moulijn 2003)
are more severe than for nonreactive adsorption desulfurization, requiring the
presence of H2 at temperatures between 300 and 400 C and pressures between
2 and 20 bar. However, less hydrogen (and with lower purity) is required compared
to ultra-deep HDS and the fact that sulfur is captured by the adsorbent prevents
possible recombinations between H2S and the hydrocarbons in the stream. During
regeneration, sulfur is recovered as H2S, S or SO2, depending on the procedure
applied.
Most of the research regarding reactive desulfurization has dealt with metallic
particles (mainly Ni) dispersed on metal oxides (ZnO, Al2O3, SiO2) (Tawara et al.
2001; Park et al. 2008). ConocoPhillips developed a process called S-Zorb SRT
which consists in a fluidized bed of adsorbent operating between 340–410 C and
2–20 bar, requiring hydrogen purity above 50% (Song 2003; Babich and Moulijn
2003). The adsorbent is undisclosed but is known to be based on reduced metals and
metal oxides that are sulfided during operation (most likely Ni/ZnO + SiO2 + Al2O3).
This technology can remove sulfur to levels below 10 ppmw from naphtha and
diesel in a single step. Regeneration is carried out in a separate vessel. The process
was implemented in Borger Refinery in Texas in 2001 and a second unit came
online in Ferndale, Washington in 2003. The technology was bought by Sinopec
in 2007.
2.3 Mechanisms of Sulfur Adsorption
2.3.1 π-Complexation
Donor–acceptor complexes are known to form between the π-electron system of

aromatic rings (i.e., benzene and thiophene) and adsorption sites with electron–
donor character. Here, the aromatic ring adsorbs parallel to the solid surface,
preventing any steric hindrance from alkyl groups (Hernandez-Maldonado et al.
2005). Common examples of adsorbents that form π-complexes are alumina (Irvine
1998) and activated carbon (Salem 1994). The electron density of the aromatic
species is influenced by the nature of the substituent groups and therefore differ-
ences in electron affinity exist between organosulfur molecules and sulfur-free
aromatics. However, low selectivities for sulfur removal are often observed due
Fig. 5.3 Interaction

between
methylbenzothiophene on
PdCl2/carbon (adapted from
Wang and Yang 2007)
to the low concentration of the organosulfur compounds and to the abundance of

sulfur-free aromatics that remain in the fuels after conventional HDS (Salem 1994).
The selectivity of π-complexation increases by the incorporation of dispersed
metal ions on the adsorbents. The empty s-orbitals of transition metal cations can
form π bonds with a lone electron pair of sulfur while their d-orbitals can back-
donate electron density to the antibonding π-orbitals of the thiophene rings
(Hernandez-Maldonado et al. 2005). This results in a stronger adsorption of sulfur
molecules and hence higher selectivity and capacity. An increased selectivity
towards thiophenic molecules for Cu+ exchanged zeolites was predicted by molec-
ular orbital calculations and corroborated experimentally (Takahashi et al. 2002).
PdCl2 supported on activated carbon showed the high capacity to remove
benzothiophene from model jet fuel. A synergetic effect was proposed between
the carbon support and the Pd2+ ions where the thiophene ring interacts with the
metal through π-complexation while the benzene ring adsorbs strongly on the
carbon support, Fig. 5.3 (Wang and Yang 2007).
2.3.2 Direct Sulfur–Adsorption Site Interactions
The relatively high selectivity of some solid adsorbents towards trace organosulfur
compounds in fuels after HDS cannot be explained solely by the π-complexation
mechanism. Considering the eight possible configurations of thiophene in organo-
metallic complexes (Sanchez-Delgado 1994), Song and coworkers (Velu et al.
2005) pointed out that while six of them involve interactions with the π-electrons
of aromatic rings (and therefore are not selective for thiophene over benzene
cycles), the η1S and S-μ3 configurations are formed via direct sulfur–metal inter-
actions, see Fig. 5.4. The authors showed by molecular orbital calculations that the
highest occupied molecular orbital (HOMO) of thiophene (TP), benzothiophene
(BT), and dibenzothiophene (DBT) is localized more on the sulfur atom, whereas
the HOMO of alkylbenzenes and naphthalene is localized more on the conjugated
ring (Ma et al. 2002). Consequently, preferential adsorption is likely to take place
through the interaction of the HOMO on sulfur and the lowest unoccupied molec-
ular orbital (LUMO) on surface (metal) species. Suitable selective adsorption
centers are Lewis acid sites, functional groups with electron donor properties, and
surfaces with electronic defects.
η1S S-μ3 η4 η5
S
M
S S
S M
M M
M
M M M
S S
S S
M M M M
η4S - μ2 η4S - μ3 η2 η1C
Fig. 5.4 Possible adsorption configurations of thiophene in organometallic complexes (adapted

from Ma et al. 2002)
2.3.3 Bulk Incorporation in Reactive Adsorption Desulfurization
The reactivity of organosulfur compounds during reactive adsorption desulfuriza-

tion has been reported to be higher for substituted thiophenes and benzothiophenes
than for thiophene (Babich and Moulijn 2003), indicating that the reaction mech-
anism (i.e., coplanar adsorption, see above) is different from HDS reactions
(Hernandez-Maldonado et al. 2005). In the presence of organosulfur compounds,
there is a thermodynamic drive for some supported and bulk metal oxides (e.g.,
CuO, ZnO, MoO3, NiO, Al2O3, MnO, and Co3O4) to incorporate sulfur in the form
of metal sulfides, resulting in high theoretical capacities (Babich and Moulijn
2003). In practice, high sulfur uptakes have only been observed when metals are
dispersed on the metal oxides (Tawara et al. 2001). A synergetic mechanism for
reactive sulfur adsorption on Ni/MexOy has been tentatively proposed where
hydrogenolysis of the organosulfur compound is catalyzed by the Ni sites, and
the produced H2S is rapidly re-adsorbed on ZnO which is then sulfided to ZnS,
Fig. 5.5.
3 Nanostructured Adsorbents for Selective Adsorption

Removal of Sulfur Compounds
As mentioned above, the main challenge of SARS is to find suitable solid adsor-
bents for the process, with high sulfur capacity at low temperatures and pressures,
fast adsorption–desorption kinetics, adequate renewability and with high selectivity
to adsorb sulfur in the presence of competing species such as aromatics, olefins, and
Fig. 5.5 Schematic

representation of
hydrogenolysis of
thiophene using Ni/ZnO
(adapted from Babich and
Moulijn 2003)
cyclic paraffinic hydrocarbons. In response to these demanding requirements, a

range of potential sulfur adsorbents have been investigated including activated
carbons, ionic liquids, supported metals, metal oxides, zeolites, and metal organic
frameworks (MOFs). The desulfurization performance of each group of materials
depends mainly on their chemical composition, the specific structure, and physico-
chemical properties. In this context, the use of nanostructured adsorbents for SARS
is particularly attractive since their high surface area and porosity improves the
diffusion of sulfur compounds to the actives sites of the solid, facilitating parallel
adsorption via π-electrons of the aromatic rings. In addition, it is possible to tune
their adsorption properties by functionalization and by deliberate creation of defects
during their synthesis. This section provides an overview of relevant literature
concerning the use of promising nanostructured adsorbents for SARS including
zeolites (Sect. 5.3.1), MOFs (Sect. 5.3.2), mesoporous silicas, and carbon-
nanostructured adsorbents such as carbon nanotubes and graphene-like materials
(Sect. 5.3.3).
3.1 Zeolites
Zeolites are crystalline aluminosilicates formed by a network of tetrahedral SiO4

and AlO4 linked by shared oxygen atoms. The substitution of Si4+ by Al3+ in the
ionic structure generates higher electron density on the bridging O atoms, which
needs to be balanced by the addition of a positive ion, typically H+ (Brønsted sites)
or metal cations (Lewis sites). A remarkable characteristic of zeolites is the
occurrence of a well-defined nano-pore structure that turns them into effective
molecular sieves of the very large surface area. Their large surface area, their
sieving properties, and the possibility to tailor the Brønsted and Lewis character
by tuning their composition render zeolites very interesting materials for adsorption
applications.
Most of the research concerning the use of zeolites for SARS has focused on
investigating the adsorption performance of Y zeolite. Besides showing strong
acidity and an excellent hydrothermal stability, Y zeolite is attractive because its
cage-like cavities (~13 Å) interconnected by a wide 3D pore system (diameter
7.4 Å) (Kunhao et al. 2015) are able to accommodate large molecules such as
alkylated dibenzothiophene, Fig. 5.6. Many studies have dealt with the removal of
sulfur from model diesel, gasoline, and jet fuels comprising a variety of
organosulfur compounds such as thiophene, benzothiophene, dibenzothiophene,
Fig. 5.6 Schematic representation of Y zeolite (adapted from Weitkamp 2000)
and 4,6-dymethildibenzothiophene (~1–800 ppmw S). Typically, the experiments

have been carried out at low adsorption temperatures (20–150 C) and pressures
(1–2 bar). Depending on the operating conditions, the synthesis method and
the pretreatment, the adsorption capacity of Y zeolites ranges from ~0.1 to
15 mgS gads 1.
Many studies have shown that Y zeolites exchanged with transition metal ions
(Cu+, Ni+, Zn2+, Pd2+, and Ag+) exhibit higher capacities and selectivities to adsorb
sulfur compared to NH4Y and NaY zeolites, mainly due to the formation of stronger
π-complexation bonds between the organosulfur compounds and the transition
metals. Yang et al. (2001) synthesized Cu+Y and Ag+Y zeolites for the removal
of thiophene in the presence of benzene and found higher sulfur capacities and
selectivities compared to activated carbon, modified alumina, and other zeolite
structures. The desulfurization performance decreased in the order Cu+Y Ag+
Y > Na-ZSM-5 > activated carbon > NaY > modified alumina H-USY. In a
subsequent study, Yang et al. (Hernandez-Maldonado et al. 2005) synthesized a
monolayer CuCl/γ-Al2O3 adsorbent and studied its performance in the desulfuri-
zation of commercial diesel and jet fuels containing 140 and 365 ppmw S, respec-
tively. Although CuCl/γ-Al2O3 showed a lower capacity than Cu+Y, it was more
stable. Cu+Y is easily oxidized to Cu2+Y by oxygenates and moisture in the fuel,
losing its π-complexation ability. Xue et al. (2005) studied the removal of thiophene
and benzothiopene from model gasoline containing toluene and heptane and ranked
the desulfurization performance as Ce4+Y > Ag+Y > Cu+Y > Na+Y. Bhandari
et al. (2006) reported that Ni+Y and Cu+Y zeolites have higher adsorption capac-
ities for benzothiophene and 4,6-dimethyldibenzothiophene (DMDBT) than Y
zeolites containing Fe2+, Zn2+, and Na+ with the trend: Ni2+Y > Cu+Y > Fe2+
Y > Zn2+Y > Na+Y. In a more recent work, Zhang et al. (2008) assessed the
removal of dibenzothiophene and 4,6-dimethyldibenzothiophene using various Na+
Y exchanged zeolites and found that the adsorption capacities decreased in the
order: AgY CuZnY > ZnNdY > ZnY > CuY > NiNdY NaY.
There are some discrepancies in the ranking of the desulfurization performance
obtained for the same Y zeolites in the works mentioned above. This suggests that
the capacities and selectivities of the materials do not depend exclusively on their
chemical composition but can be influenced by other factors such as the type of
sulfur species, the method used to synthesize the zeolite and the experimental
adsorption methods. In general, it has been found that Ce-exchanged Y zeolites
show high capacities and selectivities for organosulfur compounds over aromatics
since adsorption occurs mainly via direct sulfur–metal (S–M) interactions rather
than via π-complexation (Velu et al. 2005; Song et al. 2014a). Hernandez-
Maldonado et al. (2005) and Dastanian and Seyedeyn-Azad (2010) reported that
vapor phase (VPIE) and solid-state (SSIE) ion exchange techniques lead to more
efficient adsorbents compared to the conventional liquid phase ion exchange
method (LPIE). The authors found that VPIE and SSIE minimize cation hydrolysis
effects, avoiding unwanted species into the zeolite framework that result in low
sulfur uptakes. Dastanian and Seyedeyn-Azad (2010) and Bakhtiari et al. (2016)
showed that the stirring time, calcination temperature, and aging period used during
the synthesis of Y zeolites play important roles in the final sulfur adsorption
properties. The variations in the capacities and selectivities reported by different
authors can also be attributed to the specific adsorption methodology used. Tradi-
tionally, batch (Song et al. 2014b), fixed-bed (breakthrough-type) (Velu et al. 2005;
Hernandez-Maldonado et al. 2005; Bhandari et al. 2006), and flow calorimetry
(Ng et al. 2005) tests have been used to investigate the sulfur adsorption properties
of Y-zeolites.
Zeolites Y exhibit higher selectivities for substituted thiophenes and
benzothiophenes than for thiophene in the following order 4,6-DMDBT > 4-M-
DBT > DBT > BT > TP, indicating that selectivity increases with the π-electron
density of the aromatic rings (Hernandez-Maldonado et al. 2005; Song et al.
2014a). Some authors have studied the competitive adsorption of organosulfur
compounds in the presence of nitrogen heterocycles, aromatics, and olefins (Song
et al. 2014a; Han et al. 2016; Ng et al. 2005). FT-IR studies on Ag+Y, Ce4+Y, and
Ag+Ce4+Y carried out by Song et al. (2014a) demonstrated that nitrogen-containing
organics such as pyridine adsorb more preferentially than organosulfur compounds
due to stronger interactions with the acid sites of the zeolite. In addition, pyridine
occludes the pores of the zeolites reducing the space available for adsorption of
thiophenic molecules. The authors reported that the uptake of organosulfur com-
pounds by Ag+Y zeolites decreases in the presence of aromatics and olefins since
they also form π-complexes, leading to competitive adsorption. They found that the
decrease in sulfur uptake was minimal for Ag+Ce4+Y zeolites since alongside
π-complexation, adsorption occurs via S–M interaction. Many authors have
shown that the adsorption equilibrium of ion-exchanged Y zeolites can be ade-
quately described by simple Langmuir and Freundlich isotherms and by more
advanced models such as the Langmuir–Freundlich (Sips) isotherm (Xue et al.
2005; Takahashi et al. 2002; Yang et al. 2001; Bakhtiari et al. 2016). The heat of
adsorption of Y zeolites ranges from 10 to 40 kJ mol 1, decreasing linearly with the
sulfur coverage (Lee and Valla 2017; Yang et al. 2001; Ng et al. 2005). Lee and
Valla (2017) found that, in comparison to NaY, Y zeolites exchanged with transi-
tion metal ions exhibit higher heats of adsorption, revealing a stronger interaction
between the species and the metal ions. In general, ion-exchanged Y zeolites
exhibit fast sulfur adsorption kinetics which can be described by pseudo-first
order models. Song et al. (2014b) assessed the performance of Cu+Y and Cu+Ce
4+
Y zeolites between 20 and 100 C and found an optimal sulfur uptake around
50 C. While there is a thermodynamic drive for adsorption at low temperatures, the
existence of a maximum sulfur capacity can be explained by low diffusion rates

below 50 C.
3.2 Metal Organic Frameworks
Metal organic frameworks (MOFs) are highly ordered materials consisting of

metallic nodes (ions or clusters) coordinated to rigid organic molecules to form
one-, two-, or three-dimensional networks, Fig. 5.7. The possibility to choose
among various metallic centers and organic linkers (that can be functionalized)
allow the physicochemical properties of MOFs to be tuned for a particular appli-
cation. In the specific case of catalysis, gas storage, and adsorption, the most
attractive features of MOFs are their high specific surface area (10,400 m2 g 1),
their large pore apertures (98 Å), their low density (0.13 g cm 3), and their ability to
accommodate guest molecules (Chughtai et al. 2015).
In recent years, there has been an increasing interest in exploiting the adsorption
properties of MOFs to remove pollutants from water and fossil fuels. In the case of
fossil fuels, most studies have used model diesel and gasoline to assess the
performance of different MOFs in the removal of organosulfur compounds, in
particular thiophene, benzothiophene, dibenzothiophene, and alkylsubstituted
dibenzothiophenes. Experiments are usually carried out at atmospheric pressure
and at relatively low adsorption temperatures (20–100 C). Depending on the type
of MOF and on the solvent and the operating conditions used, the adsorption
capacities range from 2 to 112 mgS gads 1, which are significantly higher than
those of Y zeolites.
Cychosz et al. (2008) pioneered the use of MOFs for SARS studying the removal
of BT, DBT, and DMDBT from isooctane with five different materials: MOF-5,
MOF-177, HKUST-1, UMCM-150 and MOF-505. MOF-5 and MOF-177 are
constructed from Zn4O(COO)6 secondary building units (SBUs) while HKUST-1,
UMCM-150, and MOF-505 are Cu paddlewheel structures. The authors did not find
any correlation between the surface area of the materials and the amount of sulfur
adsorbed. Conversely, they observed that the adsorption performance of all three
Cu materials was clearly superior to the Zn frameworks. UMCM-150 and MOF-505
Fig. 5.7 Schematic representation of MOFs synthesis (adapted from Chughtai et al. 2015)
were the MOFs with the highest sulfur uptake which was ascribed to the presence of
coordinatively unsaturated Cu-metal sites. Blanco-Brieva et al. (2013) assessed the
sulfur adsorption performance of Fe-BTC (C9H3FeO6), MIL-53 (Al) (Al(OH)
C8H4O4), and HKUST-1 (Cu3(C9H3O6)2) MOFs and found that HKUST-1
exhibited the highest BT and DBT uptake due to a very strong interaction between
the sulfur atom and the open Cu sites. Similar results were reported by Peralta et al.
(2012) using real FCC naphtha and various types of MOFs as adsorbents. The
authors observed that HKUST-1 and CPO-27-Ni exhibited the highest sulfur uptake
and explained their results based on the presence of accessible coordinatively
unsaturated metal sites. They also demonstrated that HKUST-1 and CPO-27-Ni
have higher capacity and are more selective than Y zeolites in the presence of other
aromatic compounds.
It has been reported that the adsorption capacity of MOFs can be significantly
enhanced by the incorporation of transition metals after the synthesis. Khan et al.
(2016) found that the BT uptake of MIL-47 doubled when it was impregnated with
a CuCl2 solution. The authors attributed the enhancement to the formation of
π-complexes between the organosulfur compounds and Cu1+ ions produced during
the pretreatment of the sample. Shi et al. (2011) reported a significant increase in
the adsorption capacity of MOF-5 when it was impregnated with Mo(CO)6. How-
ever, the authors did not observe any proportional trend between the amount of
sulfur adsorbed and the content of Mo(CO)6 in the sample, probably due to pore
blockage at the molybdenum loadings used.
It has been reported that the sulfur uptake of MOFs decreases in the presence of
other organic species (particularly aromatics) due to competitive adsorption.
Cychosz et al. (2008) measured the BT, DBT, and DMDBT adsorption isotherms
of five MOFs in isooctane and isooctane/toluene mixtures, and observed a fivefold
decrease in the organosulfur uptake when toluene was present. Nevertheless, MOFs
were found to be more selective towards sulfur molecules compared to a commer-
cial NaY zeolite used as a benchmark. Shi et al. (2011) reported that a Mo(CO)6/
MOF-5 reduced its DBT adsorption capacity by 90% in the presence of benzene.
Contrary to these works, in a desulfurization study using real gasoline, Peralta et al.
(2012) found that the sulfur uptake was not influenced by sulfur-free aromatic
molecules but decreased significantly in the presence of olefins and nitrogen
compounds. In a recent study, Khan and Jhung (2012) measured the sulfur capacity
(DBT and DMDBT) of a series of MOFs with a MIL-53 topology in the presence of
diethyl ether and water, which are oxygen-containing molecules that are usually
present in gasoline and diesel pools. They observed a significant enhancement in
the adsorption performance which was attributed to the structural flexibility of the
MIL-53 material. In agreement with these observations, other authors have
suggested that the breathing/flexibility properties of MOFs play a key role in the
discrimination between thiophenic and nitrogen compounds (Van de Voorde et al.
2013). The availability and nature of open metal sites in MOFs also seem to be
crucial factors with regard to the selective adsorption of nitrogen- and sulfur-
containing organics. Maes et al. (2011) assessed the sulfur adsorption performance
of a vast range of MOFs and found that MOFs with hard Lewis open metal sites
(Fe3+, Cr3+, Al3+) exhibit strong uptake of N-compounds and only weak affinity
for sulfur, whereas materials exposing soft Lewis open metal sites (Cu2+, Co2+ and
Ni2+) were highly selective to S-compounds.
Contrary to Y-zeolites, the sulfur uptake of MOFs decreases significantly during
regeneration with inert gases at high temperature, mainly due to a loss in crystal-
linity and porosity. However, MOFs can be effectively regenerated by polar
solvents such as ethanol, methanol, and isopropanol (Blanco-Brieva et al. 2013).
Blanco-Brieva et al. (2013) investigated the multicycle stability of HKUST-1 after
adsorption of DBT. It was found that the adsorption capacity and crystallinity of the
HKUST-1 adsorbent remained constant after several adsorption-regeneration
cycles using methanol as a solvent. Although more comprehensive studies are
needed to understand the adsorption equilibria and kinetics of organosulfur com-
pounds on MOFs, it has been reported that Langmuir isotherms and pseudo-second
order models can adequately describe the equilibrium and kinetics of the materials,
respectively (Khan and Jhung 2012).
3.3 Mesoporous Silicas and Carbon-Nanostructured

Adsorbents
Mesoporous silicas and some nanostructured carbons are receiving intense attention
as solid adsorbents due to their large specific surface area, adequate pore size
distribution, and unique chemical properties. Capacities above 20 mgS gads 1
have been reported for SARS, which is significantly larger than those observed
with promoted Y zeolites.
In a pioneering work using nanostructured carbons, Nazal et al. (2015) assessed
the removal of DBT from model diesel fuel using multi-walled carbon nanotubes
(MWCNTs) and graphene oxide (GO), and found that the capacity of the materials
was significantly increased by promoting them with 5 and 10% Al2O3
nanoparticles. They attributed the enhancement to the introduction of Lewis acid-
ity. Fallah et al. (2015) demonstrated that the passivation of carbon nanoparticles
with polyethylene glycol (PEG-200) enhanced the porosity and introduced acidic
functional groups on the carbon framework that result in high adsorption capacities
of BT, DBT, and DMDBT. GO has been used as support for hydrotalcites (HTs)
and was shown to increase the DBT uptake compared to the unsupported materials,
Fig. 5.8 (Menzel et al. 2016). The enhancement is attributed to an improved particle
dispersion which favors the accessibility of sulfur to the adsorption sites. The
HT/GO hybrids exhibited good regenerability and selectivity in the presence of
biphenyl.
The surface chemistry, i.e., the presence of functional groups and acid sites, has
been found to be as crucial for mesoporous silicas as for carbon nanostructures.
Anbia and Karami (2015) compared the adsorption performance of a nanoporous
carbon prepared using Al-SBA-15 as a template (CMK-3) with that of SBA-15 and
Al-SBA-15. The following order in DBT uptake was found: CMK-3 > Al-SBA-
Fig. 5.8 Sulfur capacity of

HT and HT/GO (adapted
from Menzel et al. 2016)
15 > SBA-15. CMK-3 exhibited the highest uptake (40 mgS gads 1) due to a larger
mesopore volume and specific surface area. The adsorption capacity of SBA-15
was significantly enhanced by the addition of Al due to the formation of Brønsted
and Lewis sites of medium acidity. The presence of transition metals in the
mesoporous silica structures has also been shown to enhance the sulfur capacity
of the adsorbents. PdCl2/SBA-15 was reported to have an increased capacity for
benzothiophene and showed good regenerability by isooctane flushing (Rodrigues
et al. 2014). Ag-impregnated mesoporous aluminosilicate nanoparticles
(Al-MCM-41) prepared using a plasma treatment also exhibited remarkable sulfur
uptakes from commercial jet fuel JP-8 (41 mgS gads 1) and were very stable upon
adsorption–desorption cycles (Hauser et al. 2016). The performance of Ag-Al-
MCM-41 was superior to Ag-MCM-41 since the presence of intraframework Al
introduced Brønsted acidity and aided in the dispersion and retention of Ag ions.
So far, very little attention has been given to the competitive adsorption of
organosulfur compounds using mesoporous silicas and carbon nanostructures.
General trends indicate that GO and MWCNTs adsorb selectively thiophenic
molecules in the presence of aromatics and olefins such as benzene, naphthalene.
and cyclohexene (Fallah et al. 2015). Similar to Y zeolites, preliminary studies
suggest that the carbon nanostructures exhibit higher selectivities for substituted
thiophenes than for thiophene (Khaled 2015). It has also been observed that the
DBT uptake of GO is significantly enhanced in the presence of oxidizing agents
such as n-octanal (Zhang and Wang 2017).
Mesoporous silicas and nanostructured carbons are typically regenerated using
solvents such as ethanol, acetonitrile, toluene, and heptane (Nazal et al. 2015;
Fallah et al. 2015; Khaled 2015) or by thermal treatment in air. In the case of
carbonaceous adsorbents, the temperature should be maintained below 350 C to
prevent the combustion of the materials under the oxidizing atmosphere. For both
types of materials, the sulfur adsorption equilibria have been adequately described
by Freundlich and Langmuir isotherms whereas pseudo-second order and linear
driving force models have been used to describe the adsorption kinetics (Khaled
2015; Xiong et al. 2015).
4 Concluding Remarks
Selective adsorption removal of sulfur (SARS) is a promising technology for ultra-

deep desulfurization of refinery streams. Contrary to conventional
hydrodesulfurization (HDS), SARS is carried out at low temperatures and pressures
with minimal hydrogen consumption. This prevents olefin hydrogenation and thus
maintains the properties of the fuels (e.g., octane and cetane numbers). SARS is
also a cost-effective strategy to remove heavy thiophenic compounds that remain
after HDS. However, the main challenge of SARS is to find suitable solid adsor-
bents for the process, with high sulfur capacities, fast adsorption–desorption kinet-
ics, adequate regenerability, and with high selectivity to adsorb sulfur in the
presence of competing species.
Among the range of potential sulfur adsorbents, the use of nanostructured
materials for SARS is particularly attractive since their high surface area and
porosity improves the diffusion of sulfur molecules to the active sites. In addition,
it is possible to tune their adsorption properties by functionalization and by delib-
erate creation of defects during their synthesis. The most widely studied
nanostructures for selective sulfur removal are zeolites, metal organic frameworks
(MOFs), mesoporous silicas, and carbon nanostructures. All of them show capac-
ities that are at least in the range of precompetitive and commercial adsorbents. The
performance of the different nanomaterials depends on the chemical composition,
the nature of the sulfur molecules in the fuels, the presence of competing species,
and the operating conditions. Zeolites have the advantage that the acid–base
properties can be modified in a very controlled way by changing their bulk
composition or through the incorporation of transition metals. The highest uptakes,
however, have been reported for MOFs, but the stability of these structures during
regeneration remains a big challenge. In contrast, nanostructured carbons and
mesoporous silicas exhibit better regenerability and have adsorption properties
that can be readily tuned but have relatively low capacities and selectivities.
Research efforts are still needed to get a deeper understanding of sulfur adsorp-
tion/desorption to allow better design of adsorbents. Investigation of competitive
adsorption, and the influence of regeneration conditions on the stability and per-
formance of the adsorbents in multicycle experiments are research areas that
deserve particular attention. Likewise, the mechanical properties of the
nanostructures need to be assessed and potentially improved by the use of binders.
Acknowledgements The authors are grateful to Robert Menzel and Milo Shaffer for discussions
and to John Blamey for proofreading. This work was supported by EPSRC (UK) under grants
EP/K014749/1 and EP/N010531/1.
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Diana Iruretagoyena obtained her Ph.D. under the supervision of Professor David Chadwick
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College London, where she currently works as Research Associate. Her research focuses on the
interfaces of reaction engineering, applied catalysis, separation processes, and materials science
combining laboratory experiments and modelling work. Diana’s research has resulted so far in a
number of scientific publications and has been presented at international conferences and semi-
nars. In addition, she was awarded the Julia Higgins Centenary Prize 2014 from the Department of
Chemical Engineering.
Raul Montesano obtained his Ph.D. under the supervision of Professor David Chadwick in the
Department of Chemical Engineering (2014) at Imperial College London, where he was awarded
the Townend Prize. Currently, he works as a Research Engineer in R&D Chemicals at Haldor
Topsøe.
Chapter 6
Nano-MoS2 and Graphene Additives in Oil
for Tribological Applications
Yufu Xu, Yubin Peng, Tao You, Lulu Yao, Jian Geng, Karl D. Dearn,
and Xianguo Hu
Abstract Nano-additives have attracted lots of attentions in recent years due to

their special performances. A traditional lubricating additive MoS2 with nano-scale
and a novel additive graphene were reviewed in this chapter. The synthesis
methods, properties, and tribological applications of these two kinds of nano-
additives dispersed in media have been reported. Nano-MoS2 has three main
nanostructures including nano-ball particles, nano-sheets, and nano-tubes. The
wide accepted lubricating mechanisms for the MoS2 nano-balls, nano-sheets, and
nano-tubes are nano-bearing effects, slippery roles, and combined actions of rolling
and sliding, respectively. Exfoliation and transfer seem to be the main pattern for
MoS2 nano-balls. For graphene, the adsorption and tribo-reaction account for its
lubricating properties. A synergistic lubricating effect for using graphene and MoS2
together dispersed in oil was found. Graphene was proved to extend the retention of
MoS2 on the surfaces and prevent the oxidation of MoS2. Simultaneously, MoS2
prevented the graphene from being ground into small and defective platelets. Both
of them help to form a thicker adsorbed and tribo-film which result in a lower
friction and wear. Other properties and applications of nano-MoS2 and graphene are
also reviewed. It shows that these two nano-additives have diverse functions and
great potential for industrial applications.
Keywords Nano-MoS2 • Graphene • Nano-additives • Tribological application
Y. Xu (*) • Y. Peng • T. You • J. Geng • X. Hu

Institute of Tribology, School of Mechanical Engineering, Hefei University of Technology,
Hefei 230009, China
L. Yao
School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei
230009, China
K.D. Dearn
Department of Mechanical Engineering, School of Engineering, University of Birmingham,
Edgbaston, Birmingham B152TT, UK

152 Y. Xu et al.
1 Introduction
A general demand from Society for a more sustainable and environmentally

friendly development has led to an increasing interest and a growing corpus of
work on energy-saving and emission reduction technologies (Price et al. 2011). The
internal combustion engine is one such technology that has seen huge improve-
ments in fuel efficiency, reduced overall energy consumption and emissions,
and a key aspect of this has been improvements to the lubrication system
(Abdelaziz et al. 2011).
With the development of the nanotechnologies, the use of nano-additives added
to base oils has been shown to reduce friction and wear due to their excellent
lubricating effects. Some common solid particle lubricants such as nano-MoS2 and
graphene have made the transition from concept to the application and are showing
great potential in the industry. However, there still exists a gap between the
scientists and industrial engineers, relating to a general willingness to use the
newly formulated additives (Zhmud and Pasalskiy 2013). If emissions and fuel
consumption targets are to be met, then nano-additives, added to lubricant formu-
lations will be a vital component for industry to deploy to meet these objectives.
In this chapter, the progress and particularly the tribological behaviors of some
key nano-additives dispersed in base oil are reviewed, and the trends in future
developments of nano-additives are discussed in order to accelerate their
application.
2 An Introduction to and the Tribological Behavior

of Nano-MoS2
Molybdenum disulfide (MoS2) has a layered two-dimensional structure. Its crystal

structure contains 1T-MoS2, 2H-MoS2, and 3R-MoS2. 1T-MoS2, per unit cell, has
an octahedral structure with S atoms and one Mo atom; 2H-MoS2 has a hexagonal
structure and two S-Mo-S units per primitive cell, and 3R-MoS2 has a hexagonal
structure and three S-Mo-S units per primitive cell. Their respective structures are
shown in Fig. 6.1. Among these MoS2 crystals, 1T and 3R-MoS2 are metastable and
2H-MoS2 is stable under normal conditions. But no matter which crystal, each S
atom is surrounded by 3 Mo atoms, and each Mo atom is surrounded by six S atoms
consisting of S-Mo-S covalent bonds (Dickinson and Pauling 1923), such that the
atom ratio of Mo and S is 1:2.
The layered structure of MoS2 has excellent tribological properties which are
attributed to a combination of its low Van der Waals force between the molecule
layers and strong covalent bond in the molecule. When MoS2 bears a shear stress,
molecular layers slide easily over one another. This is the reason that MoS2 has
been widely used as a solid lubricant and used as an additive of lubricating oils. It
6 Nano-MoS2 and Graphene Additives in Oil for Tribological Applications 153
Fig. 6.1 Hexagonal structure of MoS2 (a), a schematic illustration of the 1T- MoS2 (b), 2H-MoS2,
and 3R-MoS2, and the repeat unit of the MoS2 layers (c) (Ye et al. 2015)
has been proved that the size of MoS2 particles has a significant effect on their
performances and so in the following section some typical nanostructures of MoS2
are reviewed.
2.1 MoS2 Particles: Nano-balls
Compared with MoS2 sheets, MoS2 nano-ball particles have some particular char-
acteristics, including no dangling bonds that make them more stable. Additionally,
the small size of the MoS2 nanoparticles may result in some other enhanced
physical properties.
2.1.1 Preparation of MoS2 Nano-balls
Rosentsveig et al. (2009) used a four-step method to produce an inorganic

fullerene-like (IF) MoS2, which constitutes a typical nano-ball particle. The process
includes four consecutive steps: (1) Evaporation of the molybdenum oxide (MoO3)
powder at a temperature of between 700 and 750 C; (2) the reduction and
condensation of the vapor into MoO3x nanoparticles at 780 C; (3) the
sulfurization of the first few layers of the oxide nanoparticles; (4) the complete
sulfurization of the nanoparticles with a slow diffusion-controlled reaction at a
temperature above 840 C. This method allows the sulfurized degree to be con-
trolled (Fig. 6.2); it is however a complex procedure that consumes a large amount
of energy.
Precipitation is another popular approach used for producing MoS2 nano-balls
due to the relatively gentle synthesis conditions. As an example, Huang et al. (2005)
added 28 g Na2S and 5 g (NH4)2MoO4 into 250 mL distilled water, allowing the
reaction to occur over an hour. During the reaction, hydrochloric acid was added to
154 Y. Xu et al.
Fig. 6.2 TEM images of IF-MoS2 nanoparticles with no oxide (a) and remaining oxide (MoO2) in
the core (b) (Rosentsveig et al. 2009)
Fig. 6.3 TEM images of the IF-MoS2 nanoparticles from produced using precipitation methods
(Huang et al. 2005)
the solution in order to control the acidic pH. After this, the as-prepared MoS3
precursor was desulfurized in a gas mixture of hydrogen-argon at 1173 K for 8 h.
The final nano-balls had diameters varying from 70 to 120 nm (Seen from Fig. 6.3).
Hu et al. (2007) prepared molybdenum sulfide particles with Na2MoO4 and
CH3CSNH2 by a quick (c. 5 min) homogenous precipitation technique in an
alcohol–water solution at 82 C. The resultant amorphous MoSx nano-ball particles
were then desulfurized under H2 flow at an elevated temperature for 50 min. This
method seems to be another alternative method that can be used to synthesize nano-
ball MoS2.
2.1.2 Characterization of MoS2 Nano-balls
Transmission electron microscopy (TEM) can be used to observe MoS2

nanoparticles, operating levels of resolution that are much higher than light
Fig. 6.4 SEM image of MoS3 precursor (Huang et al. 2005)
Fig. 6.5 XRD (a), TEM (b), and HRTEM (c) of the MoS2 nano-ball particles (Hu et al. 2009b)
microscopes, due in part to the small de Broglie wavelength of electrons. It can also
be used to show structure, morphology, and to check the aggregation of nanoparticles.
Scanning electron microscopy (SEM) is another effective tool to observe the
form of nanoparticles. As an example, Fig. 6.4 (Huang et al. 2005) shows a MoS3
precursor produced by Huang, with a clear spherical shape, with a diameter of
~150 nm. However, the aggregation of the nanoparticles is severe as no dispersing
media can be used with this method.
X-ray powder diffraction (XRD) can be used to assess the crystal structure of
MoS2 nanoparticles. The work of the Institute of Tribology at Hefei University of
Technology has proved that the MoS2 nanoparticles have the similar XRD spectra
in Fig. 6.5 with the standard curve of MoS2 in PDF number 37-1492. Its holly
structures are also shown in TEM in Fig. 6.5.
The crystallinity and shape of MoS2 nano-balls are the main characteristics that
affect frictional properties. These two properties are governed by the parameters
and conditions selected during synthesis. Crystallinity governs the order degree of a
MoS2 layer which is composed of closed shells nano-balls. Perfectly crystalline
MoS2 nano-balls have a well-crystalline order with few defects present in closed
shells, whereas poor crystallinity shows some extent of disorder with many point
defects (Fig. 6.6). Moreover, perfectly crystalline MoS2 nano-balls will have good
physical properties. The shape of a MoS2 nano-ball is not a perfect sphere most of
the time. There are corners of the structure which are likely to induce stress
156 Y. Xu et al.
Fig. 6.6 HRTEM images of perfect (a, a1) and incomplete crystalline MoS2 nano-balls (b, b1)
(Lahouij et al. 2014)
concentrations. With this in mind, therefore the more perfectly crystalline and
spherically shaped that the MoS2 nano-ball is the higher the ability resist deforma-
tion (Lahouij et al. 2014).
2.1.3 Dispersion of MoS2 Nano-balls in Base Oil
MoS2 nanoparticles have lots of functions including lubrication, catalysis (Li et al.
2011b), functional materials, and so on (Radisavljevic et al. 2011). Among them,
one of the most important functions for MoS2 seems to be lubrication. Usually, it is
used as an additive in base oil or grease. Thus, the choice of the base oil is very
important for improving the lubricating properties of MoS2 nanoparticles. For
example, an industrial oil composed of many fractions of hydrocarbons has been
used for dispersing MoS2 nanoparticles (Aralihalli and Biswas 2013). However, the
industrial oil has contained many other additives with a variety of roles. To reduce
the effects of the other additives, paraffin oil is often chosen as a base oil for use
with MoS2 nanoparticles (Huang et al. 2005) because of the similar components
with traditional mechanical oils. Poly alpha olefin (PAO) has attracted lots of
attention, with excellent thermal stability and anti-oxidation properties, as a base
oil with MoS2 nanoparticles in recent years (Rosentsveig et al. 2009). Moreover, Xu
et al. have tried some renewable bioenergies, such as bio-oil, as the base oil for
MoS2 micro-sheets, which have also shown good lubricating effects.
It has been reported that the addition of the nanoparticles on their own in base oil
has little effect on the tribological properties of a tribo-systems. But it takes effect
after using a dispersing agent (Aralihalli and Biswas 2013; Desai and Banat 1997;
Moshkovith et al. 2006). This suggests that the selection of the dispersive agent and
method of mixing are very important. Zhou et al. (2008) used an extractant Cyanex
301 (di-(2,4,4-trimethylpentyl) dithiophosphinic acid) to modify the surface of
MoS2 nano-hollow spheres in liquid paraffin. Results showed that the modified
MoS2 had better extreme pressure, antiwear, and antifriction properties than com-
mercial MoS2. Sorbitol monooleate was selected by Huang et al. (2005) as the
dispersing agent for IF-MoS2 in paraffin oil. The mixture was stirred with a high-
speed dispersion machine before ultrasonic treatment.
Dispersant agents can be grafted or adsorbed on nanoparticles with
ultrasonication or stirring. The chemical affinity between dispersants and
nanoparticles is the main factor that affects the dispersion. When chemical affinity
is low, the particles can be easily separated from the base oil and the nanoparticles
will agglomerate again under the effect of friction (Aralihalli and Biswas 2013).
It is important not to increase the concentration of dispersants to levels that are
too high in the lubricant. Under such conditions, though the nanoparticles will be
well dispersed, a large amount of dispersant agent will reduce the life of the
lubricant and increase friction. As shown in Fig. 6.7, the tribological benefits of
MoS2 were eliminated when 5% dispersant was used. However, when the disper-
sant concentration was adjusted to 0.05%, the friction coefficient decreased. The
reason for this is that with high concentrations of dispersants, MoS2 nanoparticles
cannot be adsorbed on the rubbing surface and reduce the friction coefficient
(Rabaso et al. 2014a).
2.1.4 Comparison with Micro-MoS2
MoS2 nanoparticles have better lubricating properties than MoS2 micro-particles

(Hu et al. 2010). According to the Risdon’s investigation (Risdon and Gresty 1975),
the energy consumed on transportation in the USA during the period 1963–1974
can be reduced by 4.4% with a proper dispersion of 1% weight commercial
molybdenum disulfide in the engine oil. Thus, it can be inferred that more fuel
can be saved by the introduction of nano-MoS2. Hu’s results (Hu et al. 2010)
158
Fig. 6.7 Friction coefficient of PAO + 1% IF-MoS2 + 5% dispersant (left), and PAO + 1% IF-MoS2 + 0.05% dispersant (right) (Rabaso et al. 2014a)
Y. Xu et al.
0.10
liquid paraffin(LP)
micro-MoS2 + LP
0.09
Average Friction coefficient MoS2 nano-balls + LP
MoS2 nano-slices + LP
0.08
0.07
0.06
0.05
0 0.5% 1.0% 1.5% 2.0%

Content of MoS2 (wt.%)
Fig. 6.8 Effects of the concentration of MoS2 on the average friction coefficient (Hu et al. 2010)
showed that the addition of MoS2 nano-balls in liquid paraffin at a concentration of

1.5 wt% resulted in a better antifriction and antiwear properties than micro-MoS2.
Figure 6.8 shows a friction coefficient reduction of 21% and 10%, respectively,
when compared to those of 1.5% micro-MoS2 and 1.0% nano-slices.
2.1.5 Effect of ZDDP on Tribological Properties
ZDDP (Zinc Dialkyl Dithiophosphates) is an important oxidation and corrosion

inhibitor often found in fully formulated lubricating oil which extends the oxidation
resistance of lubricating oil. It also has excellent antiwear properties but has no
effect on friction. Lamellar MoS2 nanoparticles derived from nano-sheets or the
exfoliation of nano-balls are easily oxidized to MoO3 which degrade the friction-
reducing properties of MoS2. When ZDDP and MoS2 nanoparticles exist together,
both friction coefficient and wear are reduced significantly. It is believed that there
is a synergistic effect between ZDDP and MoS2: the MoS2 is believed to be
embedded into ZDDP chemical reaction film and therefore reinforces its antiwear
effect, at the same time, the ZDDP film provides protection for the MoS2 from
being oxidized resulting in the improvement of the antifriction behaviors (Tomala
et al. 2015; Aldana et al. 2014).
160 Y. Xu et al.
Fig. 6.9 Friction coefficient of perfect (SC) and poorly crystalline (SpC) on HFRR (Rabaso et al.
2014b)
2.1.6 Effect of Crystallinity on Tribological Properties
The tribological properties of MoS2 nano-balls to some extent are dependent on its
structural characteristics and particularly its crystallinity. MoS2 nano-balls that are
perfectly crystalline have a better ability to resist deformation, whereas MoS2 with
incomplete crystallinity are easily deformed and exfoliated under the similar sliding
conditions (Lahouij et al. 2014). Rabaso et al. (2014b) compared the frictional
properties of MoS2 with poorly crystalline structures with similar average diame-
ters (150 nm). They found that perfect MoS2 nano-balls played a significant role in
friction-reduction during running in, however, the friction coefficient increased
after this due to the lack of perfect MoS2 nano-balls. On the contrary, poorly
crystalline MoS2 maintained a stable low friction coefficient as shown in Fig. 6.9.
The difference is because poorly crystalline can be easily exfoliated and transferred
onto the rubbing surfaces forming an adsorbed layer. Perfect crystalline
nanoparticles were much harder to exfoliate before being squeezed out from the
rubbing interfaces, thanks to the better physical properties. In addition to the
frictional process, the MoS2 adsorbed film formed during the early stages of
rubbing was gradually worn off. Due to the two reasons above, there were few
MoS2 particles remaining between the frictional interfaces resulting in the increase
of the friction coefficient.
Fig. 6.10 A MoS2 nano-

ball bearing two different
forms of pressure: isotropic
(a), normal stress (b)
(Joly-Pottuz et al. 2006)
2.1.7 Effect of Different of Pressure on Exfoliation Behavior
MoS2 nano-balls can be ruptured under a high normal stress on the frictional
interfaces. However, this will not happen in oil though oil pressure might be
much higher than critical ruptured normal stress. That is because oil pressure is
isotropic and the shape of the nano-ball is quasi-spherical which makes bearing
force of MoS2 uniform (Fig. 6.10) (Joly-Pottuz et al. 2006).
2.1.8 Tribological Mechanisms
MoS2 nano-balls have excellent lubricating properties as lubricating oil additives.

There are three main frictional mechanisms that can explain this property: rolling,
sliding, and exfoliation-transfer (third body) as shown in Fig. 6.11 (Tevet et al.
2011).
1. Rolling: MoS2 nano-balls roll as a ball bearing across frictional interfaces under
relatively low normal stress. The roller is dependent on the shape of nano-balls
which should be quasi-spherical structures.
2. Sliding: Similar to nano-sheets, friction happens between external surfaces of
the nano-balls under higher normal stress. The behavior of sliding is due to the
shape of nano-MoS2 particles, which is not perfectly spherical but of a faceted
polyhedron structure. The corner of the faceted polyhedron structure can be
easily distorted by asperities on the rough mating surfaces.
3. Exfoliation and transfer (third body): Exfoliation is the main action of behavior
under high normal stress resulting in deformation and even rupture of the nano-
balls. Under the combined effects of the normal stress and shear stress, the
external surface of the nano-ball particles can be exfoliated producing MoS2
162 Y. Xu et al.
Fig. 6.11 Schematic of the three main tribological mechanisms of MoS2 nano-balls: rolling (a),
sliding (b), and exfoliation and transfer (third body) (c) (Tevet et al. 2011)
nano-sheets which can be adsorbed on the rubbing surfaces providing a protec-

tive layer and reduced the friction coefficient.
Among these three behaviors, rolling is generally accepted as the most prevalent
mechanisms of friction reduction, because they cannot be detected directly only by
micro-frictional tests on the single MoS2 nano-balls.
Particle size and crystalline perfection of the MoS2 nano-balls are the most
important factors that affect tribological behavior (Rosentsveig et al. 2009). Gen-
erally, due to a nano-bearing effect, the small MoS2 nanoparticles have better
antiwear and friction reducing properties than larger nanoparticles. However,
with the decrease of particle size, the aggregation effects of the MoS2 can increase
and chemical stability reduces, which might result in reduced lubricity. Hence, the
particle size is very important in the efficacy of the additives. It is believed that
exfoliation, rolling friction, and third body transfer of MoS2 sheets into surface
asperities are the prevalent mechanisms that can explain the excellent tribological
properties of MoS2 nanoparticles (Rosentsveig et al. 2009).
There are no active dangling bonds in the closed-structure MoS2; consequently,

the oxidation temperature of MoS2 nano-ball particles is ~100 C higher than that of
2H-MoS2. Moreover, under some testing conditions, the MoS2 nano-ball particles
had better lubricating properties than MoS2 nano-sheets. This was ascribed to the
chemical stability of the layer-closed spherical structure of nano-balls. The detailed
mechanisms for this are shown in Fig. 6.12. In air or when used in liquid paraffin
nano-sheets, due to the rim-edge site of the nano-sheets, they are easier to oxidized
into MoO3, there was a poor lubrication. MoS2 nano-ball particles are relatively
stable and can bear the shearing via rolling and elastic deformation.
a
Basal surface with
chemical inertness Shearing
Air and LP
Active Easily
rim-edge Rubbing
surface Difficultly MoO3
Air and LP
5nm
Shearing Shearing
b Air and LP
Basal surface with Difficultly

chemical inertness
MoO3
Rolling Elastic deformation
Rubbing
Air and LP
MoO3 Easily
Shearing
150nm
Exfoliation
Fig. 6.12 TEM images and schematics of the lubrication mechanisms of MoS2 nano-slices (a)
and MoS2 nano-balls (b) (Hu et al. 2010)
2.2 MoS2 Nano-sheets
In recent years, the study of graphene-like two-dimensional layered materials has

attracted great interest due to the successful exploration of graphene (Zhang et al.
2016b; Huang et al. 2012; Xu et al. 2013). Among them, MoS2 nano-sheets are the
popular research molecular as a result of their distinct structure and superior
properties. Functionalization, hybridization, and modification of MoS2-based
nano-sheets have seen them used widely in various applications. Here, the prepa-
ration, characterization, and properties of nano-sheets are reviewed.
2.2.1 Preparation of MoS2 Nano-sheets
It has been demonstrated that most of the methods for preparing 2-D nano-material
such as graphene are effective for MoS2 nano-sheets. The classic and straightfor-
ward way to prepare the nano-sheets is micro-mechanical cleavage (Radisavljevic
et al. 2011). Using this top-down approach, a high-quality 2-D nano-material can be
obtained (Lopez-Sanchez et al. 2013). However, the shortcomings of this method
are also obvious. The productive efficiency is low and it is difficult to synthesize the
164 Y. Xu et al.
Fig. 6.13 Schematic illustration of electrochemical lithiation and exfoliation process for the
fabrication of 2D nano-sheets from layered bulk crystals (Zeng et al. 2011)
2D nano-sheets in large quantities. Moreover, the geometry can be very difficult to

control precisely.
Ion-intercalation exfoliation is another popular method that can be used for the
preparation of MoS2 nano-sheets. As shown in Fig. 6.13, there are three steps in this
method: (1) introduction of Li+ ions into the interlayer of bulk MoS2; (2) immersion
of LixMoS2 nano-sheets into water; and (3) ultrasonic processing of the solution.
Bottom-up methods have been used to fabricate MoS2 nano-sheets with desired
size and thickness. Choudhary et al. (2014) adopted a sputter–chemical vapor
deposition (CVD) technology to synthesize large-area, high-quality, and layer-
controlled MoS2 nano-sheets on Si-based substrates. They also demonstrated that
the single-layer MoS2 over an area of 2 inches wafers with the domain size of
10–15 μm2, showing good potential in future flexible, high-temperature, and radi-
ation hard electronics/optoelectronics. Although CVD is an effective method for
producing high-quality MoS2 nano-sheets, there are some obvious disadvantages
with the synthesis conditions, such as high temperatures, the requirement for a
vacuum, and specific substrates, which restrict the practical applications of MoS2
nano-sheets (Zhang et al. 2016b).
Owing to specific merits such as cheap raw materials, size and thickness
controllable, high productive efficiency and no requirements on the substrates,
solution-based methods have become prevalent in recent years. Smith et al.
(2011) prepared MoS2 nano-sheets through 1.5 mg mL1 sodium cholate as a
surfactant to exfoliate bulk MoS2 in aqueous solutions. In a typical run, ultrasonic
treatment can be used for the solution lasting 30 min, followed by centrifugation at
1500 rpm for 90 min.
2.2.2 Application of MoS2 Nano-sheets
One of the most important applications for MoS2 nano-sheets is a substitute of

noble metal catalysts such as Pt/C. It has been proved that the active edges of MoS2
can be used as the active center for electro-catalysis (Zhang et al. 2016a). Electro-
catalytic performance can be improved by reducing the dimension and by exposing
the edges of the 2-D MoS2.
Efficient energy storage is an important challenge for sustainable development.
MoS2 nano-sheets can be used in energy storage devices. One such application is in
Li-ion batteries, which have been shown to be a highly efficient energy storage
system. Although the charge capacity of the bulk MoS2 is easy to reduce after use,
after intercalating Li-ion into the interlayer of MoS2, fewer layers of nano-sheets,
the composites exhibited a high energy density capacity of 750 mA h g1 even after
50 cycles (Du et al. 2010). Na ion intercalation in MoS2 sheets has also shown
promising results. Bang and his coworkers (2014) reported a simplest method for
enhancing the productive efficiency of MoS2 nano-sheets in 1-methyl-2-
pyrrolidinone with the assistant of sodium hydroxide. They also proved that at
the high current densities, the exfoliated MoS2 electrode exhibited better capacities
than the pristine particle electrode (Fig. 6.14), indicating improved properties of the
exfoliated MoS2 nano-sheets with the reduced diffusion lengths of Na ions.
Wu et al. (2012) used electrochemically reduced single-layer MoS2 nano-sheets
for sensor applications. It was found that the prepared MoS2 nano-sheets had good
conductivity and high electrochemical sensitivity to detect glucose and
Fig. 6.14 Charge–discharge curves (a) and the cycling properties and their coulombic efficiencies
of the MoS2 nano-sheets (b); the rate capability of pristine MoS2 powder and the prepared MoS2
nano-sheets at various current densities (c) (Bang et al. 2014)
166 Y. Xu et al.
Fig. 6.15 Friction coefficient of the base oil with different additives: Without additives (a), MoS2
micro-particles (b), and MoS2 nano-sheets (c) (Wu et al. 2010)
biomolecules. Thus, reduced MoS2 nano-sheets can be used in the development of

novel electrode materials and can supply a novel platform for the sensing applica-
tions. Li et al. (2012) used MoS2 film-based field-effect transistors to detect NO at
room temperature. The results showed that a single-layer MoS2 nano-sheet had a
rapid response to NO, but the current was unstable. A few-layer (less than 5) MoS2
nano-sheet assembly presented both stable and sensitive responses to NO up to
0.8 ppm.
Another important application for MoS2 nano-sheets is as lubricating additives.
According to Wu et al. (2010), with the addition of MoS2 nano-sheets in liquid
particles with concentration of 1.5 wt%, the friction coefficients decreased signif-
icantly and are shown in Fig. 6.15. In addition, MoS2 nano-sheets have a lower and
more stable friction coefficient than commercial MoS2 micro-particles with the size
of 3–5 mm, owing to the surface effect just as can be seen graphene (Huang et al.
2006). This can be explained by the fact that MoS2 nano-sheets have a larger
surface area and higher chemical activity, which makes them easier to adsorb on
to rubbing surfaces in the form of a stable tribo-film, reducing the friction and wear.
Hu et al. (2009a) prepared MoS2 nano-sheets with a thickness of 30–70 nm via a
monolayer-restacking process and studied tribological behaviors on a four-ball
tribometer. Experimental results indicated that MoS2 nano-sheets had better
antifriction, antiwear, and extreme pressure properties than micro-MoS2
(Fig. 6.16). The excellent tribological properties of MoS2 nano-sheets were attrib-
uted to a surface effect, dimension effect of the nanoparticles, and a complex tribo-
film composed of MoO3 and FeSO4 on the worn surfaces.
Fig. 6.16 PB values (a), average friction coefficient (b) and wear scar diameter (c) of liquid
paraffin with MoS2 nano-sheets and MoS2 micro-sheets (Hu et al. 2009a)
2.2.3 Tribological Mechanisms of MoS2 Nano-sheets
As shown in Fig. 6.17, there are some S dangling bonds on the rim of MoS2 nano-
sheets. When they enter into frictional interfaces, MoS2 nano-sheets could be
adsorbed onto the frictional interfaces forming an adsorbed film depending on the
formation of S-O or S-Fe bonds. The O and Fe came from the oxide layer on the
surfaces of the substrate. The adsorbed film prevented frictional interfaces from
direct contact and improved the tribological properties.
Due to the chemical activity of dangling bonds, MoS2 nano-sheets could be
oxidized to MoO3 and progressively sulfated, where oxygen might come from air or
water during the sliding process. Fleischauer and Lince (1999) compared tribolog-
ical properties of a typical MoS2 film in which the sulfur was substituted for
different contents of oxygen. They found that friction coefficient increased with
increases in oxygen content at first, up to a saturation point of 3% followed by a
decrease. It is still higher than pure MoS2 when oxygen content exceeded the
critical value (Fig. 6.18).
168 Y. Xu et al.
Fig. 6.17 Schematic a b S S S S

illustration of possible
formation mechanisms of
Mo Mo Mo Mo O
MoS2 adsorbed film on the Fe Fe
iron oxide layer (a) and the
S S S S
metal atom (b) (Tannous O S O S
et al. 2011) Fe
S S S S
O Mo Mo O
Mo Mo Mo Mo O
Fe
S S
O O S S S S
Fe Fe
Fe Fe Fe Fe
Fig. 6.18 Variation of

friction coefficient with the
oxygen concentration in the
film (Fleischauer and Lince
1999)
Onodera et al. (2009) drew similar conclusions by simulating single sheet MoS2
lubrication with computational chemistry methods. They proposed that the excel-
lent tribological properties of MoS2 sheets were attributed to the increase of
coulombic repulsion energies between the two sulfur layers reacting with the iron
surfaces as shown in the Fig. 6.19. With oxygen introduced into MoS2, coulombic
interaction energy reduced and roughness of MoS2 layer increased. These resulted
in the rising of the friction coefficient. MoS2 layers became flat again and decreased
the friction coefficient with further increases in oxygen contents.
2.3 MoS2 Nano-tubes
The MoS2 nano-tubes, an analog of carbon nano-tubes, are considered to derive

from lamellar compounds (Chen et al. 2001; Dresselhaus et al. 1996). The discovery
Fig. 6.19 Average frictional force (a), Ra of top MoS2 layer on sliding surface (b); total interlayer
coulombic interaction energy (c); coulombic attractive and repulsive energies (d) along with
oxygen concentration in MoS2 structures; schematic illustration (e) for lubricating properties of
MoS2 single sheet (Onodera et al. 2009)
of the carbon nano-tube has aroused great interest for the one-dimensional nano-
tubes such as MoS2 due to their small dimensions, high anisotropy, and special tube-
like structures (Remskar et al. 2001). In this section, the preparation, characteriza-
tion, and application of MoS2 nano-tube will be described and discussed.
170 Y. Xu et al.
2.3.1 Preparation and Characterization of MoS2 Nano-tube
Remskar et al. (2001) used 5 wt% C60 as a catalyst during the production process. In
a typical run, the reaction conditions were controlled as follows: reaction time:
22 days; temperature: 1010 K; reactor: silica ampoule; pressure: 103 Pa. The SEM
and TEM images of the nano-tubes are shown in Fig. 6.20. The conversation rate
was about 15% for MoS2 nano-tubes.
Template synthesis is another path to obtain MoS2 nano-tubes. Zelenski and
Dorhout (1998) used aluminum oxide templates to prepare near-mono-dispersed
MoS2 nano-tubules. As shown in Fig. 6.21, the fibers in the picture were synthe-
sized in 0.1 M (NH4)2MoS4 DMF solutions. They were separated from the template
by the dissolution of the template using 1.0 M NaOH solutions. Figure 6.21b
presents an end-on view of the nano-tubes and confirms their hollow nature.
Nath et al. (2001) developed a simple synthesis method of MoS2 and WS2 nano-
tube. The first step was to prepare MoS3 precursors via decomposition of (NH4)2

MoS4 at 400 C in an argon atmosphere. Then, the precursors were heated at

1200–1300 C under H2 atmosphere. MoS2 nano-tubes were formed, and the
TEM images are shown in Fig. 6.22. It can be seen that the external diameter of
the nano-tube is about 20–30 nm, and the wall thickness is about 10–15 nm. There
are also some onion-like clusters in the Figure, suggesting the existence of an
intermediate stage between MoS3 precursors and MoS2 nano-tubes (Margulis
et al. 1993). Feldman et al. (1995) used the gas-phase reaction between MoO3
and H2S in a reducing atmosphere at high temperature and also got high-rate growth
of MoS2 nano-tubes.
Fig. 6.20 SEM and TEM images on different length scales. (a) Bundles appear to self-assemble
into various different microscopic structures. (b) The bundles end in sharp points. (c) A split tip of
a bundle terminating in strands 4 nm wide. (d) Expanded electron transmission view of a strand
composed of an only few individual nano-tubes (Remskar et al. 2001)
Fig. 6.21 A TEM image of the MoS2 tubes after the dissolution of the aluminum oxide template
(a). A TEM image of a bend in a tubule of MoS2 emphasizing the hollow nature of the tubules (b)
(Zelenski and Dorhout 1998)
Fig. 6.22 TEM images of MoS2 nano-tubes: (a) Images of several nano-tubes; (b) and (c) high-
resolution images of the nano-tubes; and (d) nested-shell and onion-like clusters with a hollow
core (Nath et al. 2001)
2.3.2 Applications of MoS2 Nano-tubes
Besides the synthesis and characterization of MoS2 nano-tubes, studies have been
focused on a great number of particular properties and applications (Deepak and
172 Y. Xu et al.
Fig. 6.23 Catalytic

abilities of MoS2 nano-
tubes (Chen et al. 2002)
Jose-Yacaman 2010), for instance, mechanical properties (Hassanien et al. 2005),

field emission properties (Nemanič et al. 2003), in hydrogen storage applications
(Chen et al. 2003) and as catalysts (Chen et al. 2002).
Chen et al. (2002) synthesized an open-ended MoS2 nano-tube and used it as the
catalyst of methanation of CO and H2 at relatively low temperatures (Fig. 6.23).
Techniques such as this contribute to new ways of reducing the environmental load
resulting from CO emissions. By analyzing the shear and Young’s moduli of the
MoS2 nano-tubes, Kis et al. (2003) used an atomic force microscope to study the
interaction between the MoS2 nano-tubes, finding the MoS2 nano-tube ropes were
highly anisotropic and very weak.
Chen et al. (2001) prepared MoS2 nano-tubes by heating (NH4)2MoS4 in hydro-
gen/thiophene. They studied the electrochemical properties. It was found that the
highest capacity was 260 mAh g1 because of a highly nano-porous structure,
suggesting a potential application in electrochemical catalysis and high-energy
batteries.
Analogously to MoS2 nano-tube, WS2 nano-tubes, can be used for tips in
scanning-probe microscopy (Rothschild et al. 1999). They have been successfully
applied in the inspection of microelectronics circuitry. With improvements in
productivity for producing these, the application of MoS2 nano-tubes will widen
to include nanolithography, photocatalysis, sensors, and others (Tenne 2006).
MoS2 nano-tubes also have excellent lubricating properties whether as lubricat-
ing oil additives or prepared as self-lubricating composite materials (Mertens and
Senthilvelan 2016; Zhou et al. 2007). However, due to their thin and long structure
and chemical inertness, MoS2 nano-tubes are hard to disperse in lubricating oil
which limits their tribological application. Modification, treatment, or the addition
of a dispersion agent is an effective method to improve dispersion in oil of nano-
tube (Khalil et al. 2016; Chen et al. 2005). Kalin et al. (2012) investigated the
frictional properties of MoS2 nano-tubes as oil additives. They found that the
lubrication mechanism was mainly exfoliation and deformation which was similar
to that of MoS2 nano-balls. Exfoliated nano-sheets were adsorbed onto the rubbing
surfaces, and compacted and deformed to form a boundary film. With these two
combined effects, MoS2 nano-tubes reduce friction and wear significantly.
3 Graphene and Its Tribological Applications
Graphene, just like the structured MoS2, is a 2-D layered material with sp2-bonded
carbon, that has received substantial attention (Novoselov et al. 2004; Li et al. 2009;
Bonaccorso et al. 2015) due to its good conductivity, excellent mechanical proper-
ties, potential applications in electrochemical energy storage (Raccichini et al.
2015), microelectronics, and lubricating additives (Wu et al. 2015; Yao et al.
2014). In this section, the preparation, characterization, and applications of
graphene are reviewed to give a view on the increasingly wide scope of
applications.
3.1 Preparation and Characterization of Graphene
Graphene was firstly prepared by Geim et al. at the University of Manchester in

2004 by using tape (Novoselov et al. 2004). This was the work for which they were
awarded the Nobel Prize in Physics in 2010. From this point, graphene has attracted
substantial research attention such that its synthesis, characterization, its unique
structures, and superior properties are well studied.
3.1.1 Exfoliation in Liquid or Gas
Exfoliation of graphite in liquid or gas is a physical method to obtain graphene.

Hernandez et al. (2008) demonstrated that dispersion and exfoliation of graphite in
N-methyl-pyrrolidone to obtain graphene-blended solutions with a concentration of
0.01 mg ml1. However, the yield of single-layer graphene was low at about 1%.
3.1.2 Modified Mechanical Exfoliation
Recently, in order to improve the yield of production of single-layer graphene, Xu

et al. (2016) used a friction-induced exfoliation from graphite to graphene in
esterified bio-oil. They dispersed flake graphite into the esterified bio-oil and then
measured the tribological response of the dispersed graphite after ultrasonication
for 20 min. Testing was performed on a ring-on-plate tribometer. It was found that
174 Y. Xu et al.
both load and sliding speed had an important effect on the quality of the graphene.
Higher loads and lower sliding speed were helpful to form the single-layer
graphene. In addition, higher loads also contributed to friction and wear reduction
in the tribosystem due to the formation of a thicker tribofilm.
3.1.3 Epitaxial Growth
Due to the low efficiency of the mechanical exfoliation method, epitaxial growth
has become one of the most important methods to produce the graphene film on
certain substrates such as SiC and transition metals (Oshima and Nagashima 1997).
Yang et al. (2013) used a plasma-assisted deposition epitaxial growth method to
obtain the single-domain graphene on hexagonal boron nitride. The graphene was
produced at ~500 C. A schematic illustration of this process is shown in Fig. 6.24,
suggesting a typical edge growth of carbon atoms. The sp2 carbon structure of the
graphene was confirmed by Raman spectra in Fig. 6.24b. The AFM images also
showed the existence of single-layer graphene.
Fumihiko and Hiroki (2011) grew graphene on a SiC (0001) substrate under the
temperatures varying from 600 to 915 C by thermal decomposition of a cracked-
ethanol source. This is an example of one kind of gas-source molecular beam
epitaxy (MBE) methods. The experimental results showed that higher temperatures
were helpful to prepare high-quality single-layer graphene. Unfortunately, the
growth rate decreased with the increase in temperatures. Moreover, there was a
network of fin-like ridge shapes of graphene (Fig. 6.25).
However, the epitaxial growth method for producing graphene has some disad-
vantages. For instance, it requires some harsh conditions, including high tempera-
ture, high vacuum, special atmosphere, and substrates. The synthesized graphene is
also hard to separate from the substrate. It is also hard to produce graphene on a
large scale in the industry.
3.1.4 Chemical Vapor Deposition
Chemical vapor deposition (CVD) has been used to produce high-quality thin films
on substrates in the semiconductor industry. In recent years, this technique has also
been applied to synthesize graphene. The principle is to deposit volatile precursors
onto the substrate.
A single- and few-layer (less than 10) graphene film with a large area (~cm2) was
prepared by Reina et al. over a Ni surface using CVD technology (Reina et al.
2008). But the lateral size was limited to 20 μm. The domain boundaries have
proved adverse to the transport properties. Thus, graphene with a larger area is still
the pursuit of the scientists. Li et al. (2011a) prepared single crystal graphene with a
domain size of up to 0.5 mm (Fig. 6.26), which were grown at low-pressure and
high-temperature chemical vapor deposition (8 mTorr at 1035 C) on copper-foil
enclosures using methane as a precursor. The flow rates and partial pressures of the
6 Nano-MoS2 and Graphene Additives in Oil for Tribological Applications
Fig. 6.24 Schematic illustration of the growth mechanism (a); Raman spectra for hexagonal MLG (h-MLG) grains (red), BLG film (blue), and bare h-BN
surface (black) (b). (c–e) AFM images of as-grown graphene on h-BN at different stages including small grains nucleation (c), coalescence of grains (d), and
continuous monolayer graphene with some second-layer nuclei on top. A height profile was extracted along the dashed white line cut in d, with white and cyan
175
arrows indicating the first and second layer, respectively. The scale bars in c–e are 500 nm. f, g, Zoom-in AFM image of as-grown graphene showing aligned
hexagonal grains (f) or pits after plasma etching (g). The scale bars in f, g are 200 nm (Yang et al. 2013)
176 Y. Xu et al.
Fig. 6.25 Topographic

AFM image of graphene (a)
and the height of the line in
the AFM image (b)
(Fumihiko and Hiroki 2011)
Fig. 6.26 SEM images of

graphene on copper grown
by CVD: Graphene domain
grown at 1035 C on Cu at
an average growth rate of
6 μm/min (a). Graphene
nuclei formed during the
initial stage of growth (b).
High-surface-energy
graphene growth front (c)
(Li et al. 2011a)
KMnO4 +
(NH4)2S2O3 Hydrolysis 30% H2O2 Sonication Reduction Reduced
Stage I graphite Oxidized Graphite oxide Graphene
Graphite graphene oxide
bisulfate(GB I) graphite (OG) (GrО) oxide (GO)
H2SO4 (conc) H2SO4 (conc.) (RGO)
Fig. 6.27 The preparation process of reduced graphene oxide (Tkachev et al. 2012)
methane were less than 1 sccm and 50 mTorr, respectively. The transport properties
of the graphene film were measured, and the mobility of the films was found to be a
little bit higher than 4000 cm2 V1 s1, indicating further improvements for this
graphene film should be possible.
CVD methods can produce high-quality graphene with a large area, with the
products easily separated or transferred from substrates. In addition, CVD-derived
graphene can be processed at relatively low temperatures and ambient pressure.
However, the thickness of the graphene is hard to control and the yield remains low.
3.1.5 Reduced Graphene Oxide
A reduced graphene oxide method for the production of graphene in aqueous

solution has attracted great interests due to its low cost, easy processability, and
high efficiency. The process includes three steps: (1) preparation of oxide graphite
from graphite using strong oxidants such as concentrated sulfuric acid, concentrated
nitric acid, and potassium permanganate; (2) ultrasonic process for separating the
lattices of oxide graphite; (3) reduction of the graphene oxide with reducers such as
hydrazine hydrate and sodium borohydride.
Tkachev et al. (2012) used a modified Hummers method to prepare graphite
oxide and then synthesized the graphene oxide by ultrasonic processing. The final
reduced graphene oxide was obtained after the appropriate amount of graphene
oxide and ethanol was mixed and reacted at 200–380 С for 10–90 h. A typically
detailed process for preparing reduced graphite oxide is shown in Fig. 6.27.
3.2 Properties and Applications of Graphene
Graphene has become a star molecule over the last c.10 years because of the ability
to its particular structure and properties such as electrochemical, mechanical, and
other properties. The progress of the main properties of graphene is reviewed in this
section.
3.2.1 Electrochemical Properties
Electrons in graphene have a character that can be described by a linear dispersion

relationship. It has been confirmed that at room temperature the electron mobility of
178 Y. Xu et al.
single-layer graphene amounts to 15, 000 m2 V1 s1. Therefore, graphene has
many potential applications in microelectronic devices (Geim and Macdonald
2007). Geim and Macdonald (2007) noted that the conductivity of graphene was
much higher than that of single-walled carbon nano-tubes by about 60 times. In
addition, they found that graphene had higher surface negative charge, better
stability, and signal-to-noise ratio than single-walled carbon nano-tubes, indicating
the potential of graphene in the detection of some small molecules such as dopa-
mine and serotonin by graphene electrodes.
Shan et al. (2016) used graphene to increase the conductivity and electrochem-
ical stability of MoS2 since MoS2 has a high theoretical specific capacity (about
670 mA h g1) but low cycle charging performance. A unique film–foam–film
structure was designed to solve this problem. The experimental results showed that
the appropriate structures resulted in a high, reversible Li storage capacity of
1200 mA h g1 and a longer lifetime, suggesting its potential application in high-
energy-density batteries.
3.2.2 Mechanical Properties
With the potential application of graphene in nanoelectromechanical systems, the

mechanical properties of monolayer or few-layer graphene (less than 5) have
aroused great interest. Frank et al. (2007) used an atomic force microscope to
measure the effective spring constants of the graphene sheets with a thickness
between 2 and 8 nm ranging from 1 to 5 N m1 and Young’s modulus of graphene
sheets is 0.5 TPa, which is a half of bulk graphite.
Young’s modulus was studied by molecular dynamics and was predicted higher
than 1 TPa (Van Lier et al. 2000). According to Lee et al. (2008) and Zhu et al.
(2010), Young’s modulus and fracture strength of a defect-free graphene were
1.0 TPa and 130 GPa, respectively, being measured by an AFM indentation
approach (Fig. 6.28).
3.2.3 Optical Properties
Of main interest for graphene is the comparison of the permittivity features.

Falkovsky (2008) investigated the transmittance of graphene in the optical region
and found that optical properties were affected by the interband electron transitions.
Moreover, the transmittance of graphene in the visible spectrum range was not
affected by the frequency and had a constant value depending on its fine structure.
3.2.4 Extreme Pressure Properties
The extreme pressure value (PB) of oil is an important parameter when evaluating
the load carrying capacity of lubricating oil. Nano-scale lubricating particles being
Fig. 6.28 Images of graphene membranes: SEM images of a large graphene flake spanning an
array of circular holes 1 μm and 1.5 μm in diameter. Scale bar, 3 μm (a). Non-contact mode AFM
image of one membrane (b). Schematic of nanoindentation on suspended graphene membrane (c).
AFM image of a fractured membrane (d) (Lee et al. 2008)
Fig. 6.29 Effect of concentration of MoS2 nano-sheets (left) (Hu et al. 2009a) and graphene
(right) on the PB value (Lin et al. 2010)
mixed with oil can penetrate into rubbing surface during sliding and protect rubbing
surfaces from contacting directly and can form an adsorbed layer. Because of the
excellent antiwear properties, nanoparticles with a low concentration can improve
PB values significantly. As shown in Fig. 6.29, comparing with the base oil or base
oil with flake graphite, MoS2 nano-sheets and graphene can increase PB value to
approximately 2 and 1.6 times, respectively, at optimum concentrations (Hu et al.
2009a; Lin et al. 2010).
180 Y. Xu et al.
3.2.5 Dispersion Properties
The advantage of nanoparticles is that they can penetrate into mating surfaces
during the frictional process even in severe boundary lubrication. However,
nanoparticles tend to agglomerate due to nanometric size effects. The size of the
agglomeration might amount to a few microns which make the particles much less
likely to penetrate into frictional interfaces, and so they cannot reduce the friction
and wear of the tribosystem. Therefore, the dispersive properties of the nano-
lubricating additives are very important. Modification treatments are a chemical
reaction method to graft a modifier on the nanoparticles to improve the dispersive
properties. The modifiers commonly have an oleophylic functional group of long
chain alkane. Although graphene has excellent tribological properties, the disper-
sion of graphene in oil is poor which leads to coagulation and precipitation of
graphene quickly because of chemical inertness.
The modification is an effective approach to forming stable dispersions and
preventing aggregation of graphene. Lin et al. (2010) modified graphene by using
stearic and oleic acids. The modifiers, cyclohexane and dried graphene, were
heated and stirred at 80 С for 5 h. There were some residual oxygen-containing
functional groups, as a result of the incomplete diminution of reduced graphene
oxide, that could react with carboxyl groups of stearic and oleic acids. Therefore as
a result of the long chain molecular structures of stearic and oleic acids, modified
graphene has better dispersive properties than the pristine graphene as shown in
Fig. 6.30.
Fig. 6.30 Dispersive stability of graphene in lubricating oil (Lin et al. 2010)
3.2.6 Tribological Properties and Applications of Graphene
Graphene has excellent tribological properties as lubricating oil additive in part due
to its layered structure similar in many respects to MoS2. Eswaraiah et al. (2011)
synthesized ultrathin graphene with a thickness of ~2 nm via reducing graphene
oxide with focused solar radiation. The tribological properties were investigated by
using a four-ball tribometer. They found that the ultrathin graphene dramatically
reduced average coefficient friction and wear loss at a relative low concentration in
a formulated engine oil as shown in Fig. 6.31. Also, graphene can significantly
improve the load capacity of a lubricant owing to its excellent antiwear perfor-
mances especially at a concentration of 0.025 mg mL1. In addition, graphene in
the base oil could be adsorbed on the frictional interfaces and formed a physically
adsorbed film. The adsorbed film protected the rubbing surfaces and reduced wear
and the coefficient of friction.
According to the results in Fig. 6.31, graphene has an optimal concentration. The
antifriction and antiwear behaviors deteriorated when the concentration of
graphene exceeded the optimal concentration. This can be explained by the fact
that graphene can form an adsorbed film protecting frictional interfaces at an
Fig. 6.31 Tribological properties of graphene dispersed in engine oil: Coefficient of friction (a),
wear scar diameter (b), and load capacity (c) (Eswaraiah et al. 2011)
182 Y. Xu et al.
Fig. 6.32 Schematic of the lubrication mechanisms of graphene as oil additives at different
lubricating states (Zhang et al. 2011)
optimal concentration. However, when the concentration exceeded the critical

value, the lubricating oil in the friction region is reduced by the aggregation of
graphene, which makes the oil film discontinuous and reduces the lubricating
effects. The corresponding lubrication mechanisms of graphene as an oil additive
in the different lubricating state are shown in Fig. 6.32 (Zhang et al. 2011).
4 Synergistic Lubricating Behaviors of Graphene

and MoS2
Previous studies (Kalin et al. 2012; Wang et al. 2014; Rabaso et al. 2014b; Marquart
et al. 2013; Kogovšek et al. 2013; Zhang et al. 2012; Xu et al. 2015b) have shown
that the tribological mechanisms of MoS2 are interlayer slippage, rolling deforma-
tion, and a slippery exfoliation. But the MoS2 particles are easily removed during
the frictional process, which affects their long-term effects. Considering good
adhesive and lubricating properties of graphene (Lin et al. 2011; Kandanur et al.
2012; Berman et al. 2013; Zhang et al. 2014; Fan and Wang 2014), the joint use of
graphene and MoS2 seems to be a good choice. Currently, graphene/MoS2 com-
posites have been selected as a photoresponsive coating (Huang et al. 2014),
electrochemical sensors (Feng et al. 2014), catalyst supports (Zhai et al. 2015)
and for lithium storage (Ma et al. 2014). Xu et al. (2015a) have systematically
(a) 1.0
0.9 (b)
Average Friction coefficient
0.060 WSD of Stationary ball
WSD and WSW (mm)

0.8
WSW of Rotational Ball
0.048 0.7
0.6
0.036
0.5
0.024 0.4
0.3
0.012 0.2
0.1
0.000
0:0 0:1 1:4 2:3 1:1 3:2 4:1 1:0 0.0
0:0 0:1 1:4 2:3 1:1 3:2 4:1 1:0
Graphene/MoS2 Graphene/MoS2
Fig. 6.33 Average friction coefficient (a) and WSD and WSW (b) of graphene and MoS2
dispersed in base oil with different mass ratio (Xu et al. 2015a)
studied the lubricating properties of graphene/MoS2 composites; the results and

tribological mechanisms are reviewed in detail in the following sections.
4.1 Tribological Behaviors
Tribological tests were performed on a four-ball tribometer. The dispersive media

was bio-oil and detailed frictional conditions were as follows: concentration of the
additives: 0.5 wt%; Load:300 N; Rotating speed: 1000 rpm; Sliding time: 30 min.
As shown in Fig. 6.33, the MoS2/graphene composite had a lower friction coeffi-
cient and wear loss including wear scar diameter (WSD) and wear scar width
(WSW) than MoS2 or graphene. This suggested a clear synergistic lubricating
role of graphene/MoS2 composites.
The effect of the loads on the tribological behavior of the graphene/MoS2
composite is shown in Fig. 6.34. The friction coefficient, WSD and WSW of
esterified bio-oil (EBO), increased with load, due to the smaller micro-intervals
between the friction pairs under higher loads (Xu et al. 2014b). There was a great
decrease in the friction coefficient and wear loss of the EBO with graphene/MoS2
composite additives, up to 300 N. Exceeding this load, the friction coefficient and
wear loss remained stable or increasing. At the same time, for the same load, the
EBO with graphene/MoS2 composite additives showed the best lubricity in all the
four lubricants. This confirms the synergistic lubricating effects between graphene
and MoS2.
4.2 Friction and Wear Mechanisms
In order to explore the friction and wear mechanisms of the graphene/MoS2

composites, XPS spectra of the typical elements on the rubbed surfaces are
184 Y. Xu et al.
0.08
1.0
(a)
Average friction coefftcient
0.07 (b)
0.06 0.8
WSD (mm)
0.05
0.6
0.04
0.03 0.4
0.02
0.2
0.01
0.00 0.0
100 200 300 400 500 100 200 300 400 500
Load (N) Load (N)
1.0
(c)
0.8
WSW (mm)
0.6
0.4
0.2
0.0
100 200 300 400 500
Load (N)
Fig. 6.34 Average friction coefficient (a), WSD (b), and WSW (c) of steel specimens under
different loads (Xu et al. 2015a). Notes: Filled star EBO; Filled circle EBO+0.5 wt% graphene;
Filled square EBO+0.5 wt% MoS2; Filled triangle EBO+0.3 wt% graphene+0.2 wt% MoS2
shown in Fig. 6.35. The position of the two C1s peaks suggested the existence of
carbon or sp3 C (C–C/C–H) and sp2 C (C¼C/C¼O) (Xu et al. 2014a), respectively.
This indicated that the adsorbed film was made from carbon or organics, coming
from the graphene or base oil. The largest areas of C1s peaks of graphene/MoS2
blends suggested the formation of the thickest adsorbed film containing graphene
and organics. The O1s peak can be ascribed to hydroxides or sulfates, confirming
the existence of an adsorbed film with organics or a tribo-film with sulfates. The
O1s peak at 530.3 eV was attributed to Fe2O3, suggesting the tribo-oxidation of the
substrate during sliding. The Fe2p peaks belonged to Fe2O3, and no simple Fe0 peak
was found, confirming the existence of a complete tribo-oxide film on the rubbing
surfaces. The Cr2p peaks belonged to Cr2O3 and CrN, respectively. This confirmed
a tribo-oxidation and tribo-reaction during the sliding process.
For graphene/MoS2 lubrication, the two main Mo3d peaks at 232.6 and 235.8 eV
were ascribed to MoO3 (Hu et al. 2009b). Another peak at 229.7 eV was ascribed to
Mo3d of MoS2, but this peak was not detected for MoS2 lubrication. Moreover, the
two S2p peaks at 169 eV and 161.6 eV were indexed to SO42 and MoS2,
respectively (Moulder et al. 1995). When MoS2 was used independently (c), the
peak at 161.6 eV in the curve was very weak, suggesting that MoS2 was easily
(b) 532 530.3

(a)
C1s 284.8 O1s
288.7
Isp /Isp =9.95/1
3 2
Intensity (a.u.)
(d)
Intensity (a.u.)
(d)
2
sp C(C=C/O) Isp /Isp =7.68/1
3 2
(c)
Ia/Ib/Ic/Id=1/1.77/1.34/3.51 (c)
3
sp C(C-C/H) Isp /Isp =7.32/1
3 2
(b) (b)
Ia/Ib/Ic/Id=1/1.55/1.12/2.55
Isp /Isp =6.39/1
3 2
(a) (a)
300 297 294 291 288 285 282 279 276 542 540 538 536 534 532 530 528 526 524 522
Binding energy (eV) Binding energy (eV)
(c)
Fe2p (d)
Cr2p 585.9 576.1
724.5 710.9 586.7 576.9
584.2
574.4
719.7
Intensity (a.u.)
Intensity (a.u.)
(d)
707 (c)
(d)
(c) (b)
(b)
(a)
(a)
744 736 728 720 712 704 696 595 590 585 580 575 570 565
(e)
Mo3d (f)
S2p 169
232.6
235.8
Intensity (a.u.)
Intensity (a.u.)
161.6
(d)
229.7
(d)
(c)
(c)
240 236 232 228 224 220 177 174 171 168 165 162 159 156 153
Fig. 6.35 XPS spectra of the worn surfaces of the rotating specimen lubricated by base oil (a),
base oil with graphene additives (b), base oil with MoS2 additives (c), base oil with graphene/
MoS2 composite additives (d) (Xu et al. 2015a)
oxidized during sliding. That is, the introduction of graphene was helpful to the
adhesion of the MoS2 on the frictional surface and further prevents the oxidation of
MoS2.
The friction and wear mechanisms were summarized as follows. For graphene,
the main antifriction and antiwear components were the small graphene particles,
and ploughing was the dominant form of wear. For MoS2, the MoS2 with the
smaller surface area was the main lubricant but it is easy to be removed from the
186 Y. Xu et al.
frictional surface or oxidized. For graphene/MoS2 composites, a thicker tribo-film

was formed to play an antifriction and antiwear role. The synergistic lubricating
effect of graphene and MoS2 allows complete graphene and unoxidized MoS2 to
remain on the sliding surfaces.
5 Conclusions
In summary, in this chapter, two kinds of nano-additives MoS2 and graphene have
been reviewed. The preparation methods, properties, and applications have also
been discussed. Both MoS2 and graphene have various functions and applications
and their tribological properties have been explored this chapter. For MoS2, differ-
ent structures have different physical properties. Nano-MoS2 showed obvious
advantages over the more conventional micro-MoS2. In a widely accepted opinion,
rolling is the main antifriction and antiwear mechanism for nano-MoS2 particles.
The slippery role is the friction-reducing mechanism of MoS2 nano-sheets and the
combined actions of rolling and sliding account for the excellent lubricating effect
of MoS2 nano-tubes. However, exfoliation and transfer cannot be ignored when
explaining the tribological behaviors of nano-MoS2. More combined applications
of nano-MoS2 with different structures require further study.
As for graphene, good adsorption onto the frictional surfaces is helpful to the
lubricating behaviors of graphene. However, the effects of the layer, area, and
defects in the graphene on the tribological behaviors still remain unknown and need
further clarification in the future. The graphene/MoS2 composites showed excellent
synergistic lubricating effect. The mechanisms were attributed to the protective
roles of the graphene preventing the oxidation of MoS2 and also MoS2 preventing
graphene being destroyed and reduced into small, defective additives. The MoS2
used in the composites was micro-MoS2, nano-MoS2 composites needed to be
studied further. To conclude, both graphene and MoS2 as lubricating additives
have a bright future and more specialized applications will be researched and found.
Acknowledgements This work was supported by the National Natural Science Foundation of
China (Grant No. 51405124), and the Tribology Science Fund of State Key Laboratory of
Tribology, Tsinghua University (Grant No. SKLTKF15A05). In the UK, the research was
supported by the Engineering and Physical Sciences Research Council, grant number
EP/L017725/1.
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Chapter 7
Hydrodesulfurization (HDS) Process Based
on Nano-catalysts: The Role of Supports
Alimorad Rashidi, Fatemeh Mohammadzadeh,

and Sedigheh Sadegh Hassani
Abstract Nowadays, market demand of middle distillate such as naphtha, kero-

sene, and diesel fractions with low sulfur content is augmented. Sulfur oxides which
are released to the air by combustion of this kind of fuels are one of the critical
problems of the environment. Hydrodesulfurization (HDS) is one of the most
important catalytic processes which have been offered for solving these kinds of
difficulties.
Conventional HDS catalysts are MoS2 together with some metals from the
transition metal series supported on γ-Al2O3 that are promoted by either cobalt or
nickel.
A lot of research has been focused on HDS catalysts improvement for different
industries, where they investigated various catalyst supports, active phases, and
catalyst synthesis methods.
Recently, nano-materials are extensively used for catalytic HDS process. Carbon
nanostructures such as carbon nanotubes (CNTs) draw scientists’ attention because
of their high mechanical strengths, purities, and thermal stability.
In this work, an overview of HDS process and various types of catalysts for
removal of sulfur compounds from fuels is indicated. In addition, improved cata-
lysts using nanotechnology including carbon nanotubes, graphene, and nano-
alumina are investigated.
Keywords Hydrodesulfurization • Nano-catalyst • Carbon nanotubes • Graphene •

Nano-alumina • Sulfur compounds
A. Rashidi (*) • S. Sadegh Hassani

Nanotechnology Research Center, Research Institute of Petroleum Industry, Tehran, Iran
F. Mohammadzadeh
Process Engineering Section, Petroleum Engineering Department, Iranian Offshore Oil
Company, Tehran, Iran

194 A. Rashidi et al.
1 Introduction
In the last few decades, requirements to healthier and cleaner transportation fuels
have become one of the most important subjects of discussion. Natural gas, fossil
fuel, and some refined petroleum products (gasoline, kerosene, fuel oils, and diesel
fuel) contain various sulfur compounds such as sulfides, thiols, thiophenes,
benzothiophenes, and alkyl-substituted derivatives, most of which come from
fluid catalytic cracking (FCC) unit (Babich and Moulijn 2003). These compounds
not only are dangerous for the environment but could also poison the reforming
catalyst and corrode the refinery equipment. In 2005, the European Union and US
regulation restricted the sulfur content in gasoline and diesel to 30–50 ppm, while
this amount was reduced to 10 ppm in 2010 (Deng et al. 2010) and it is expected to
be less than 5 ppm in 2020 (Castillo-Araiza et al. 2015). On the other hand, the
demand for high-quality petroleum grows up increasingly.
Implementation of environmental legislation to enhance the quality of oil along
with market demand for low sulfur gasoline and high octane number has made great
efforts to improve the quality of fuels. Hydrotreating process (HDT) which includes
a sequence of important processes such as hydrodesulfurization (HDS),
hydrodenitrogenation (HDN), and hydrodearomatization (HAD) for light and mid-
dle distillates, and hydrodemetallization (HDM) and hydrodeasphaltenization
(HDAs) for heavy oils are fundamental techniques to remove or decrease sulfur
components. These processes lead to more qualified productions and feedstocks
(Nikulshin et al. 2016).
Middle distillate fraction has been more interest due to the importance of
producing clean gasoline, jet and diesel fuels, and kerosene for the environment.
Hence, many researchers have been focused on the sulfur removal from engine fuel
using catalytic hydrodesulfurization process.
2 Hydrodesulfurization Process
Hydrodesulfurization (HDS) is an important catalytic process in which the sulfur

compounds are converted to hydrocarbons and hydrogen sulfide that can easily be
separated from natural gas and refined petroleum products; in this way, sulfur
dioxide (SO2) emissions from fuel combustion can be decreased.
Sulfur, even in low concentrations, poisons the precious metal catalysts (plati-
num and rhenium) in the catalytic reforming units which are used to upgrade the
octane rating of the naphtha streams.
In this regard, in the industrial HDS process, the resulted hydrogen sulfide (H2S)
gas has been converted to sulfuric acid (H2SO4) and elemental sulfur.
The general conditions for HDS process are, temperature: 500–825 F, hydrogen
pressure: 150–3000 psig, hydrogen flows: 250–10000 SCF/bbl, feed space velocity:
0.5–5.0 volumes of liquid per volume of catalyst per hour (Schuman and Shalit
7 Hydrodesulfurization (HDS) Process Based on Nano-catalysts: The Role of Supports 195
1971). The process conditions depending on the type of cutting oil and its sulfur
compounds will be different. The fraction boiling up to 160 C usually contains
alkane thiols, aliphatic sulfides, and alicyclic sulfides that easily react with hydro-
gen in conventional hydrotreating process and completely removed. More complex
thiophenes and bicyclic sulfides are found in higher boiling fractions. These
compounds are more difficult to convert via hydrotreating. Hydrodesulfurization
mechanism of thiophenic compounds is carried out via two pathways. In a first way,
the sulfur atoms are directly removed from the ring and in this way, the ring is
broken (hydrogenolysis pathway). In a second way, the aromatic ring is hydroge-
nated and then sulfur atoms are removed (hydrogenation pathway). Both pathways
occur simultaneously and some parameters such as feed compound, reaction con-
dition, and type of catalyst determine the predominant reaction (Babich and
Moulijn 2003). Experimental results show that acidic supports facilitate the ring
opening of hydrogenated intermediates and thus are suitable for this procedure
(Santes et al. 2005). Many studies have been conducted to investigate the mecha-
nism of HDS reactions through the integration of experimental results with the
theoretical models (Krebs et al. 2008).
Thermodynamic data for the hydrogenation of sulfur compound which leads to
the production of hydrocarbons and hydrogen sulfide shows that this reaction is
possible thermodynamically over a wide range of temperatures. Nevertheless, the
hydrogenation behavior of various sulfur compounds is probably different from the
standpoint of thermodynamic, for example, the hydrogenation of saturated sulfur
compound is favored at high temperature while increasing the temperature will
decrease the thermodynamic driving force for thiophens. However, there is no
thermodynamic limitation for hydrogenation of diverse sulfide compounds,
although decreasing the reaction rate and the interference of competitor reactions
cause problems in the implementation of the process (Schuman and Shalit 1971).
In this conventional process which is run out industrially, the warm oil fraction is
mixed with hydrogen gas and then passed through the catalytic reactor; in this way
the sulfur compounds with various structures and molecular weight are
hydrogenated.
In the most usual cases, HDS process is carried out in fixed bed reactors with the
cocurrent supply of oil stream and hydrogen. This reactor structure design causes to
produce a mixed gas with inappropriate relative concentration. The high concen-
tration of H2S at the outlet reactor inhibits the complete sulfur removal (Babich and
Moulijn 2003). Furthermore, the relatively large size of catalyst used in fixed bed
reactor causes pressure drop and decreasing the internal diffusion and production of
extreme heat because of exothermic reactions which can lead to creating hot spots
and catalyst deactivation consequently.
In the recent years, some of the refining units exploit slurry reactors due to some
advantages including simple construction and lower cost, efficient temperature
control, less pressure drop, better performance of the catalyst, discharging the
used catalysts, and bringing the fresh catalysts concurrently (Deng et al. 2010).
Countercurrent operation is another new reactor system that could provide a
preferable concentration profile. In this system, the oil feed is entered into the
reactor at the top and the hydrogen gas at the bottom and H2S gas is removed at the
top that prevents the reentry at the reactor outlet. The ebullated bed reactor is
another type of HDS reactor that is designed especially for heavy refinery steams.
This reactor benefit is good heat transfer and less coke formation. In another new
approach, a combination of hydrotreating with other reactions as aromatizing and
octane boosting is taken into consideration (Babich and Moulijn 2003).
Non-HDS based desulfurization technology is another approach that does not
use hydrogen for desulfurization of sulfur compound from oil. In this way, sulfur is
removed by shifting the boiling point through alkylation, extraction, adsorption,
precipitation, and selective oxidation methods (Babich and Moulijn 2003).
Researchers try to promote the HDS process via different aspects such as
construction of catalysts with high activity and lifetime, improving the design of
reactors, and recently using a new internal catalyst to realize countercurrent flow
(Deng et al. 2010; Song and Ma 2003).
3 Industrial HDS Catalysts and Their Activity
A well-known catalyst which is traditionally used in HDS process is Co–Mo, Ni–

Mo or W crystallites that are well dispersed over alumina support (El Kady et al.
2010). The binary sulfide catalysts are highly regarded too because these systems
cause very strong catalytic synergies. For example, individual Mo or Co sulfides
shows very low activity as an HDS catalyst, but when combine to each other present
very high activity (Okamoto 2008). A complete review of preparation of catalyst
methods for HDS process is presented in some papers (Toulhoat and Raybaud 2013;
Souchay 1969; Von Pope 1983; Campos-Martin et al. 2009; Vrinat et al. 2005; Dhar
et al. 2003). In order to reduce the sulfur content of diesel and gas oil fuels, less than
15 ppm and 10 ppm, respectively (Bigdeli and Fatemi 2015; Michel et al. 2012),
catalysts with higher strength are required.
The development of new catalysts is required for the optimization of HDS
process. The synthesis method, activation procedure, type of support and active
compound, promoter and posttreatment can affect the catalyst performance.
It is proven that sulfur and olefin compounds compete with each other on the
catalyst and this is while hydrogenation of olefins causes to drop in octane number.
Therefore, to keep a high octane number it is necessary to eliminate or limit the
olefins reaction by using selective catalysts (Fontaine et al. 2010).
Improving selectivity has a key role in catalyst performance and could be
fulfilled by adding diverse promoters to the catalyst composition (Mey et al.
2004), poisoning the hydrogenation sites selectively (Hatanaka 2005), balancing
the basic–acidic properties of the support, and the amount of H2S in feed (Fontaine
et al. 2010). However, it should be noted that increasing the amount of H2S has an
inhibiting effect on both hydrodesulfurization and hydrogenation of olefins.
Type and quality of support also lead difference in catalyst performance via
dispersing active component over and affecting the metal–support interaction
which in turn influence the catalyst functionalities. In order to select of an appro-

priate catalyst some criteria such as promoting effect on the active phase are
important. For example, Co and Ni sulfides effects on active phase of MoS2 lead
to the formation of “CoMoS” or “NiMoS” phases, respectively (Toledo-Antonio
et al. 2009).
Moreover, surface area, thermal stability, pore diameter, pore volume, geomet-
rical functions, acidity, and mechanical strength are considered as key parameters
for catalyst performances. Many materials were studied and experimental results
showed that γ-Al2O3 is an ideal support with favorable characteristics, because it
possesses high surface area, thermal stability, and regeneration. Also, its pore
structures can be controlled simply (Nikulshin et al. 2014). However, the severe
interaction between alumina and catalytic metals occurs that causes difficult
sulfidation of components. Furthermore, acidic and basic sites on this support
form coke (Stanislaus et al. 2010).
Generally, two types of sites are observed on traditional catalysts based on Al2O3
support: monolayer MoS2 slabs that are so-called Type I and multilayer or highly
stacked MoS2 slabs which named Type II (Toledo-Antonio et al. 2009). Type II of
CoMoS or NiMoS is a highly active site (Nikulshin et al. 2014) because strong
bonds between molybdenum and the support are observed (Coelho et al. 2014)
while the majority of sites belongs to the type I in alumina-supported catalysts.
However, it is extremely complicated to constitute them.
In order to form these active slabs, increase Mo oxides dispersion, improve
catalyst acidic characteristics, and reduce the interaction between catalysts compo-
nents and supports, some additives like P and B are applied (Villarroel et al. 2009;
Klimova et al. 2010; Dumeignil et al. 2006; Ferdous et al. 2004; Robles et al. 1999).
The other materials like MgO (Trejo et al. 2008), C (Nikulshin et al. 2014), TiO2
(Guo et al. 2013), SiO2 (Valencia and Klimova 2011; Gutiérrez and Klimova 2011),
ZrO2 (Vrinat et al. 1994), zeolite-like Na-Y, USY, and hybrid of alumina with them
(Saih et al. 2005; Ren et al. 2016; Cui et al. 2013) exhibit superior performance as a
support. Some of these oxides such as ZrO2 and TiO2 represent good reactivity
(Escobar et al. 2008). For example, in Mo/TiO2 catalysts, TiO2 has a role as an
accelerator in reduction and sulfidation of Mo because of its redox and semicon-
ducting characteristics (Caero et al. 2003). However, because of their low surface
area, weak thermal stability, and unfavorable mechanical characteristics, their
commercial application is restricted (Faro and dos Santos 2006).
Investigation shows that mixed oxides (TiO2/Al2O3 and ZrO2/Al2O3) are suit-
able as a support due to their larger surface area than the oxides alone (Robles et al.
1999). However, catalysts based on mixed oxides are deactivated fast.
4 Nano-catalyst in HDS Process
Recently, nanotechnology has been extensively considered as a useful technology

in various industries and preparation of nano-materials has attracted more and more
attention (Gutiérrez and Klimova 2011; Mohammadi Meman et al. 2014; Morales-
Ortũno et al. 2015). Thus, many reports have been published about the synthesis of
nano-materials and many kinds of nano-catalysts for developing the HDS process.
Nano-particles with the high surface area as active phase of catalysts are
extensively used for catalytic reactions (Aghabozorg et al. 2015).
Parviz et al. (2011) reported preparation of unsupported MoO3 and Co–MoO3
catalysts in the presence of different organic additives such as urea (CO(NH2)2),
PEG200 (HO(C2H4O)nH), EDTA (C10H16N2O8), and sorbitol (C6H14O6). Various
kinds of MoO3 microstructures and nanostructures were obtained by utilizing
different additives. They clearly showed that nanostructure and promoted catalysts
had excellent response in the hydrodesulfurization reaction of naphtha than micro-
structure catalysts. They observed that the amount of sulfur of the feed was reduced
from 2420 to 24 ppm when urea-prepared promoted catalyst was utilized.
Ren et al. (2016) studied HDS of dibenzothiophene and
4,6-dimethyldibenzothiophene feed on NiW-ETS-10/Al2O3 and NiW-ETS–Ti
Reach /Al2O3 (ETS-10 is the microporous titanosilicate) catalysts at 260 C.
They recognized the WS2 slabs of NiW-AT-ETS/Al2O3 had an average length of
2.66 nm and layer number of 3.3 nm which showed more slabs and shorter slab
length than the original one. They demonstrated that weak interaction between WS2
as active phase and alumina supports was due to the presence of Ti species. They
also reported that NiW-ETS–Ti Reach/Al2O3, which was named as NiW-AT-ETS/
Al2O3, had higher activity in HDS of DBT and 4,6-DMDBT. They supposed that
shorter length of WS2 active phase leads to higher stacked layers and better
dispersion of active sites on support in comparison of NiW-ETS-10/Al2O3 which
was named as NiW-ETS-origin/Al2O3 were the reasons for 96.5% and 86.9%
activities of DBT and 4,6-DMDBT hydrodesulfurization, respectively.
5 Types and Roles of Supports
5.1 Nano-alumina Support
The potential of alumina support in catalytic activity can be improved by control-

ling its size and morphology in the mesopore size (Lee et al. 2016; Rashidi et al.
2010, 2012). In this regard, by altering the physical and chemical properties of
support, the activity and selectivity of prepared catalysts can be optimized
(Aghabozorg et al. 2015).
F. Rashidi et al. have prepared some new catalysts using micro- and nano-
alumina support with CoMoP and CoMoB active metals in hydrodesulfurization
Fig. 7.1 TEM micrograph of the nano-γ-Al2O3 prepared with 2-propanol and sulfuric acid
Fig. 7.2 HRTEM images on nano-catalysts Co–Mo/nano-alumina
of straight-run light gas oil (SRLGO) with 13500 ppm sulfur compounds (Rashidi
et al. 2013). TEM micrographs of the nano-γ-Al2O3 prepared with 2-propanol and
sulfuric acid are shown in Fig. 7.1. Also, Fig. 7.2 shows HRTEM images on nano-
catalysts Co–Mo/nano-alumina.
Synthesized nano-alumina support was characterized using Accelerated Surface
Area and Porosimetry System (ASAP), where the surface area, pore size, and pore
volume are compared with commercial alumina support and presented in Table 7.1.
Also, the synthesized catalyst performance was investigated and compared with
the commercial catalyst. They stated that presence of P and B in the catalyst
structure increased the acidity of the catalyst by diminishing the interaction
between metals and support and also caused Co metals placed on the edge of
MoS2 particles.
Table 7.1 Physical properties of the supports

Sample Surface area (m2/g) Pore volume (cm3/g) Pore size (Å)
New nano-γ-Al2O3 403.05 1.69 104.59
Commercial-γ-Al2O3 246.20 0.50 70.30
They claimed that among the prepared catalysts, CoMoPB/nanoAl2O3 with a

better dispersion of Mo and Co showed the higher activity than others and was able
to decrease the sulfur content of diesel fuel to below 10 ppm.
They attributed the gasoil HDS activity to the stacking number and Co/Mo ratios
of the CoMoS sites of the catalysts. They deduced that the active species of CoMoS
II placed on the edges of MoS2 slabs. In addition, they found that higher Co/Mo
ratio caused higher Co efficiency. These results lead to the further HDS respon-
siveness. Also, Co and Mo dispersion and the stabilization of metals were improved
via acidic nature of nano-alumina.
Liu and coworkers’ (2012) experiments displayed higher HDS response for
4,6-DMDBT when bimodal mesoporous nanorod γ-Al2O3 support was prepared
by the hydrothermal process. They used different quantities of PEG for better
γ-Al2O3 crystal growth. Their studies indicated that supports with a higher amount
of PEG (24 g PEG) had higher stacking layer number and higher activity. Their
experiments revealed that bimodal mesoporous nanorod alumina had high surface
area, lower lattice defects, and lower support interactions. This reason led to the
higher dispersion of active phases and increasing the acidic sites. They reported that
CoMo-BMA-4 had 98.5% conversion.
Wang and coworkers (2016) synthesized mesoporous alumina supports with
crystal forms of γ, θ, and δ using boehmite sol and PEG and tested them in
hydrodesulfurization of DBT and 4,6-DMDBT and compared their activities with
commercial one. The θ and δ were obtained by thermal treatment of γ-alumina at
high temperatures. They discovered that NiMo/δ-Al2O3 had higher conversion and
catalytic response in all cases (99.6% conversion of DBT and 65.8% conversion of
4,6-DMDBT) at 613 K, 4.0 MPa, 200 ml/ml (Hydrogen/oil), and 150/h. They
expressed several reasons for these phenomena. For example, characterization
results declared δ-Al2O3 supports had a larger pore size (18.3 nm), surface area
(114 m2/g), and pore volume (0.56 cm3/g) than the other supports. They had open
pore channel so Ni–Mo metals could be impregnated easier in these channels. It
caused better dispersion and stacking of a number of active sites over these
catalysts.
This kind of prepared catalyst with moderate acid sites could facilitated the
transformation of the reactants to the active sites and thus improved HDS of DBT
and 4,6-DMDBT. Also, appropriate textural properties and suitable metal support
interaction (MSI) of NiMo/δ-Al2O3 were reported.
5.2 Carbon Nanotubes Support
Also, carbon nanotubes (CNTs) as a novel nano-material are promising candidates

because of their special properties such as high surface area (300–1500 m2/g),
thermal stability, high mechanical strength, electronic properties, and several
adsorption sites (Thi Vu et al. 2012; Nakhaei Pour et al. 2010; Graham et al. 2009).
Generally, they are classified in two groups, single-walled which are monolayer
graphene sheets that are rolled into a cylinder and multiwalled carbon nanotubes
that contain rolled up multilayer graphene with diameters from 2 to 25 nm. Before
hydrogenation process, the ends of the multiwall or single wall CNTs are opened
for catalyst application (Yu et al. 2008). Several kinds of nano-particle such as Pt
and Pd (Kiani et al. 2013) can be entered in and/or deposited on the CNTs structure
to improve their activity as catalysts.
In Pawelec et al. article (2006), CNT supported CoMo catalysts performance had
comprised with activated carbon or γ-Al2O3 supported catalysts in HDS of thio-
phene or dibenzothiophene. It was reported that CoMo/CNT had supreme activity
due to their nanosized and electron donor aspects.
Nakhaei Pour et al. (2010) compared Co–Mo/SWCNT and alumina
Co–Mo/γ-Al2O3 as the catalyst supports during hydrodesulfurization process of
naphtha. They characterized synthesized SWNT using BET and XRD, which are
shown in Fig. 7.3. and Table 7.2.
180
160
140
120
Intensity
100
80
60
40
20
0
10 20 30 40 50 60 70 80
Angel (2θ)
Fig. 7.3 XRD of Co–Mo/SWCNT catalysts after reaction
Table 7.2 Physical properties of SWCNT support

Sample Surface area BET (m2/g) Pore volume (cm3/g) Pore size (Å)
SWCNT 303.25 0.76 10.02
XRD graph showed carbon as catalysts support and molybdenum sulfide of

consumed catalysts after reaction. They deduced Mo contents were converted to
the molybdenum sulfide.
They observed that MoO2 and MoO3 were the active sites on the CNT and
γ-Al2O3 supports, respectively. They reported that carbon nanotubes had hydro-
phobic nature which resulted in weak interaction between Co/Mo and support. In
calcinations stage, CNT caused reduction of Mo through heat treatment because Mo
oxides gathered on the surface of support preliminary.
They claimed that comfortable reduction of active metals on the CNT supports
was performed which facilitated the dispersion of Co–Mo particles on support and
improved the acidity of CNT. Therefore, high isomerization and the cracking
reaction of sulfur compounds could be observed in these kinds of catalyst that
leads to the enormous HDS responsible behavior.
Results showed that CNT supported catalysts adsorbed high quantity of sulfur at
operating temperature above 583 K since active phases on this catalyst were
reduced more comfortably.
Khorami and Kalbasi (2011) investigated on the HDS of naphtha by multiwall
carbon nanotube supported Co–Mo catalyst in a fixed bed reactor. The operational
condition of the reactor was reported as below: 310 C, 15 bar and liquid hourly
space velocity: 4/h. They acquired catalyst with 10–20 nm clusters and support with
10 nm pore diameters that improved Co/Mo particles dispersion on the support. The
activity of catalyst with total amounts of Co and Mo about 7% weight percent was
examined for HDS of naphtha with 1270 ppm sulfur species like
methylisopropylsulfide, t-amylmercaptan, isoamylmercaptan, ethyl sec butyl sul-
fide, etc. It was observed that all of the sulfur compounds displayed 88% conversion
regardless of their molecular weights.
Shang et al. (2007) synthesized MoO3/CNT, Co–Mo/CNT with different atomic
ratio of Co/Mo and γ-Al2O3 supports and examined their behavior in
hydrodesulfurization of dibenzothiophene. As the other researchers’ reports, they
revealed that Co–Mo/CNT had higher activity than Co–Mo based γ-Al2O3 catalyst
due to the weak interaction of CNT support with metals spices, unlike γ-Al2O3
supports. They also postulated that reducibility of catalysts was depended on the
atomic ratios of Co/Mo. They tested their catalysts with 0–1 atomic ratios of Co/Mo
and concluded that the more atomic ratio, hence 0.7, lead to the more active spices
in the catalysts. For MoO3/CNT catalysts, they observed well dispersion of Mo on
CNT catalysts when the catalyst loading was lower than 6% and proper scattering
of MoO2 particles when catalyst loading was 8%. MoO2 particles have a more
effective role on sulfidation process than MoO3 because of their comfortable
conversion capability.
In another research (Chen et al. 2004), DBT adsorption on sulfide and oxide of
Co–Mo catalysts on CNT, activated carbon (AC) and γ-Al2O3 were studied.
Characterization using NH3-TPD technique indicated the higher activity of sulfide
catalyst than oxides since a number of acidic sites on sulfide compounds were more
than ones on oxide catalysts. Moreover, despite AC has higher surface area and pore
volume than CNT and γ-Al2O3, CoMoS/AC showed weaker acidity because a
number of acidic sites were decreased after CoMoS and CoMoO loading on the
AC. They found that the activity of CoMoS/CNT was about 97%. It means that
almost all (90%<) of the DBT molecules were adsorbed on CoMoS/CNT. They
deduced it may be related to the CoMoS/CNT end-on mode and presence of several
onion vacancies (vacant orbit which is electron acceptor) in the MoO2 metals as
active phases.
Soghrati et al. (2012) prepared Co–Mo catalyst supported on CNT-coated
cordierite monoliths (2Al2O3: 5SiO2: 2MgO) and tested them in HDS of naphtha.
FESEM results of CNT-coated monolith determined the good distribution of
CNTs on the monolith which caused to attain catalysts with the higher surface area,
pore volume and mesoporous layer of CNTs with adhesion properties. A compar-
ison of CoMo/monolith (A), CoMo/CNT, and CoMo/FACNT (CNT-coated mono-
liths) revealed that FACNT supported CoMo catalysts had higher activity than the
others. Besides, when the metal content of the catalysts (CoMo) was increased to
10 wt%, the S conversion reached to 98.08%. It means that sulfur content of
naphtha declined from 2670 to 53 ppm at 310 C.
Eswaramoorthi et al. (2008) survived the effect of NiMo/MWCNTs catalysts on
gas oil which was obtained from Athabasca bitumen. They evaluated their catalysts
in different Ni and Mo contents of catalysts in various temperatures which showed
different results in HDN and HDS of gas oil. Experimental results illustrated the
reduction of Mo elements from Mo6+ to Mo4+ and Mo0 in two steps and different
temperatures. By increasing the amount of Ni, for example, for 0–4.5 wt% Ni/12 wt
% Mo/MWCNTs, well dispersion of MoO3 particles was seen. In addition, when Ni
content increased to 3 wt% over 12 wt% Mo/MWCNTs, the number of active sites
of MoS2 enhanced. In addition, the catalysts activity of MWCNT support was
higher than that of Al2O3 at low temperatures (345–360 C) but at higher temper-
atures (375 C) they displayed equal value. They believed that it was due to the
catalysts tendency to have maximum activity at higher temperatures.
5.3 Graphene Support
In the recent years, graphene as a new carbon material with a planar sheet with sp2
carbon–carbon bonds attracts the scientist attentions due to their high specific
surface area, supreme mechanical, electronic and thermal properties, high elastic-
ity, and good mobility (Rao et al. 2009; Zhu et al. 2010).
Some articles investigate graphene performance as catalyst support (Hajjar et al.
2016a) in HDS process. Z. Hajjar et al. (2016b) have synthesized graphene by CVD
technique in atmospheric pressure and 900–1000 C and with solid camphor
(C10H16O), hydrocarbon source that contains hexagonal and pentagonal rings like
methyl carbon, and methane gas as carbon precursors. They obtained a 5-layer
graphene with a high yield of 90%. They conclude from BET results that obtained
graphene from camphor had higher specific surface area and pore volume than
Table 7.3 Physical properties of the graphene support

Sample Surface area (m2/g) Pore volume (cm3/g) Pore size (Å)
Graphene 850 2.11 100
Fig. 7.4 XRD pattern of Graphene
methane precursor. They declared that more acidic sites were observed on the
camphoric based catalysts. The physical characterization of the synthesized
graphene is shown in Table 7.3.
Furthermore, from XRD patterns (Fig. 7.4), it could be observed, the graphene
sample clearly shows the (002) reflection associated to 2Ө about ~29.8 which
indicate graphene sheet and (100) and (101) reflections associated to 2Ө about
46 that overlap together.
Also, the Raman spectrum of graphene, Fig. 7.5, shows three main peaks G, D,
and 2D. The ID/IG, the ratio D and G band intensities, is an important parameter to
show carbon structure disordering and heteroatom doping, which higher value is
reflective of more defects formation in graphene structure and heteroatom existence
(Sun et al. 2015; Yuezeng et al. 2013).
They have also expanded their studies on the other synthesis methods of
graphene (Hajjar et al. 2015). They have employed in situ and simultaneous
chemical exfoliation method in graphene oxide–MoS2 composite synthesis in
order to accelerate the synthesis procedure. They claimed that smaller and more
uniformly dispersed particles and higher and stronger acidic sites were obtained via
this method.
Fig. 7.5 Raman spectra of porous graphene

In both cases, catalysts were compared with industrial Co–Mo/γ-Al2O3

supported catalysts for HDS of naphtha with 1350 ppm sulfur content. The obtained
results showed better reduction of active materials on graphene-based catalysts at
lower temperature due to the weaker interaction between supports and Co–Mo
metals. Their experience revealed that graphene-based catalyst had higher activity
than industrial ones in hydrodesulfurization. Results showed that catalytic conver-
sion of both cases was 100% while industrial catalyst had 92.6% conversion. BET
results were obviously showed that specific surface area and pore size of graphene
were higher than γ-Al2O3. In the first case, the number of active species on
graphene-based catalysts perceived to be decreased at a lower temperature which
was attributed to the weaker interaction of carbon-based supports with metals as
catalysts. In the second article, sulfidation was performed by feed at first and so
MoS2 was formed initially and could act as active phase. Graphene oxides have
weak interaction between supports and catalyst.
6 Conclusion
Sulfur compounds which are released to the air by combustion of fuels are one of
the critical problems of the environment. Hydrodesulfurization as an important
catalytic process is used to solve this problem. To reduce a number of sulfur
compounds in oil stocks, improved processes and novel active catalysts have
been introduced. The improved catalysts activity can be achieved by controlling
the size, surface area, porosity, active phase dispersion, morphology, surface
composition, and thermal stability.
In the HDS process, the most important applicable supports are nano- and
mesoporous materials such as carbon nanotubes, graphene, and γ-Al2O3.
The γ-Al2O3 is an important support for HDS process. It has bimodal pore
structures, i.e., the smaller pore with high surface area for HDS reactions and the
larger pores for bulky reactants to diffuse in pores. In these supports, it is significant
to produce fourfold (AlIV) and fivefold (AlV) aluminum acid centers in order to
have better chemical reactions. By controlling the size of them in nano or meso
scale, a lower amount of coke is obtained. By controlling the morphology and slab
stacking numbers of active species in alumina-supported catalysts in nano and
meso scales, suitable MoS2 slab layers can be obtained and complete conversion
achieved
Moreover, graphene and CNT supports have high surface area. Therefore,
dispersion of nanoclusters over catalysts is increased and lower loading of metals
on catalysts surfaces is needed which leads to economical costs.
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Chapter 8
Mechanisms of Desulfurization by
Nanomaterials
Waqas Ahmad and Imtiaz Ahmad
Abstract A variety of materials are used as catalyst and adsorbent during the
desulfurization of petroleum products, and nanomaterials also find its application in
this field. In different desulfurization process, the behavior of nanomaterials
towards desulfurization is different. In the case of hydrodesulfurization process,
the catalyst used are CoMo or NiMo sulfides supported on various supports. The
catalysts bear anion vacancy or coordinatively unsaturated sites, where the sulfur
compounds adsorb and react with hydrogen, to set free sulfur as H2S. The structure
of the catalyst deeply influences its HDS activity; rim and edge model proposed
suggests that the rim and edge sites of the catalysts sheets stacked together are more
active for HDS of larger molecules. The activity of the catalysts enhances with
reducing its crystalline structure. The catalysts used in oxidative desulfurization
(ODS) include supported and unsupported metal oxides, polyoxmetalates, and
transition metals as cations. During ODS reactions, the catalysts either act as an
oxygen carrier, by converting into peroxo species or then enhance the dissociation
of the oxidant to boost up the selective oxidation of the sulfur compounds. In
adsorptive desulfurization, the adsorbent materials selectively retain the sulfur
compounds by π-complexation or physical adsorption. In some cases, the adsor-
bents assist in cracking of sulfur compounds during the adsorption process.
Keywords Nanocatalysts • Desulfurization mechanism • Hydrodesulfurization •

Sulfides catalysts • Oxidative desulfurization • Polyoxometalates • Adsorptive
desulfurization • Reactive adsorption
1 Introduction
Nanomaterials have brought a revolution with a variety of technological applica-

tions including electronics, medicines, molecular biology, polymers, fabrics, glass,
food products, automotive, sensors, coating, and catalysis. The same has found its
place in oil and gas industries. In the petroleum industry, desulfurization of the
W. Ahmad (*) • I. Ahmad

Institute of Chemical Sciences, University of Peshawar, 25120, Peshawar, KPK, Pakistan

212 W. Ahmad and I. Ahmad
petroleum products is a challenging job. The obnoxious effects of sulfur in petro-

leum in the form of corrosion problems, catalysts deactivation, and environmental
pollution necessitates eliminating sulfur to the minimum level (Ahmad 2015). At
the present, catalytic hydrodesulfurization (HDS) is the sole industrial technology
to cater the desulfurization of petroleum; however, research is underway to find
more effective and convenient techniques. Among the developing desulfurization
techniques, adsorptive desulfurization, oxidative desulfurization (ODS), and
bio-desulfurization (BDS) are worth mentioning (Campos-Martin et al. 2010;
Song and Ma 2003).
Owing to their high catalytic and adsorption activities, nanomaterials are exten-
sively used for desulfurization of petroleum products. In some techniques like HDS
and catalytic ODS, nanomaterials are used as catalysts whereas in adsorptive
desulfurization these are used as adsorbent materials. So far a variety of nano-
sized materials has been used as catalysts in industrial processes or in research
experiments for desulfurization of petroleum distillate fractions. This chapter gives
an insight of various desulfurization techniques and the action mechanism for
various nanomaterials catalyst or adsorbent used in each technique. The aims of
this chapter include the following:
1. To elaborate the basic principles of hydrodesulfurization (HDS), oxidative
desulfurization (ODS), and adsorptive desulfurization (ADS)
2. To highlight the various types of nanomaterials catalyst used in each of the
above desulfurization techniques
3. To explain the mechanism of action for nanomaterials during each desulfuriza-
tion process
2 Hydrodesulfurization Catalysts
Hydrodesulfurization (HDS) is currently the only industrial process used for

removal of sulfur from petroleum distillate fractions with the prime objectives to
reduce the sulfurous emission in products and avoid the poisoning of noble metal
catalysts by sulfur during the downstream processing of the products. In HDS
process, the feed is treated with gaseous hydrogen under high pressure at an
elevated temperature in the presence of catalysts in fixed bed or fluidized bed
reactor. The sulfur is removed in the form of gaseous H2S in the flue gasses, and
the H2S is used to produce elemental sulfur by clause process. The typical operating
conditions of the HDS process are: hydrogen pressure 30–3000 psi, temperature
300–500 C, hydrogen flow/recycle rate 250–10,000 SCF/bbl, and feed space
velocity of 0.5–5 V/V/hr. The process conditions may be varied based on the sulfur
content of the feed, the nature of the feed, and the degree of desulfurization required
(Javadli and Klerk 2012). The catalysts used are metal sulfides, commonly CoMo
and NiMo sulfides supported on γ-alumina, alumina-silica, or zeolite supports
(Furimsky 1996; Knudsen et al. 1999; Ma et al. 1994; Shafi and Hutchings 2000;
Vasudevan and Fierro 1996). Commonly used supports for the active phase
8 Mechanisms of Desulfurization by Nanomaterials 213
catalysts are silica-alumina molecular sieves and mesoporous silica molecular

sieves such as MCM-41, zeolites, metal oxides, titania (TiO2), carbon and com-
posites of these materials, etc. (Olguin et al. 1997; Segawa et al. 2000; Song and Ma
2003). The main characteristics of the support materials are dispersion ability of
active phase and possession of Lewis and Bronsted acidic sites which play an
important role towards increasing the catalyst efficiency.
Generally, the active catalysts components are Co-Mo-S, Ni-Mo-S, and Mo-Ni-
W-S, and various metals such as W, Ni, Fe, and Co are added to the catalyst as
promoters. The promoters influence the binding energy of the metal-sulfur bond,
and the strength of this bond is an important factor in enhancing the efficiency of the
catalyst. The addition of some noble metals like Pd, Ru, and Pt to the active
catalytic species has been found to markedly increase the catalyst efficiency;
however, these are very susceptible to poisoning by sulfur (Song and Ma 2003).
New commercial developments in the HDS catalysts brought some modification in
the catalyst with improved efficiency such as CoMo and NiMo based STARS
(Super Type II Reactive Sites) and NEBULA (New bulk activity) by Akzo Nobel
catalyst preparation technology (Brevoord et al. 2000; Conference Exhibition 2000;
Mayo et al. 2001; Song and Ma 2003), and Criterion NiMo and CoMo CENTINEL
catalysts, by criterion catalyst and technologies (WS 2001).
Nanostructured noble and non-noble metal phosphide, nitrides, and carbides
have been developed as novel high activity HDS catalysts. Reduction of metal
chlorides or oxides in a hydrogen atmosphere under controlled temperature is a
common route for the synthesis of nano-metallic phosphides. These catalysts show
enhanced catalytic activity than the conventional Mo, Ni, W, Co sulfides, specifi-
cally NiP shows the highest activity than other metal phosphides due to its high
intrinsic activity and a high degree of dispersion. Phosphide also shows resistance
to inhibition in hydrodenitrogenation. Some noble metal phosphides, e.g., Rh, Pd,
Ru, and Pt phosphides, have shown enhanced HDS activity and stability than
non-noble metal phosphides. Metal nitrides are produced by reducing the metal
precursors in NH3 or the N2 environment. Similarly, metallic carbides are prepared
by reducing metal precursors in acetylene followed by in nitrogen under controlled
temperatures. Metallic nitrides and carbides catalysts offer the advantage of the
high acidity of the support material. However, the major drawback of metal
phosphides, carbides, and nitrites is their low degree of dispersion of the active
sites per unit mass of the catalyst. Also initially these catalysts show high HDS
activity but later the activity declines as the active sites are sulfurized during the
HDS process (Liu et al. 2013).
Under the conditions of the HDS process, the main hydrodesulfurization reac-
tion involves the addition of H2 to the hydrocarbon molecules, during which the
sulfur atom is converted to H2S, which is removed in gaseous forms in the flue
gasses. The removal of N and O atom from the hydrocarbon molecules also occurs
in the same way, besides the saturation of olefins also occurs similarly. The
hydrodesulfurization of nonaromatic sulfur compounds, i.e., sulfides and thiols,
occurs through cleavage of C–S bond and subsequent formation of S–H and C–H
bonds.
However, in the case of thiophenic compounds, the reaction is complex and is

shown to proceed through two pathways, hydrogenation and hydrogenolysis.
Hydrogenation involves the successive addition of the H atoms to all the atoms of
the molecules including sulfur atom, which leads to subsequent cleavage of the ring
and removal of sulfur as H2S from the ring. Whereas, hydrogenolysis proceeds by
selective addition of hydrogen to the sulfur and carbon atoms at C–S bond resulting
in subsequent cleavage of the C–S bond and removal of sulfur as H2S (Scheme 8.1).
Generally, both pathways occur simultaneously but depend on the catalysts selec-
tivity which can prefer any of these two, generally, NiMO/Al2O3 favor the
hydrogenolysis whereas CoMo/Al2O3 favor hydrogenation pathway (Knudsen
et al. 1999; Ma et al. 1994; Vasudevan and Fierro 1996).
The alkylated benzo and dibenzothiophenes are resonance stabilized due to
electron donating effects of the alkyl groups, besides because of the steric hindrance
created by alkyl groups, these compounds are resistant to HDS reactions under
normal operating conditions. The alkylated benzo and dibenzothiophenes are there-
fore termed as refractory sulfur compounds. The HDS reactivity of various sulfur
S
Hydrogenation Pathway Hydrogenolysis Pathway
Dibenzothiophene
+H2 -H2S
+H2
S S
-H2S +H2 +H2
+H2
Scheme 8.1 Hydrogenation and hydrogenolysis pathways for hydrodesulfurization of

dibenzothiophene
compounds is shown to be increasing in the following order (Gates and Topsøe

1997; Shafi and Hutchings 2000).
4, 6 R2 DBT < 4 R DBT < R DBT < DBT < R BT < BT

< R Th < Th
ðTh ¼ thiophene; R ¼ Alkyl groupÞ
The mechanism of the hydrodesulfurization reactions in the presence of sulfided

catalyst has been studied by a number of researchers (Babich and Moulijn 2003;
Kubota et al. 2014; Song and Ma 2003). Earlier workers proposed that the acidic
sites on the catalysts do not take part in the HDS reaction, rather the CoMo and
NiMO provide the active sites for the reaction. Lipsch et al. studied the mechanism
of the hydrodesulfurization over CoMo catalyst and suggested that MoO3 is mainly
responsible for desulfurization reaction (Lipsch and Schuit 1969). During prior
activation of the catalyst by reduction and sulfidation with H2 and H2S, anion
vacancies are formed through reductive removal of bonded oxygen atoms in
MoO3. The anion vacancy also called coordinatively unsaturated sites, where the
molybdenum centers are stabilized at the edges of MoS2 crystallites. The sulfur
compounds, i.e., thiophene, adsorbs at the anion vacancy site, at the transfer of
hydrogen leads to cleavage of one C-S bond resulting in ring opening (Owens and
Amberg 1961). The transfer of hydrogen atom further leads to the breaking of the
C–S bond, removing S as H2S and the resulting butadiene desorbs (Owens and
Amberg 1961). Further saturation of C¼C bond or butadiene may occur at the same
site or another site (Scheme 8.2).
There are a large number of research studies which reveals that activity of the
HDS catalyst is greatly dependent on the structure of the catalyst. It has been shown
that in crystallites of MoS2 catalyst, the most active sites are located on the edge
planes and the basal planes are relatively inert. According to Rim and Edge model,
Scheme 8.2 Mechanism of HDS of thiophene over MoS2

Basal plane
H2S + R-H
Rim plane
S MoS2 slabs
H2S + R-H Van der Waal forces
Edge plane between slabs
Scheme 8.3 Rim–Edge model of MoS2 and HDS of sulfur compounds
proposed by Daage and Chianelli, unsupported MoS2 crystallites have layered

structure in which sheets of MoS2 are stacked one above other and held together
by weak Van der Waal forces. The hydrogenation of large molecules which show
steric hindrance occurs on the top and bottom layers of MoS2 slabs, called rim sites.
Whereas the hydrogenation and hydrogenolysis of the sulfur compounds are cata-
lyzed on all edge planes, the basal planes are considered catalytically inactive. In
the case of single or bilayers, the selectivity is dominated by the presence of
coordinative instauration. For smaller sulfur compounds, where the no steric inter-
ference is involved, there is no rim and edge effects, and the molecule is catalyzed
at all active sites on the surface (Daage and Chianelli 1994) (Scheme 8.3).
Jhonsen et al. reported that when the MoS2 sheets are dispersed by exfoliation,
they offer high catalytic activity (Joensen et al. 1986). In the case of exfoliated
MoS2, the fraction of edge sites is greater, where the hydrogenolysis of C–S bond
occurs (Thian 2008).
Tuxen et al. investigated the influence of size on the activity of MoS2
nanoclusters and role of edge and corner sites for adsorption of model sulfur
compounds, i.e., dibenzothiophene and 4,6-dimethyldibenzothiophene, during
hydrodesulfurization reactions. The adsorption phenomenon was studied by high-
resolution STM, using different sizes of MoS2 nanocluster, which revealed that the
size of the nanoclusters is the main factor that influences the adsorption behavior
and selectivity and the threshold value for the size of nanocluster was 6 Mo atoms
on the cluster edge. In the case of large nanoclusters, with Mo atoms above the
threshold value, the S vacancy is formed on the cluster edges but due to sterical
hindrance DBT cannot bind at these sites. Whereas in the case of nanocluster
smaller than the threshold value, the S vacancies are formed at corner site where
strong adsorption of DBT can occur without any hindrance. The high desulfuriza-
tion activity is thus related to the size of the catalysts (Tuxen et al. 2010).
3 Oxidative Desulfurization (ODS)
Oxidative desulfurization (ODS) involves the selective oxidation of organic sulfur

compounds in petroleum, and consequently the removal of the oxidized compounds
from the feed by solvent extraction or adsorption over solid adsorbent (Campos-
Martin et al. 2010; Javadli and Klerk 2012). During oxidation step, the organosulfur
compounds are converted into more polar oxidized form, i.e., sulfones; owing to
their high polarity, sulfones can be easily separated from nonpolar oil phase through
extraction with polar solvents or adsorption over solid adsorbents. For ODS process
no specific high-temperature high-pressure reactor is required and it can be oper-
ated under mild conditions, i.e., low temperature and ambient pressure with high
efficiency, also the process does not require expensive hydrogen, therefore the
process is more economic than hydrodesulfurization.
The important factor in the ODS is the selective oxidation of the sulfur com-
pounds in the nonpolar hydrocarbon phase, therefore very selective oxidants are
required to attain high efficiency. The most commonly used oxidants in the ODS of
liquid fuels include organic peracids, hydroperoxides, molecular oxygen, ozone,
hydrogen peroxide, etc. (Campos-Martin et al. 2010; Gaofei et al. 2009). The
removal of oxidized sulfur compounds from the oil phase is also a key step towards
high efficiency of the ODS process, which can be effectuated by solvent extraction
of the adsorption process. Most commonly the solvent extraction is used which is
easy, less time consuming and does not require energy. The commonly used
solvents for extraction of oxidized sulfur compounds in the ODS include dimethyl
formamide, acetonitrile, dimethyl sulfoxide, toluene, methanol, ethanol, etc.; some-
times blends of different solvents are used to enhance the extraction efficiency.
Whereas the adsorbents most commonly used for removal of oxidized sulfur
compounds from the feed oil include silica, alumina, activated carbon, etc.
In ODS process, the reactivity of the sulfur compounds towards oxidation
increases with increasing the electron density on the sulfur atom in the organosulfur
compounds. Higher the electron density on the sulfur atom, more readily it can be
oxidized through an electrophilic attack on the oxygen atom. Since the alkyl groups
act as electron donating groups, therefore the presence of alkyl side chains in the
aromatic sulfur compounds increases the electron density on sulfur compounds and
in turn increases its reactivity towards oxidation. Among various aromatic sulfur
compounds, the reactivity order is given as (Otsuki et al. 2000):
4, 6 DMDBT > 4 MDBT > DBT > BT > Th
In the case of HDS, the reactivity of sulfur compounds decreases with increasing
alkyl side chains due to steric hindrance, and the reactivity order in sulfur com-
pounds is the reverse of ODS. Therefore, the sulfur compounds which are highly
resistant to be treated through HDS can be easily removed through ODS process.
A variety of catalysts are used in the ODS to improve the efficiency of the
oxidant and thereby enhance the selective oxidation of sulfur compounds in the feed
oil. The use of catalysts increases the extent of desulfurization by many folds, for
the same oxidation system. The presence of catalyst also reduces the consumption
of oxidant during ODS process. Mostly, the heterogeneous catalyst offers high
activity than the homogenous catalyst since the separation and recycling of the
homogeneous catalysts are difficult, therefore heterogeneous catalysts are
commonly used in ODS process. The catalysts used in ODS can be divided into
three categories, bases on the structure and mechanism of oxidation. These are:
1. Supported and unsupported metal oxides
2. Nanostructured POM
3. Transition metal ions or salts
The mechanism of oxidation for these catalysts primarily depends upon the
nature of the oxidants with which they are used. Some catalysts directly participate
in the reaction through the active site and some provide their surface area for the
reaction; however, in general, all these catalysts transport oxygen from the oxidant
to the sulfur atom, no matter whatever the oxidant is used.
3.1 Supported and Unsupported Metal Oxides
A number of metals oxides either in supported form or unsupported form has been
investigated for catalyzing the ODS reactions, which have shown promising results.
The most commonly used metal oxides for ODS of model and real oil in the
presence of different oxidant systems include the oxides of Mo, V, W, Cu, Ce,
Ti, etc. in unsupported form or supported on various supports like alumina, silica,
titania, etc. (Al-Shahrani et al. 2007; Caero et al. 2005; Chica et al. 2006a; Garcı́a-
Gutiérrez et al. 2006; González-Garcı́a and Cede~no-Caero 2009; Ishihara et al.
2005; Maciuca et al. 2008; Wang et al. 2003). Studies have revealed that during the
ODS process, these metal oxides form an intermediate peroxo species with the
oxidant, which selectively oxidizes the organosulfur compound.
Gracia et al. investigated the ODS of model sulfur oil and diesel oil in the
presence of polymolybdates supported on alumina, i.e., MoOx/Al2O3, using H2O2
as an oxidant in acetonitrile solvent. It was proposed that during the ODS reaction
the heptamolybdate and octamolybdate form a hydroperoxomolybdate species by
nucleophilic attack of H2O2. The peroxy oxygen behaves as strong electrophiles
and by nucleophilic attack of a sulfur atom, the hydroperoxymolybdate oxidizes the
sulfur compounds to respective sulfoxides and then sulfone. During oxidation of
sulfur compounds, the hydroperoxymolybdate species get reduced, which is then
reoxidized by the oxidant (Garcı́a-Gutiérrez et al. 2006). It has been shown that
polyoxomolybdates in the presence of H2O2 in the ratio of H2O2/Mo < 1 leads to
formation of [Mo7O22(O2)2]6 and [Mo8O24(O2)2(H2O)2]4 crystalline species,
based on hepta and octamolybdate framework, in which the terminal oxygens
(bridging oxo) are substituted by peroxogroups (Larking and Stomberg 1972;
Trysberg and Stomberg 1981). The substitution of peroxo group in mono and
di-peroxohepta molybdate at terminal Mo atom has been confirmed by 17O-NMR
(Pettersson et al. 2003). The formation of peroxomolybdate species is found to be
dependent on temperature which helps in decomposition of H2O2, pH, polar
solvent, and concentration of H2O2. Different types of molybdates supported on
alumina were investigated for ODS of model oil, and it was shown that by
MonO2n+10 (20-2n)-
Hepta/octa molybdate
H2O2
H 2O 2
H 2O H 2O
(20-2n)- (20-2n)-
MonO2n+8(O2)2(H2O)2n-14 MonO2n+9(O2)(H2O)n-7
H2O
Di-peroxo molubdate Mono-peroxo molybdate
H2O2
Scheme 8.4 The equilibrium between octa/hepta molybdate, mono-peroxo molybdate, and
di-peroxomolybdate
nucleophilic attack of hydrogen peroxide on bridging oxo ligands of hepta and

octamolybdates on alumina surface, a hydroperoxymolybdate group is formed. The
hydroperoxomolybdate species on the reversible loss of water molecule leads to the
formation of a monoperoxo species, in which by coordination to high valent Mo
atom, the peroxo group is activated electrophilically. Similarly, by a subsequent
nucleophilic attack of H2O2 and loss of water molecule, a diperoxo species may
also be formed. The mono and diperoxo species remain in equilibrium with the
hepta and octamolybdate precursor. Further, the oxidation of sulfur compounds
involves the nucleophilic attack of sulfur atom on the peroxo group of mono or
diperoxo species to form sulfoxide, whereas the monoperoxo species is regenerated
to polymobdate and the diperoxo species is regenerated to monoperoxo species. In
the similar manner, the sulfoxide is oxidized into sulfone in the second attack on the
peroxospecies (Garcı́a-Gutiérrez et al. 2008). Vegara-Mendez et al. verified this
mechanistic hypothesis using DFT analysis in water and acetonitrile as solvents and
concluded that the reactive peoxymolybdate intermediate could be formed during
the ODS reaction in water and acetonitrile phases (Vergara-Méndez et al. 2011)
(Scheme 8.4).
Molybdates are also used as ODS catalysts with oxidants other than H2O2,
commonly with organic hydroperoxides, air, or molecular oxygen. A variety of
hydroperoxides is used as efficient oxidants for ODS of the model and real oil
samples including tertiary-butylhydroperoxide (TBPH), cumenehydroperoxide,
cyclohexanoneperoxide, and tert-amylhydroperoxide (Chang et al. 2010; Chica
et al. 2006b; Zhou et al. 2009a, 2006b). In ODS reactions based on hydroperoxide
oxidation system, oxides of Mo supported on various supports has been widely used
(Chica et al. 2006b; Ishihara et al. 2005; Venkateshwar Rao et al. 2007; Wang et al.
2003) (Scheme 8.5).
Wang et al. used molybdate MoO3 supported on alumina and many other oxides
supported on alumina including CrO3, V2O5, Nb2O2, ZrO3, NiMO, NiCoMo, etc.
for ODS of model oil and kerosine oil in the presence of t-butylperoxide as oxide, in
which MoO3 was found to be the most effective catalyst. It was suggested that
oxidation of sulfur compounds is carried out by a peroxo complex formed by MoO
H
H O
O
O
O
O Mo
H H H H
O O O
Mo O Mo
O
O
S
O O Mo
O S
S O Mo
O
H O O
O Mo
S
H
Scheme 8.5 Mechanism of oxidation of thiophene by molybdates
and t-butylperoxide (Wang et al. 2003). When MoO3 is dispersed on alumina, due
to the polarization of Mo–O bond the coordination of hydroperoxide with Mo–O
bond is promoted. A five-membered peroxo complex is formed, in which the
electrophilicity of the peroxo oxygen is enhanced, and leads to oxidation of sulfur
compounds (Scheme 8.6).
Besides molybdates, other metal oxides such as tungstates and vanadates are
also reported to follow the similar mechanism for ODS, involving formation of
peroxocomplexes in the presence of H2O2 or hydroperoxides as oxidants
(Al-Shahrani et al. 2007; González-Garcı́a and Cede~no-Caero 2009, 2010; Yan
et al. 2007; Yazu et al. 2004). The detailed mechanism of the ODS catalyzed by
tungstates in the presence of H2O2 as oxidant is provided by Gracia et al. (Garcı́a-
Gutiérrez et al. 2014). In this study, ODS of diesel oil was investigated by several
types of tungsten compounds such as Tungsten (VI) oxide, tungstic acid, ammo-
nium tungstate, ammonium metatungstate, and phosphotungstic acid supported on
various supports such as alumina, silica, titania, titania–alumina, and zirconia. It
was shown that the mechanism of ODS by tungstates is similar to that followed by
molybdates as discussed above. Here the reaction of H2O2 with polyoxotunstates in
solution produces polynuclear peroxo complexes. The electrophilic attack of H2O2
O
O O δ−
δ+
δ+ δ− δ−
O Mo O
δ+
O Mo O O Mo O
O
H
O H O H
O O
O
S
S
O
δ+ δ−
O Mo O
O
δ+ δ−
O Mo O
O H
O O
O
H
S
O
O
Scheme 8.6 Oxidation of sulfur compounds by MoO3 and t-BuOOH
on the bridging oxo ligands of polyoxotungstate leads to formation of

peroxopolyoxotugstates, like [H2W12O33(O2)7]6 and [H2W12O39(O2)]6. One
such peroxo complex anion [H2W12O39(O2)]6 has been isolated as its salt and
characterized by FT-IR, 1H-NMR, and polarographic studies to have Keggin type
structure. The monoperoxoanion formed undergoes reversible loss of water mole-
cule to form a hydroperoxytungstate intermediate. The sulfur compound is stepwise
oxidized to respective sulfoxide and sulfone by nucleophilic attack of sulfur atom
on the peroxo group of the intermediate, regenerating the tungstate anion.
Supported and unsupported metal oxides are also used for ODS of the model and
commercial oil in the presence of air or molecular oxygen as oxidant. However, the
ODS under air or molecular oxygen occurs at a relatively high temperature and high
pressure than usually required in the presence of H2O2 and organic hydroperoxides.
The ODS using air or O2 as oxidants involves the formation of hydroperoxide
which further carries out the oxidation of sulfur compounds, therefore a source of
hydroperoxide is also required in the reaction medium. The alkyl aromatics present
in the oil feed serve as a hydroperoxide source. In order to study the mechanism of
formation of hydroperoxide during ODS with molecular oxygen or air, the model
reaction has been studied in the presence of alkyl benzenes as a source of hydro-
peroxide. The generation of hydroperoxide occurs at elevated temperature (up to
140 C) and follows free radical mechanism as shown in the reaction scheme
(Sundararaman et al. 2010). Once the hydroperoxide is formed, it leads to oxidation
of sulfur compounds in the way how the organic peroxides work (Scheme 8.7).
CH C
+ O2
Initiataion step
+ HOO
C C OO
+ O2 Propagation step
C OO CH C OOH C
+ +
C OO
2 Oxidized non radical products Terminataion step
O O
S C OOH C OH S
+ 2 2 +
Scheme 8.7 Oxidation of thiophene by molecular oxygen
Sundraman et al. studied the ODS of jet fuel and diesel fuel using O2 as oxidant
in the presence CuO unsupported and supported on alumina at a temperature range
of 100–140 C, and concluded that the process involves the in situ formation of
hydroperoxides utilizing the alkyl aromatic in the feed oil (Sundararaman et al.
2010). The extent of desulfurization in the diesel oil was higher than the jet fuel oil.
Because of the higher aromatic content in diesel oil, a number of hydroperoxides
produced was higher in diesel oil as determined by peroxide number, which in turn
led to high desulfurization. The formation of hydroperoxides was found to depend
upon the catalyst and the temperature. The ODS of Cold lake bitumen using air as
oxidant at 150 C resulted in 47% of sulfur removal (Javadli and de Klerk 2011).
The ODS of diesel oil using air oxidation at a temperature range of 230–300 C
under pressure of 0.1 MPa in the presence of MnO2 and Co2O3 supported on Al2O3
catalyst led to decrease in the sulfur content from 400 to 60 ppm (Sampanthar et al.
2006). It was shown that during the ODS process the aromatic content of the feed
decreased from 46.4% to 12.5%, probably due to consumption in hydroperoxides
formation. Whereas the olefin contents decreased from 2.4% to 3.6%, which was
resulted by the free radical mechanism involved. Generally, the oxidation of sulfur
compounds by so generated hydroperoxide leads to the formation of sulfoxide and
sulfone, but under conditions of high temperature and high pressure of oxygen,
overoxidation of sulfur compounds occurs which leads to cleavage of molecule and
removal of the sulfur atom as SO2. The release of the SO2 during the ODS reaction
O O
R C H R C
O O
R C + O2 R C OO
O O O O
R C OO + R C H R C OOH + R C
Scheme 8.8 Formation of peracids by aldehydes and molecular oxygen
was confirmed by purging the outlet gasses through the AgNO3 solution which led
to the formation of AgSO3. The ODS of model oil by air under 0.1 MPa pressure
and 400 C temperature using CuO/Al2O3, ZnO/Al2O3, and Cu and Pt/CeO2 also
revealed that sulfur is removed as SO2 (Lu et al. 2008). Fe(III) nitrates and
bromides loaded on activated carbon also showed high efficiency in ODS of jet
oil using air at 0.1 MPa pressure and 50 C temperature (Ma et al. 2007), and the
efficiency of catalyst was found to increase with increasing the Fe loading on the
catalyst.
An initiator or sacrificial agent may be used to readily generate the hydroperox-
ides, at low temperature and pressure. The most commonly used initiator compounds
for ODS process include various types of aldehydes, such as isobutyraldehyde,
benzaldehyde, n-octanal and hexanal, etc. (Guo et al. 2011; Murata et al. 2003;
Venkateshwar Rao et al. 2007; Zhou et al. 2009b). During this process the aldehydes
are oxidized to peracids by O2, and peracids further oxidize the sulfur compounds to
respective sulfoxide and sulfones. The formation of peracids by the interaction of
aldehydes and O2 occurs stepwise, initially, an acyl radical is formed which further
oxidizes to peroxy-acyl radical and finally to peracid as shown in the reaction scheme
below (Saleh 2015) (Scheme 8.8).
The metal oxides catalysts used for catalyzing the ODS reaction using air or O2
follow the same mechanism as reported for hydroperoxides. The peroxide or
hydroperoxide formed by auto-oxidation of alkyl aromatics forms a metal oxide
and hydroperoxide complex (Dooley et al. 2013). The metalloperoxy complex
formed leads to oxidation of sulfur compounds in a similar way as discussed in
the case of peroxides.
3.2 Polyoxometalates (POM) Catalysts
Polyoxometalates (POM) are the anionic cluster of metal oxides of group VI and V
metals, i.e., Mo, W, V, and Ge, associated with various cation as their salt (Long
et al. 2010). POM are termed as heteropolyoxometalates when some other
POM + Oxidant-O POM-O
Subtrate + POM-O Products-O + POM
Scheme 8.9 Oxidation by polyoxometalates (POM)
heteroanions are also associated such as SO42 or PO42. Structurally the POM
consists of anionic clusters made of metal oxo species linked through bridging
oxygen atoms together. Mostly the clusters contain three metals (group V and VI) in
their high oxidation state in case of isopolyoxometalates, where no other hetero-
atom is present, or in the case of heteropolyoxometalates, a heteroatom like P, Si, B,
Al, Si, and Ge, may also be present. Based on the structure, POM is of different
types which include Lindqvist type POM [M6O19]n, Anderson type [XM6O24]n,
Keggin type [XM12O40]n, and Wells-Dawson type POM [X2M18O62]n. Here X
represents heteroatom, M stands for metal, and n shows the overall charge on the
cluster (Briand et al. 2003; Putaj 2012). POM have large molecular structure and
possess versatile characteristics including high oxidation-reduction potential, pro-
ton acidity, thermal stability, and high reactivity of lattice oxygen, due to which
they are used in a variety of fields including catalysis (Long et al. 2007).
POM are extensively used in the ODS reactions as catalysts for selective
oxidation of organosulfur compounds, where they show superior activity as com-
pared to other catalysts. The oxidation reactions involving POM as catalysts follow
two types of mechanisms. The first type mechanism involves electron transfer
oxidation, in which the substrate is oxidized and the POM is reduced, the reduced
POM is then reoxidized by O2. In this case, mostly no oxygenation occurs, or may
occur but oxygen only works as an electron acceptor. The second type mechanism
proceeds through formation of active metal proxo species, by the interaction of
POM with a primary oxidant such as H2O2. The peroxo complex oxidizes the
substrate by cleavage of a peroxo bond (Neumann et al. 1995) (Scheme 8.9).
The POM is reoxidized by the oxidant. Studies have shown that ODS reaction
involving POM occurs through the second type of mechanism where the activated
peroxo POM species is formed. In ODS reaction, a highly reactive transient species,
the polyoxoperoxo complex is formed by transfer of oxygen from H2O2 to the POM
molecule. The peroxo complex formed oxidizes the sulfur compounds successively
to sulfoxides followed by sulfone, and itself gets reduced to POM species. The
POM is again reoxidized by H2O2 to form another peroxo complex which is ready
for further oxidation (Te et al. 2001). A generalized mechanism can be presented
similar to that verified by Arichi et al. (Arichi et al. 2008) using isotopic investi-
gation and GCMS techniques, in which the hydrogen peroxide acts as O-donor to
POM, rather than directly oxidizing the substrate. During interaction of H2O2 and
POM, H2O2 decomposes to form a MOO* peroxo species. The peroxo complex
cleaves homolytically to generate a reactive electrophile species. The sulfur com-
pound is oxidized by nucleophilic attack on the peroxo complex, and the POM is
regenerated (Scheme 8.10).
M O H
V O
OH O
M O O H
M O O O M O O OH
V V
H M O O
M O
-H2O
M O O O
V
M O
Scheme 8.10 Mechanism of oxidation by vanadium species
For ODS application, POM is mostly used in a supported and unsupported form
with H2O2 as the oxidant, and in the presence of a nonpolar solvent such as
acetonitrile and methanol (Gaofei et al. 2009). Since POM are soluble in the
aqueous phase, therefore a biphasic medium is required which is formed by the
addition of a polar solvent like acetonitrile and methanol to the nonpolar oil phase.
In such a biphasic medium, the sulfur compounds are oxidized by the aqueous
phase oxidant and POM. A variety of POM has been studied for ODS of the model
and real oil samples in the biphasic medium. ODS of light oil was tested with
tungstophosphoric acid (TPA) in the presence of H2O2 as an oxidant in acetonitrile-
oil (4:1) biphasic medium, which led to decrease in the sulfur level from 300 to
112 ppm at 60 C, (Yazu et al. 2001). The same oxidation system, i.e., TPA/H2O2,
also showed high efficiency in tetradecane-ethanol (Yazu et al. 2003) and octane-
acetic acid (Yazu et al. 2007) biphasic systems. Studies reveal that among different
Keggin type POM catalysts containing Si and P as heteroatoms, containing
tungstic and molybdic acid shows high desulfurization efficiency (Te et al. 2001),
also among P-based POM containing different metals, i.e., Mo, W, and V, those
containing W and Mo (i.e., H3PW6Mo6O40) are showed to be more efficient
towards ODS of diesel oil in a biphasic medium, attaining up to 97 % sulfur
removal (Wang et al. 2010).
Since the POM molecules have large molecular size, therefore due to the
interaction of bulky POM structure and alkyl groups in the alkylated sulfur com-
pound, steric hindrance is experienced which leads to decreased reactivity of
alkylated sulfur compounds. Hence in the ODS reactions using POM catalysts,
the alkylated sulfur compounds have lower reactivity than those with no alkyl
groups. As such the order of reactivity among various sulfur compounds in
5-
PMo10V2O40
O
O O
H 2O 2
V V
S S
H2O2
O
S
O
V
O
Oil Phase Ionic liquid phase PMo10V2O40 5-
Scheme 8.11 Oxidation of sulfur compounds by vanadium-based POM in the presence of ionic
liquids
POM/H2O2 oxidation system is same as reported for HDS reactions, i.e.,

4,6-DMDBT < 4-MDBT < DBT.
In order to increase the ODS efficiency of the POM, its surface area can be
increased by dispersion or support it on suitable materials. Studies have shown that
reactivity of POM in terms of desulfurization efficiency drastically increases by
supporting on various support materials such as different anion exchange resins
(AER), silica, alumina, and mesoporous silicates (Xue-Min et al. 2007; Yang et al.
2007; Yazu et al. 2003; Zhang et al. 2005). It has been observed that in the case of
real oil samples, the ODS efficiency of the POM catalysts is low, in which the
aqueous phase oxidant cannot access completely to the sulfur compounds due to
phase transfer limitations. Alternately in order to attain high desulfurization, excess
amount of oxidant is required. In order to eliminate the phase transfer limitations
and avoid the biphasic system, various techniques are used such as a combination of
POM and ionic liquids, application of surfactants with POM catalysts, or using
amphiphilic catalysts. The ODS of model oil was studied in the presence of
heteropolyanion-based ionic liquid, i.e., ([Hmim]5PMo10V2O40), synthesized by
the reaction of molybdovanadophosphoric acid (H5PMo10O40) and
N-methylimidazole, which showed 99% of sulfur removal under O/S ratio of 4:1.
It was shown that during the desulfurization process, the sulfur compounds shift
from oil phases to the ionic liquid phase where oxidation of sulfur compounds
occurs, without any nonpolar solvent. Since H2O2 is miscible with the ionic liquid,
it reacts with (PMo10O40) to form peroxospecies, and the peroxo complex oxidizes
the sulfur compounds to respective sulfones. Many another type of ionic liquids and
heteroplyacids have been studied for ODS (Zhang et al. 2013; Zhu et al. 2011)
(Scheme 8.11).
Likewise, various types of surfactants such as tertaoctyl-ammonium bromide and
hexadecyltrimethyl-ammonium bromide (CTAB) are also used during the ODS by
H2O2 O
POM N
A H 2O
Interor region
B /Aqueous phase
(A) S
C O
O
Interfacial
Emulsion droplet Exterior region
membrane
(B) /oil phase (C)
Scheme 8.12 Oxidation of DBT in emulsion droplet system
POM/H2O2 system, which has shown high ODS results under a limited amount of
H2O2 and short reaction duration (Collins et al. 1997). However, the most notable
approach is the application of quaternary ammonium salts of POM called amphiphilic
or emulsion catalysts, which consists of hetero polyoxometalate anion combined
together with a quaternary ammonium surfactant cation. Amphiphilic or emulsion
has shown promising desulfurization efficiency in the presence of H2O2, and these
catalysts eliminate the phase transfer limitations by the formation of an emulsion or
tiny droplet during the ODS reaction which provides the intimate contact of the
catalysts, oxidant, and sulfur compounds in the nonpolar oil phase. The emulsion or
amphiphilic catalysts comprise two parts, i.e., the hydrophilic part which is the POM
cluster and the lipophilic part which is the surfactant molecule consisting of the long
alkyl group. In the emulsion system formed of tiny droplets, the lipophilic part of the
catalysts is dispersed in the oil phase exterior to the droplet, and the hydrophilic POM
part is captured at the interfacial membrane of the droplet, whereas the aqueous phase
H2O2 is retained in the interior of the droplet. The POM is oxidized to peroxo
complex by the interaction with H2O2, whereas the interaction of a sulfur compound
and the peroxo complex occurs at the interface, where sulfur compounds are oxidized
to respective sulfone. At the completion of the reaction, the emulsion breaks where
the oxidized sulfur compounds and the amphiphilic catalysts are separated from the
oil. The emulsion catalysts can be reused for a number of cycles, without losing its
catalytic efficiency (Jiang et al. 2011) (Scheme 8.12).
Variety of an emulsion or amphiphilic catalysts has been investigated for ODS

of various distillate fraction, which have shown remarkable efficiency.
Phosphotungstate-based emulsion catalyst [(C18H37)2N(CH3)2]3[PW12O40] in the
presence of H2O2 has been reported to decrease the level of sulfur in diesel oil to
around 1 ppm from initial of 500 ppm sulfur (Li et al. 2004). Quaternary ammonium
salt of sodium phosphotungstate [C18H37N(CH3)3]4[H2NaPW10O36] has been
shown to reduce the sulfur content of hydrotreated diesel from 500 to 1 ppm and
that of straight run diesel from 6000 to 30 ppm, with O/S ratio of 3 under mild
conditions (Lü et al. 2006). Similarly one study reports that among different Mo, W,
and V containing emulsion catalyst, i.e., [PV2Mo10O40]4, [W6O19]2, [V(VW11)
O40]4, and [PVW11O40]4, with same tetrabutylammonium cation, used for ODS
of gas oil, the most efficient catalysts were found to be containing [V(VW11)O40]4
anion, which attained about 90% of sulfur removal (Komintarachat and
Trakarnpruk 2006). A number of studies have revealed that among different
quaternary ammonium cations used for preparation of emulsion catalysts, the
most suitable are di- or tri-methylhexadecyl ammonium cations, i.e., C16H33NH+
(CH3)2 and C16H33N+(CH3)3, which can generate the appropriate emulsion system
required for high efficiency in ODS reactions (Gao et al. 2006; Imtiaz et al. 2013;
Jiang et al. 2009; Li et al. 2004, 2005; Lu et al. 2007, 2010; Zhang et al. 2010).
Interesting fact about the emulsion catalysts is that reactivity order of the various
sulfur compounds is same as for ODS process in the presence of per acids as
oxidants, i.e.,
BT < 5 MBT < DBT < 4, 6 DMDBT
This order shows that the stearic hindrance arising due to the interaction of POM
catalysts and alkyl groups in alkylated sulfur compounds is eliminated due to the
emulsion system (Collins et al. 1997; Te et al. 2001). This indicates that in the
emulsion system better contact of sulfur compounds and the oxidants occurs.
3.3 Transition Metal Ions or Salts
A number of research reports describe the ODS of oil feed in the presence of
transition metal ions as salts or supported form in the presence of different types
of oxidants. Such catalysts are commonly used in the presence of H2O2 or per acids
but also with other oxidants. These catalysts promote the decomposition of the
oxidant species, which enhances the rate of oxidation of sulfur compounds. Dai
et al. investigated the ODS of diesel oil using Fenton’s reagent as a catalyst in the
presence of H2O2/acetic acid oxidation system using ultrasonication (US) (Dai et al.
2008). The mechanism of the reaction was shown to involve a number of reactions
in which the Fenton’s reagent dissociates H2O2, to generate active hydroxyl radicals
which are more reactive than H2O2 oxidant, and accelerate the oxidation of sulfur
compounds. The metal ion can also consume the hydroxyl radicals, therefore when
the concentration of the metal ions is above the optimum value, the ODS efficiency
declines. Results indicated that the optimum value for Fe2+/H2O2 was 0.05 mol/
mol. Furthermore, in the presence of US-Fenton’s reagent, the efficiency of the
ODS was found to be increased 2.17 times than in simple H2O2/acetic acid
oxidation system (Scheme 8.13).
Riad et al. reported the ODS of light gas oil using H2O2 in the presence of Zn
incorporated to hydroxyapatite catalysts prepared by ion exchange and wet impreg-
nation methods (Riad and Mikhail 2012). It was shown that the catalysts prepared
by ion exchange method show high efficiency than the other, by attaining 89% of
sulfur removal. The author suggested that the Zn exchanged hydroxyapatite follows
the mechanism similar to Fenton’s reaction, where the hydrogen peroxide is
decomposed by the Zn2+ ion to produce hydroxyl radical. The hydroxyl radical
further oxidized the sulfur compounds to respective sulfoxide and then sulfone.
Similarly, the ODS of model oil and various real oil samples including untreated
naphtha, light gas oil, heavy gas oil, and Athabasca bitumen was studied in the
air-assisted performic acid oxidation system in the presence of Fe2+ exchanged on
the ZSM-5 zeolite. The level of desulfurization was increased in the presence of a
catalyst, which was attributed to the dissociation of H2O2 and formation of
hydroxyl radical by the catalysts via Fenton’s mechanism.
Various other types of catalysts have also been found to enhance the desulfur-
ization yield by similar mechanism of promoting the formation of hydroxyl radical,
these include EDTA, Na, and Mg-silicates (Hao et al. 2005), silica gel (Chen et al.
2006), molecular sieves loaded with various metal oxides (Chen et al. 2007),
transition metal salts (de Souza et al. 2009), and sodium bicarbonate (Deshpande
et al. 2004). Activated carbon was found to increase the desulfurization level in case
of fuel oil from 60% to 95% in the presence of H2O2/formic acid oxidation system
(Yu et al. 2005). Zhu et al. reported that activated carbon possesses both reducing
sites and oxidizing sites which perform the same action as Fe2+ and Fe3+ ions in
Fenton’s reagents during decomposition of H2O2. The reducing sites transfer
electrons to H2O2 to form HO. (hydroxyl) radical which oxidizes the sulfur com-
pounds. However, the competitive reaction that occurs involves the reaction of
Fe2+ + H2O2 Fe3+ + OH- + OH.
Fe2+ + OH. Fe3+ + OH-
OH. + H2O2 HOO. + H2O
Fe3+ + HOO. Fe2+ + O2 + H+
[O] [O]
S S S
O
O O
Scheme 8.13 Oxidation of sulfur compounds by Fenton’s mechanism

H2O2 OH- + HO. HOO.

H2O2
Reducing Sites
Activated Carbon HO. / HOO.

S
S O
O
Oxidizing sites
HOO. H+ + O2
Scheme 8.14 Oxidation of DBT in the presence of HCOOH/H2O2 over activated carbon
hydroxyl radical with the H2O2 molecule to produce hydroperoxy radical (HOO.)
and the oxidation of hydroperoxy radical to O2 and H+ by the oxidizing site on the
activated carbon. The competitive reactions may be inhibited by adjusting the pH
(Scheme 8.14).
Since reaction accelerates the ODS processes by promoting the formation of
hydroxyl radicals, therefore less amount of oxidant is required while using these
catalysts.
4 Adsorptive Desulfurization
In adsorptive desulfurization (ADS) various solid adsorbent materials are used to

selectively remove sulfur compounds from petroleum. The adsorptive desulfuriza-
tion is a very simple process which does not require much energy and can be
operated in column or batch mode. During the contact of feed and the adsorbent, the
sulfur compounds are selectively retained by the adsorbent, the desulfurized feed is
separated, and the feed is recycled to attain more desulfurization till the sulfur
breakthrough occurs. The efficiency of the process is primarily dependent on the
process conditions and the characteristics of the adsorbent material, such as its
adsorption capacity, mechanical stability, selectivity, and regeneration capability.
A variety of adsorbent materials has been used for desulfurization of various
petroleum distillate fractions such as gasoline, naphtha, diesel oil, jet fuel oil, and
model oil which has shown promising efficiency. Commonly used adsorbent
materials in this process include carbon-based adsorbents (Haji and Erkey 2003;
Kim et al. 2006; Sano et al. 2004a, b), different types of zeolites (Hernández-
Maldonado and Yang 2002; McKinley and Angelici 2003; Mikhail et al. 2002;
Salem 1994; Salem and Hamid 1997; Velu et al. 2003), silica, alumina, metal
organic framework (MOF) (Brieva et al. 2010; Irvine et al. 1999), reduced metals
(Bonville Jr et al. 2000; Fukunaga et al. 2003; Lesieur et al. 2002; Ma et al. 2005a,
b), metal sulfides (Ma et al. 2003), metal oxides, and modified composite oxides
(Turk and Gupta 2001; Watanabe et al. 2004; Zhou et al. 2006a) etc. Metal oxides
and composite materials come in the category of the nanostructured materials,
which show enhanced desulfurization efficiency.
Mechanistically, the adsorptive desulfurization can be divided into two catego-
ries, i.e., physical adsorption and reactive or chemical adsorption.
4.1 Physical Adsorption
Adsorptive desulfurization using carbon-based adsorbents and zeolites exhibits

physical adsorption in which the sulfur compounds are retained from the feed by
the adsorbent through physical interaction or Van der Waal forces. In such case, the
sulfur compound binds up to the adsorbent in its original form or structure via
physical forces such as hydrogen bonding or electrostatic attraction. Since such
forces are weaker, the adsorbent material can be regenerated at the cost of low
energy and the sulfur compounds can be recovered without any change in its
structure. The adsorbent can be regenerated by physical processes such as heating,
dissolution, or steam stripping.
Adsorptive desulfurization using activated carbon has been investigated by a
number of researchers (Haji and Erkey 2003; Rakesh Kumar and Srivastava 2012),
but the adsorption mechanism is not fully explored. Kostas et al. investigated the
adsorptive desulfurization of model oil using nanoporous carbons of different
nature (Triantafyllidis and Deliyanni 2014) and showed that the mechanism of
adsorption is influenced by the surface properties and the texture of the activated
carbon. The study revealed three possible factors responsible for the adsorption of
sulfur compounds on the activated carbon. The volume of micropores of the
activated carbon smaller than 10 Å is of the same dimension as the size of
4,6-DMDBT, which can be retained on the surface. The oxygenated functional
groups on the surface of activated carbon interact the oxidized S compounds
(sulfones) through hydrogen bonding. Besides the interaction between the
delocalized π electrons of the aromatic sulfur compounds and that of aromatic
rings of the activated carbon also provide a means of attachment. Kim et al. also
ascribed the adsorption of sulfur compound (4,6-DMDBT) on activated carbon to
the interaction through hydrogen bonding between the sulfur atoms and the surface
oxygen functional groups (Kim et al. 2006). Sano et al. presented the same
conclusion and reported that the adsorption of the sulfur compounds is enhanced
when the oxygen functional groups on the surface of activated carbon are increased
by chemical oxidation (Sano et al. 2004b). Scheme 8.15 describes the mechanism
for physical adsorption of sulfur compounds over activated carbon.
Due to electron donating effect of the alkyl substituents in the aromatic sulfur
compounds, the electron density is increased over the aromatic ring. It is, therefore,
Scheme 8.15 Adsorption mechanism of sulfur compounds over activated carbon
the alkyl substitution in sulfur compounds exhibits synergistic effect during phys-
ical adsorption rather than declining desulfurization by posing stearic hindrance,
which is the common observation in other desulfurization techniques (Kim et al.
2006). However, this phenomenon also contributes in the limited selectivity of
physical adsorptive desulfurization, because the non-sulfur aromatic compounds
also show the similar behavior.
4.2 Chemical or Reactive Adsorption
In this type of adsorption, chemical bonding is responsible for binding the sulfur
compounds to adsorbent as a result of chemical reaction. In this process, the nature
of the sulfur compounds is altered, mostly by decomposition, whereas the sulfur
atom is bound to the adsorbent as sulfide. It has been shown that the selectivity of
the desulfurization by reactive adsorption is very high but in this process, the
regeneration of the adsorbent is very difficult (Hernández-Maldonado and Yang
2004a, c). Since the sulfur is bound to the adsorbent through chemical bonding,
regeneration of adsorbent cannot be effectuated by physical processes. The adsor-
bent can be regenerated by reduction or strong heating in air (oxidation), where the
sulfur may be removed as H2S or sulfur oxides; however, the form of sulfur
removed also depends upon the nature of adsorbent and sulfur compounds (Babich
and Moulijn 2003).
Scheme 8.16 Adsorption

of sulfur compounds by
π-complexation
Based on the route of chemisorption, desulfurization by reactive adsorption can

further be classified into two categories. The first category involves a direct reaction
between sulfur atom and the adsorbent reactive site, whereas the second involves
cracking of the sulfur compounds and the sulfur atom released further adsorbed on
the adsorbent through a chemical reaction.
4.2.1 Adsorption Involving π-Complexation of Sulfur Compounds
The former type of reactive adsorption is exhibited by composite materials or metal

supported zeolites, in which π-complexation is established between the metal atom
in the adsorbent and organosulfur compounds, whereby the sulfur compound is
removed from the oil stream. The interaction by π bonding is relatively stronger
than the Van der Waal’s attractive forces of physical adsorption, therefore the
desulfurization efficiency is high in this case. A number of transition metals
including Ag, Cu, Co, Zn, Ni, Ce, etc. supported on various supports like
zeolite Y, MCM-41, and silica gel have been used for this purpose (Hernández-
Maldonado et al. 2005; Hernández-Maldonado and Yang 2002; Ma et al. 2005b;
McKinley and Angelici 2003; Tian et al. 2005; Velu et al. 2003). Clay-based
adsorbents like bentonite modified with KMnO4 or loaded with π-complexation
species such as Fe+3, Cu+1, and Cu+2 are also used for desulfurization of model
gasoline (Tang et al. 2011).
The π-complexation mechanism has been explained by adsorption of
4,6-DMDBT over Cu+ loaded on Fujasite (Hernández-Maldonado and Yang
2004b). During complexation between Cu+ with outer electronic configuration 3d
4s and sulfur atom in aromatic ring, the thiophenic ring forms σ bond by
10 0
donating π electrons to the empty s orbital of the Cu+, in turn, the d orbital of
cation back donate electrons to the π* orbital of the thiophenic ring (Hernández-
Maldonado and Yang 2004c). It has been confirmed through experimental data and
molecular orbital calculations that the π-complexation of Cu ions with sulfur-
containing aromatic rings is stronger than with simple aromatics, i.e., containing
no sulfur atom (Takahashi et al. 2002) (Scheme 8.16).
Cu and Ag exchanged faujasite zeolites, i.e., Ag-Y and Cu(I)-Y, have been
found to efficiently remove thiophenes from the mixture of liquid hydrocarbons.
For feed containing 760 ppmw sulfur or 2000 ppm thiophene in n-octane, the order
of breakthrough and adsorption capacities for different zeolites was reported to be
as (Hernández-Maldonado and Yang 2003b):
CuðIÞ Y > Ag Y > H Y > Na Y&CuðIÞ Y > H Y > Na Y

> Ag Y
Application of Cu(I)-Y in combination with activated carbon as guard bed layer

can perform as more efficient desulfurization system, capable of reducing the sulfur
content of commercial gasoline and diesel to less than 0.28 ppmw (Hernández-
Maldonado and Yang 2003a). Similar layered bed adsorbents consisted of Cu(I)-Y,
activated carbon, and activated alumina (Selxorb) have been studied for desulfur-
ization of diesel fuels at ambient pressure and temperature, which show desulfur-
ization level up to 76 ppbw. The layered bed adsorbents containing alumina and Cu
(I)-Y can be regenerated by calcination in air at 350 C, followed by auto-reduction
of the Cu species. The organosulfur compounds can also be recovered with solvent
elution using CCl4 and N,N-DMF solvents (Hernández-Maldonado et al. 2004). A
hybrid material, as-synthesized mesoporous silica (SBA-15) containing Cu2O was
used to efficiently adsorb thiophene from model oil by π-complexation (Kou et al.
2015). Recently SiO2-NiO aerogels with different Si/Ni ratios have also been found
to be efficient adsorbents for removal of thiophenic sulfur from model oil. The
maximum saturation adsorption capacities of 6.46 and 2.13 mgS/g were attained for
thiophene and benzothiophene, respectively, using SiO2-NiO aerogel with Si/Ni of
23 (Chen et al. 2016).
4.2.2 Adsorption Involving Cracking of Sulfur Compounds
A number of adsorptive desulfurization processes are based on this mechanism,

where during the adsorption process, the sulfur compounds are cleaved by high
temperature or by H2 and the sulfur atom released during cracking chemically
reacts with the adsorbent. This technique is actually a combination of
hydrodesulfurization and adsorption. The adsorbent used in this process are com-
monly transition metal supported on basic oxides; however, most favorite adsorbent
is NiO and ZnO, or nickel-based materials supported on silica, alumina, etc.
A commercial desulfurization process based on reactive adsorption called
IRVAD process, developed by Black and Veatch Pritchard Engineering Company,
uses selective adsorbents containing alumina for adsorption of sulfur from petro-
leum (Babich and Moulijn 2003; Song and Ma 2003; Yang et al. 2003). In this
process, in a multistage reactor, the feed is allowed to contact countercurrently with
the adsorbent in 4:1 ratio, at 240 C and atmospheric pressure. In pilot plant
experiments using cooker naphtha and FCC gasoline as feed, the process operated
with 90% desulfurization efficiency (Babich and Moulijn 2003). The s-zorb pro-
cess, developed by Phillips Petroleum Co. (USA), utilizes simultaneous
Scheme 8.17 Reactive adsorption of sulfur compounds over Ni supported on ZnO in the presence
of H2
hydrotreatment and adsorption. In this process, the feed, i.e., gasoline or diesel, is
charged into fluidized bed reactor along with the adsorbent and gaseous hydrogen at
2–20 bars pressure and 340–410 C temperature, under which the sulfur is bound to
the adsorbent (Song and Ma 2003; Velu et al. 2003). The adsorbent composition is
undisclosed; however, it is thought that it consists of ZnO and NiO loaded on silica
or alumina (Gyanesh et al. 2000). The process is capable of attaining 98 %
desulfurization, and in the case of using gasoline the sulfur content was decreased
from 1100 ppmw sulfur to 25 ppm, with about 3 % reduction in olefin content of
the feed.
The mechanism of desulfurization by reactive adsorption involving degradation
of sulfur compounds has been investigated by Lichun et al. using Ni/ZnO as an
adsorbent for model oil containing DBT (Huang et al. 2011). The reactive adsorp-
tion was tested in N2 and H2 atmosphere with 0.9 MPa pressure and temperature of
250 C, which revealed that in the former case the adsorption rate was very slow
and desulfurization efficiency was poor, whereas in the presence of H2 the adsor-
bent shows high activity and capacity. The role of hydrogen was found to be
decomposition of DBT over the surface of Ni, leading to the formation of Ni3S2,
and later the sulfur is transferred to ZnO with the regeneration of Ni species. The
proposed mechanism for the reactive-adsorptive desulfurization completes in three
steps. The first step involves the cracking or decomposition of sulfur compounds,
i.e., DBT, over the Ni surface and the sulfur released during decomposition reacts
with Ni to form Ni3S2. In the second step, the hydrogenation of Ni3S2 leads to the
formation of H2S with regeneration of Ni species, whereas in the third step the H2S
is adsorbed by ZnO, to form ZnS (Scheme 8.17).
During the process, ZnO not only serves to adsorb the sulfur released from
regeneration of Ni but also functions as a cocatalyst for cracking of sulfur com-
pounds by Ni, the phenomenon has been reported by other researchers as well
(Babich and Moulijn 2003; Bezverkhyy et al. 2009; Fan et al. 2010; Tawara et al.
2000, 2001). New advancement is going on the confirmation of the mechanism and
improvement of the structural stability and reactivity of the Ni/ZnO adsorbent
(Meng et al. 2012; Ullah et al. 2016; Wen et al. 2012). Rooh Ullah et al. used
Ni/ZnO dispersed on alumina to increase the stability of the catalyst, and they
suggested the regeneration of the ZnS formed in the last step by oxidation under
high temperature where ZnS is converted into ZnO (Ullah et al. 2016).
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Chapter 9
Role of Nanomaterials as an Emerging Trend
Towards the Detection of Winged
Contaminants
Santanu Patra, Rashmi Madhuri, and Prashant K. Sharma
Abstract Hydrocarbons are very important as efficient energy sources in our day-
to-day life. But apart from their application point of view, the most concerned area
is their toxicity. A large number of literatures are being reported describing the
toxicity from the last few decades. Polycyclic aromatic hydrocarbons (PAHs) and
volatile organic compounds (VOCs) are the most common type of toxic hydrocar-
bons, most abundantly found in nature. Exhaust gas from motorbikes, combustion
of coal, wood, and petroleum products are the major sources of those hydrocarbons.
They are entering into the human or animal body by means of breathing, through
skin, food, and water samples and caused various diseases including cancer. This
makes their detection and extraction very much important. In this chapter, we have
tried to sum up the source, contamination, and health effects of those hydrocarbons
along with their detection and extraction techniques in combination with
nanomaterials, reported so far. Major emphasis has been given on nanostructure-
based sensing technique due to additional advantages and future point of view.
Keywords Polycyclic aromatic hydrocarbons • Volatile organic compounds •

Nanomaterials • Sensing • Extraction
1 Introduction
The chemistry of hydrocarbon is very popular in organic chemistry. Hydrocarbons

are known to be the simplest type of organic compounds containing only hydrogen
and carbon in their structure. They are quite abundant in modern society, in which
most commonly ingested hydrocarbons include gasoline, lubricating oil, motor oil,
S. Patra • R. Madhuri (*)

Department of Applied Chemistry, Indian Institute of Technology (Indian School of Mines),
Dhanbad, Jharkhand 826 004, India
P.K. Sharma
Functional Nanomaterials Research Laboratory, Department of Applied Physics, Indian
Institute of Technology (Indian School of Mines), Dhanbad, Jharkhand 826 004, India

246 S. Patra et al.
Fig. 9.1 Flowchart showing the general classification of hydrocarbons
mineral spirits, lighter fluid/naphtha, lamp oil, and kerosene. Basically, hydrocar-
bons can be divided into two categories: aliphatic and aromatic, depending on the
presence of benzene ring (Fig. 9.1). Aliphatic hydrocarbon is of three types
depending on the nature of bonding (Olah and Molnar 2003). That is, if only single
bonds are present in the backbone, this is known to be an alkane, if a double bond is
present, it will be known as alkene and in the case of a triple bond, it will be alkyne.
After bonding, if they form a cycle, then they will be called as cycloalkanes. They
can also be classified as saturated and unsaturated hydrocarbons (Olah and Molnar
2003). Saturated hydrocarbon has only single bonds in the structural backbone and
contains the maximum number of hydrogen atoms for each carbon atom. Unsatu-
rated hydrocarbons contain multiple bonding and contain less than the maximum
number of hydrogens per carbon. These are major classes of hydrocarbons and will
be found in detail in any basic organic chemistry books. Halogenated hydrocarbons
are a subgroup of aromatic hydrocarbons, in which one of the hydrogen molecules
is substituted by a halogen group. The most important halogenated hydrocarbons
include carbon tetrachloride, trichloroethylene, tetrachloroethylene,
trichloroethane, chloroform, and methylene chloride.
Apart from their classification and structure, they are very important in our day-
to-day life as efficient energy sources. The majority of hydrocarbons found on this
planet are coming from the crude oil, where decomposed organic matters provide
an abundance of carbon and hydrogen, which after bonding forms limitless chains
(Speight 2011). Basically, natural gas, petroleum, and coal are the three major
sources of these hydrocarbons. Natural gas is very popular for generation of
9 Role of Nanomaterials as an Emerging Trend Towards the Detection of Winged. . . 247
temperature and it is a powerful domestic cooking and heating fuel. It is a fossil fuel
formed when layers of buried plants, animals, and gases are exposed to intense heat
and pressure for thousand years. The energy obtained by plants from the sun is
stored in the form of chemical bonds in natural gas. Natural gas basically a
hydrocarbon gas consists of methane (major composition) with varying amounts
of other higher alkanes and even a lesser percentage of carbon dioxide, nitrogen,
and hydrogen sulfide (Smil 2015). In many developed countries, it is supplied
through pipes to home, where it is used for many household purposes. Petroleum
is the mixture of a large number of different hydrocarbons, most commonly alkanes
(paraffins), cycloalkanes (naphthalene), aromatic hydrocarbons, and complicated
chemicals like asphaltenes (Petrov 1987). The alkanes from pentane (C5H12) to
octane (C8H18) are refined into petrol and from nonane (C9H20) to hexadecane
(C16H34) into diesel fuel, kerosene, and jet-fuel (Simanzhenkov and Idem 2003).
Alkanes with more than 16 carbon atoms can be refined into fuel oil and lubricating
oil. Paraffin wax and asphalt are such types of alkanes with 25 and 35 carbon atoms,
respectively (Simanzhenkov and Idem 2003). The shortest molecules with four or
fewer carbon atoms are in the gaseous state at room temperature. They are known as
petroleum gases.
The third form of hydrocarbon or coal is a fossil fuel and is the altered remains of
prehistoric vegetation that originally accumulated in swamps and peat bogs. The
energy we get from coal today comes from the energy that plants absorbed from the
sun millions of years ago. Coal combustion is another source of hydrocarbons.
During coal gasification, it produces syngas. Methanol, hydrogen, carbon monoxide
with certain olefins, acetic acid, formaldehyde, ammonia, urea, and others are
present in the produced syngas. With respect to natural resources, vegetation is
the main emitter of hydrocarbons, with compounds such as ethylene, isoprene, and
monoterpenes.
Despite their natural origin and seems to be eco-friendly nature of hydrocarbons,
their toxicity and their evil effects to the atmosphere are widely reported. The
hydrocarbons which are abused for euphoric effects via the respiratory route of
exposure (e.g., toluene) are named inhalants (Tormoehlen et al. 2014). Toxicity is
related to the dose, and the chemical characteristics of volatility, lipid solubility,
viscosity, and surface tension. Those with higher volatility could be better absorbed
after inhalation. Lipophilic hydrocarbons cross the blood–brain barrier more readily
and able to effect central nervous system (CNS) more often. Hydrocarbons with low
viscosity and low surface tension may result in aspiration (Mowry et al. 2013).
There are some types of hydrocarbon exposures including:
• Children with usually unintentional ingestion of household hydrocarbons
• Workers with dermal or inhalational occupational exposures
• Adolescents and young adults with intentional inhalational abuse
Hydrocarbons are present as trace gases in the atmosphere, with methane as the
predominant hydrocarbon molecule with an approximate concentration 1.7 ppmv
(parts per million by volume) (Dewulf and Langenhove 2009). Besides methane,
other hydrocarbons are in the parts per billion or parts per trillion ranges. The main
248 S. Patra et al.
toxicity of these hydrocarbons lies in the photochemical air pollution. It is being

reported and examined that methane and hydrocarbons have a high contribution to
global warming, ozone depletion and acute, chronic toxicity with carcinogenicity
(Tormoehlen et al. 2014). In addition to the environmental side effects, hydrocar-
bons also play a critical role in the atmospheric chemistry and atmospheric hydro-
carbons have a high environmental relevance. The most important contributors in
this regard can be categorized into two major classes: (1) polycyclic aromatic
hydrocarbons (PAHs) and (2) volatile organic compounds (VOCs). Herein, we
have compiled the detection techniques used so far for detection of these com-
pounds using the help of nanotechnology.
2 Polycyclic Aromatic Hydrocarbons (PAHs)
Polycyclic (Polynuclear) aromatic hydrocarbons (PAHs) are a class of complex

organic chemicals, containing carbon and hydrogen with a fused ring structure with
at least two benzene rings (Abdel-Shafy and Mansour 2016). They may have also
additional fused rings that are not six-sided. Benzopyrene is most popular among all
the PAHs, containing five rings. They have a very low vapor pressure and present
both as gas and in associated form with particles, at ambient temperature in air. The
lighter PAHs, like phenanthrene, are present mostly in gas phase whereas the
heavier PAHs like benzopyrene are almost totally adsorbed onto particles
(Ravindra et al. 2008). Additionally, these types of compounds are carcinogenic
in nature and known as one of the first atmospheric pollutants, suspected to have a
carcinogenic effect (Ravindra et al. 2001). It has also been reported that, with an
increase in the molecular weight, the carcinogenicity of PAHs also increases, and
their acute toxicity decreases. Benzopyrene is important for being the first chemical
carcinogen to be discovered (Ravindra et al. 2008). Benz[a]anthracene and
chrysene, benzo[k]fluoranthene, benzo[b]fluoranthene, indeno[1,2,3-cd]pyrene,
benzo[j]fluoranthene, and dibenz[a,h]anthracene are identified as highly carcino-
genic and teratogenic materials. They appear as mostly colorless or sometimes
white or pale yellow-green solids. The structures of most common PAHs are shown
in Fig. 9.2.
2.1 Sources of PAHs
The best possible sources of PAHs are the incomplete combustion of fossil fuel
(petroleum, natural gas, and coal) and burning vegetation. They are always found in
a complex mixture and commonly not exist as a single product. Other important
sources of PAHs are from oil seepage, petroleum spills, and diagenesis of organic
matter in anoxic sediments. They can also be found in coal tar, roofing tar, creosote,
and crude oil. Few of the PAHs are used in medicine or to make plastics, dyes, and
Fig. 9.2 Structures of toxic and commonly reported PAHs
pesticides. Naphthalene, anthracene, phenanthrene, fluorene, fluoranthene, and

pyrene are prepared in chemical laboratories for their commercial use. According
to Ravindra et al., the sources of PAHs can be classified into five major categories:
domestic, mobile, industrial, agricultural, and natural (Wing and Bada 1992).
Beegle et al. have proposed some cosmic sources of PAHs also (2001). Domestic
emissions are mostly associated with the burning of coal, gas, oil, garbage, and
some other organic substances like tobacco or char broiled meat. According to
WHO, wood, dried animal-dung-cake, and crop waste from agricultural residue are
widely used as fuel for cooking in the developing nations. According to that report,
~75% people in India, China, and South East Asia, and 50–75% people from South
America and Africa are using these solid fuels for their daily cooking. The partial
combustion of coal (a hydrogen-to-carbon ratio <1) is a major source of PAH
compounds. According to Bostrom et al. wood burning is being reported to con-
tribute 430 kg benzopyrene, whereas gasoline and diesel vehicles together were
estimated to contribute up to 320 kg benzopyrene in Sweden (1999). Schauer and
Cass reported the similar results for Los Angeles city (Schauer and Cass 2000).
Mobile sources of PAHs are the emission from vehicles such as aircraft, railways,
shipping, off-road vehicles, automobiles, and machinery. According to Paturel et al.
the emission of PAHs from these sources is a function of engine type, load and age,
fuel type and quality (1996). For gasoline automobiles, it has been reported that the
production of PAHs is mostly depended on the air/fuel ratio. It has also been found
that the amount of PAHs in engine exhaust decreases with a leaner mixture. In their
experiments, Jones et al. (2004) found that with the increase in air/fuel combustion
250 S. Patra et al.
ratio, the high molecular weight PAHs diminished rapidly (Jones et al. 2004). The
use of diesel and diesel/electric locomotives in rail transportations is also important
sources of PAHs emission. It is also reported that ~139 tons of PAHs are emitted by
the creosoted ties of the Swiss railway network (Kohler and Kunniger 2003). The
primary aluminum production (mainly by Soderberg process), coke production,
waste burning, creosote and wood preservation, petrochemical and related indus-
tries, cement manufacture, rubber tire manufacturing, bitumen and asphalt indus-
tries, and commercial heat/power production are known as the best possible
industrial source of PAHs (Ravindra et al. 2008). In a study, carried out by Pisupati
et al. only acenaphthene, fluoranthene, and naphthalene were detected with their
emission factors ranged from 85 to 320 mg/kg of fuel fired in water boiler (2000).
The open burning of agricultural biomass is the main agricultural PAHs source. The
emission factor as determined by Jenkins et al. is highest among all and it varied
from 5 to 683 mg/kg (1996). Natural sources of PAHs can be divided into two
categories: terrestrial origin and cosmic origin. Nonanthropogenic burning of
forests, woodland, and moorland due to lightning strikes and volcanic eruptions
come under the terrestrial sources. Whereas, carbonaceous chondrites, originated in
the main asteroid belt, which are not associated with life is reported as the cosmic
sources of PAHs.
2.2 Contamination of PAHs in Atmosphere, Soil, Sediments,

and Food Samples
After the emission of PAHs from the abovementioned sources, they mainly con-
taminate the atmospheric air. In the atmosphere, PAHs are mainly found in two
separate phases, a vapor phase and a solid phase in which the PAHs are sorbet onto
particulate matter. It has been found that hydrophobic organic chemicals with a low
vapor pressure (here PAHs) will sorbet to particulate matter with high efficiency
than the chemicals with a high vapor pressure (like benzene). It has been found that
the relative distribution of PAHs in two phases will be different for the given air
samples, as different PAHs have different molecular weight, which in turn have
different vapor pressure (Abdel-Shafy and Mansour 2016). The adsorption of PAHs
is also depended on the types of suspended particulates (e.g., soot, fly ash, dust,
pollens, and pyrogenic metal oxides). Literatures have reported the continuous
deposition of PAHs to the earth surface by dry or wet deposition processes. After
deposition to the earth’s surface, PAHs can become mobile and the majority of
PAHs in the soil will be bound to soil particles (Masih and Taneja 2006). The
mobility of PAHs on earth surface, i.e., in soil, is dependent on the sorbent particle
size and the pore throat size of the soils. In a similar way as that of surface soils,
PAHs are deposited to the sedimentary environment. In rural areas, the PAHs can
settle on the surface of streams, lakes, and oceans by dry or wet deposition and
eventually they become integrated with the sediment. When they enter to the
atmosphere or soil samples, it is evident that they should contaminate the food
samples and will enter the human body. The existence of PAH in foods is admin-
istered mainly by similar physicochemical factors used to determine the absorption
and distribution in man. That is the relative solubility of PAHs in organic solvents
and water. This solubility will determine their capacity for transportation and
distribution between different environmental compartments and finally their uptake
and accumulation by living organisms (Abdel-Shafy and Mansour 2016).
2.3 Human Exposure to PAHs and Health Effects
PAHs are mainly entered into the human body by breathing contaminated air or
eating food that may contain PAHs or smoking cigarettes, or by breathing smoke
from open fireplaces. Tobacco smoke contains certain types of PAHs, which are
suspected to be human carcinogens. For nonsmokers, the main route is exposure
through food or contaminated air. High-temperature cooking (i.e., grilling, roasting,
and frying) also formed PAHs, which may enter into the human body after
accumulation. Sometimes PAHs are synthesized or absorbed by some crops like
wheat, rye, and lentils via water, air, or soil. The intake of PAHs mainly occurs from
the contaminated soil via ingestion, inhalation, or dermal (skin) exposure and from
inhalation of PAH vapors. Mechanics, street vendors, motor vehicle drivers, and the
workers of mining, oil refining, and metal working accumulate PAHs through
breathing exhaust fumes (Abdel-Shafy and Mansour 2016).
The concentration of PAHs during exposure, the toxicity of the accumulated
PAHs, the route of exposure (i.e., via inhalation, ingestion, or skin contact), and
time and length of exposure are the main factors that determine the acute effects of
PAHs. The short-term exposure to PAHs has been reported to cause impaired lung
function in asthmatics and thrombotic effects in people affected by coronary heart
disease. However, it cannot be identified which components of the mixture are
responsible for that. The high levels of pollutant mixtures containing PAHs are
known to cause symptoms like eye irritation, vomiting, diarrhea, and nausea. They
sometimes cause skin irritation and inflammation to the human body. Benzopyrene
and naphthalene are known to be direct skin irritants, while anthracene and benzo-
pyrene are reported to be skin sensitizers, i.e., they may cause allergic skin response
in animals and humans. As long-term health effects, increased risk of skin, lung,
bladder, and gastrointestinal cancers are being reported. Pyrene and benzopyrene
has been identified as the cause of cancer in laboratory animals. Wells et al. have
reported the effects of PAHs in animals, which may not be detected in human body
(2010). Further animal studies also confirm that some PAHs can affect the hema-
topoietic and immune systems producing reproductive, neurologic, and develop-
mental effects. A number of laboratory studies have done, where animals were
exposed to a certain concentration of some PAHs over long period of time and
found that they have suffered from stomach cancer from ingesting PAHs in food,
lung cancer from inhalation, and skin cancer from skin contact (US EPA 2008).
252 S. Patra et al.
Benzo(a)pyrene is reported to be the most common PAH to cause cancer in animals.

Kristensen et al. conducted some laboratory studies on mice and found that inges-
tion of high levels of benzo(a)pyrene during pregnancy resulted in birth defects and
a decreased body weight in the offspring (1995). In human body, the long-term
exposure to PAHs may form cataracts and cause kidney or liver damage and
jaundice. Naphthalene can cause redness and inflammation of the skin after long
time contact and after breathing, they may cause the breakdown of red blood cells.
Till now, no study has performed to understand the human health effects following
oral exposure to PAHs. Reactive metabolites like the epoxides and dihydrodiols of
some PAHs have the potential to bind to cellular proteins and DNA with toxic
effects and this becomes one of the major health concerns in recent days. These will
result in a biochemical disruption and cell damage, which may also lead to
mutations, developmental malformations, tumors, and cancer (Bach et al. 2003).
Extensive studies confirm that the mixtures of PAHs are more carcinogenic to
humans than individual PAHs. U.S. Environmental Protection Agency (US EPA
2008) have classified seven PAHs as probable human carcinogens: benzo(a)pyrene,
indeno(1,2,3-cd)pyrene, benz(a)anthracene, dibenz(ah)anthracene, benzo(b)
fluoranthene, benzo(k)fluoranthene, and chrysene. Workers from coal gasification,
chimney sweeper, oil refining, and roofing have the common problems of skin
cancer in most of the cases. According to Armstrong et al. excessively high rate
(16-fold higher) of lung cancer was found in coke-oven workers and this is closely
correlated with the time spent for working on top of ovens where a high benzopy-
rene concentration was obtained (2004).
2.4 Detection and Extraction of PAHs
As we discussed earlier, PAHs are very carcinogenic to animals and human being.
The atmospheric air, soil, and food samples are being continuously contaminated
by these PAHs mixtures, which makes their detection as well as extraction very
important. Gas chromatography, gas chromatography-mass spectrometry
(GC-MS), electrochemical bio-sensing, immunoassay, high-performance liquid
chromatography (HPLC), and surface-enhanced Raman spectroscopy has been
popularly applied for the determination of PAHs in various research articles.
Very recently, Taniguchi et al. have reported the detection of PAHs and
polychlorinated biphenyls (PCBs) in plastic pellets collected randomly from
41 beaches (15 cities) from the coast of the state of S~ao Paulo, south eastern Brazil
using GC-MS as the detection technique. The concentration for PAHs detection
was found in the range from 192 to 13,708 ng g1. The area was affected by both
waste disposal and industrial complex, which was reported to be the main cause of
the contamination (Taniguchi et al. 2016). A similar GC-MS analysis method was
reported by Bian et al. for the detection of PAHs in ambient air of Riyadh, Saudi
Arabia. Sixteen particle-phase PAHs were reckoned in 167 samples. Among them,
pyrene and fluoranthene were the most abundant PAH, with an average population
of 3.37 14.01 ng m3 and 8.00 44.09 ng m3, respectively. The widespread
contamination of PAHs can be attributed to the oil combustion, i.e., large annual
production and consumption, in Saudi Arabia (Bian et al. 2016). One of the recent
literatures has also reported the finding of PAHs in 23 farmland soil samples and
10 riverine sediment samples from Guiyu, China. Guiyu is known for the largest
electronic waste (EW) in China and the PAHs contamination is due to their
combustion of liquid fossil fuels or coal, for the purpose of incinerating EWs,
rather than EW combustion itself. They have determined a PAH concentration of
56–567 ng/g in the soils and 181–3034 ng/g in the sediments (Xu et al. 2016a).
Akhbarizadeh et al. have reported the quantification of aliphatic and polycyclic
aromatic hydrocarbons in coastal water and sediments of Khark Island, SW Iran
using a gas chromatography/flame ionization detector (GC-FID) for the quantifica-
tion. Twenty six aliphatic hydrocarbons (AHs), 16 polycyclic aromatic hydrocar-
bons (PAHs), and total petroleum hydrocarbons (TPHs) were found in that
particular area (Akhbarizadeh et al. 2016). Ohura et al. have determined the
concentrations of PAHs and chlorinated PAHs (ClPAHs) in different seasons at
five sampling stations in Nagoya, a Japanese megacity using a gas chromatographic
technique. They have found an annual total PAH concentration of 5200–8570 pg/m3
(Ohura et al. 2016).
The Himalayas is the highest mountain in the world, of world’s highest peaks
including Mount Everest, however, it is also not free from PAHs contaminations.
Recent literatures have reported the contamination of surface soil of Himalayan
region by PAHs, with a total concentration in the range of 15.3–4762 ng/g. PAHs
benzo(a)pyrene (BaP), benzo(a)anthracene (BaA), benzo(b)fluoranthene (BbF),
benzo(k)fluoranthene (BkF), chrysene (CHR), and indeno (1,2,3-cd) pyrene
(IcdP) are known for their carcinogenic property and they all have been found in
the Himalayan soils. It has been reported that the PAHs contamination at mountain
surface soil is the result of atmospheric deposition and sources from nearby areas
(Devi et al. 2016).
Dhanbad, Jharkhand is known for the coal city of INDIA and is one of the
polluted cities also. Therefore, from our institute, a quantitative study was carried
out to understand the PAHs concentration in the coal mines area. In the study, the
concentration variation at different locations of the city depending on the vehicular
traffic was monitored using HPLC technique. At traffic site, they have found a PAH
concentration of 1.019–10.856 μg/g and in control/rural site, the concentration was
0.640 μg/g. The higher contaminated value is due to the vehicular emission and
various coal mining activity in the surrounding area of Dhanbad city. Coal mining is
known to be the major source of these PAHs along with associated emissions from
automobile exhaust and industries, biomass burning, resuspended soil dust and
earth crust, oil combustion, and fugitive emissions (Suman et al. 2016). Recent
literatures have also reported the detection of PAHs in Tar ponds and surrounding
environments adjacent to a former coking and steel manufacturing facility using
fingerprinting technology (MacAskill et al. 2016). Fernandez-Amado has reported
an online in-tube solid-phase microextraction (IT-SPME) coupled to HPLC-
254 S. Patra et al.
photodiode array-fluorescence detection technique for the analysis of PAHs in low

volume rainwater samples (Fernández-Amado et al. 2016).
In the case of sensing or extraction, nano-sized materials are a good choice, due
to their physicochemical properties, i.e., small size of nanomaterials, large surface-
to-volume ratios, composition, shape, and unusual target binding characteristics
(Patra et al. 2016). They can markedly improve the sensitivity and specificity of
analyte detection. Herein for a better understanding of the readers, we have
classified the nanoparticles-based sensing/extraction techniques into four different
categories (Table 9.1):
1. Noble metal nanoparticles
2. Magnetic nanoparticles
3. Carbonaceous materials
4. Molecularly imprinted materials
5. Other nano-sized materials
2.4.1 Noble Metal Nanoparticles Based Extraction/Sensing Techniques
Noble metal nanoparticles are the most popular and widely studied colloidal
systems in the field of nanoscience and nanotechnology. The popularity is mainly
due to their unique characteristics like high surface-to-volume ratio, broad optical
properties, easy synthesis, facile surface chemistry, and their versatile behavior in
diagnostic assays (Conde et al. 2012). Gold (AuNPs) and silver nanoparticles
(AgNPs) are the most popular among all noble metal nanoparticles. Numerous
literature can be found on the different synthesis approaches and applications. Gold
has been utilized in India since 1000–600 BC for medical purposes in the form of
swarna bhasma (meaning, gold ash). In addition, role of gold nanoparticles as a
sensing device has widely been reported.
Wang et al. have recently reported gold nanoparticles decorated hydrophobic
porous polymer as surface-enhanced Raman spectroscopy substrate for the trace
level detection of PAHs. For the preparation of the polymer, glycidyl methacrylate
and ethylene dimethacrylate were used as monomers. The PAHs were adsorbed to
the polymer matrix through presumed hydrophobic interaction, which brings the
analytes close to the substrate. Anthracene, phenanthrene, and pyrene were selected
as probe molecules for PAH detection and show the limit of detection
(LOD) ¼ 0.93 107, 4.5 107, and 1.1 107 M, respectively. The substrate
was reported to have high reproducibility and was applied for the rapid screening of
PAHs in environmental water samples also (Wang et al. 2015a). A highly repro-
ducible and portable surface-enhanced Raman scattering (SERS) sensor for PAH
has been reported by Xu et al. using a new concept of coffee ring effect. It has been
reported that this coffee ring effect could separate PAHs from the bulk solution and
concentrate them on the closely packed AuNPs ring, which will enhance their
Raman scattering (Xu et al. 2014). To confirm this, citrate-reduced and structurally
unmodified AuNPs with 20 nm size were used. Due to this coffee ring effect,
closely packed but not aggregated AuNPs arrays were formed, this facilitated the
Table 9.1 List of nanosensors reported for the detection/extraction of PAHs
Analytical Real sample Recovery
S.N. Materials technique PAHs detected LOD analyzed (%) References
1. Au NP-GMA-EDMA SERS Anth, phen and pyrene 0.93 107, 4.5 107, Water samples – Wang et al.
1.1 10 7 M (2015a)
2. Closely packed Au NP SERS Naph, anth, pyrene, – River water – Xu et al. (2014)
ring BaP, BghiP, and IP samples
3. Au NPs/Nickel foam SERS Pyrene 108 M Tap water samples 94.4–115.0 Zhao et al.
(2015)
4. Au NPs/TiO2 NTs SERS BaP 12.6 nM Water samples 89.97–116.2 Sheng et al.
(2012)
5. CD-AuNPs SERS Anth, pyrene, chry, 100, 10, 100 and – – Xie et al. (2011)
and tpy 1000 nM
6. Bare AuNPs coupled SERS BbF, fluo, BaA, and 1.2 108, 2.0 108, Soil samples – Gu et al. (2016)
film system pyrene 5.5 108 and
6.3 108 M
7. CD-AgNPs SERS Pyrene and anth 7.5 and 10.0 μM – – Xie et al. (2010)
8. Ag NPs decorated SERS Anth, fluo, pyrene and 4.8 107, 1.3 107, Sludge samples – Qu et al. (2013)
humic acid 3,4-benzopyrene 5.5 107 and from local river
1.3 107 M
9. Bromide-coated UPLC- 15 PAHs 0.4–10.3 ng L1 River water, 59.23–87.95 Wang et al.
Fe3O4 NPs FLD wastewater, and (2015b)
tap water samples
10. Fe3O4@MPS@IL NPs mSPE- 7 PAHs 0.1–10 ng L1 Coffee and tea 87.5–104.5 Shi et al. (2016)
HPLC- samples
FLD
11. Fe3O4@SiO2@Flu mSPE- 16 PAHs 0.5–4.0 ng L1 Water samples 96.0–106.7 Cai et al. (2015)
9 Role of Nanomaterials as an Emerging Trend Towards the Detection of Winged. . .
GC-MS
12. MNP-APTES-Chol mSPE- 16 PAHs 0.2–7.8 ng L1 Drinking water 80.9–98.2 Cai et al. (2016)
GC-MS samples
255
(continued)
Table 9.1 (continued)
256
Analytical Real sample Recovery

S.N. Materials technique PAHs detected LOD analyzed (%) References
13. PDA@Fe3O4/ZIF-7 mSPE- Flu, anth, 0.71–5.79 ng L1 Rain water 92.8–99.4 Zhang et al.
GC-MS fluoranthene, pyrene, samples (2016a)
BbF and BbP
14. Ppy-PANI MSBSE- Naph, acenaph, 0.02–1.10 ng mL1 Wastewater, foun- 86–100 PAH magnetic
nanocomposite GC-FID acenaphthene, tains water, and SBSE
phen, and anth seawater samples Mollahosseini
et al. (2016)
15. Fe3O4-DVB-SO3- mSPE- Naph, acenaphthene, 1.1, 0.8, 1.1, 1.4, 0.6, 2.1, River and lake 79.9–115.3 Xue et al. (2015)
GC-MS fluo, phen, anth, and 0.7 pg mL1 water samples
fluoranthene and
pyrene
16. Thiol-modified SERS 8 PAHs 105–107 M – – Du and Jing
Fe3O4@Ag (2011)
17. Fe3O4@Au SERS 16 PAHs 5–100 nM River water – Du et al. (2016)
samples
18. mCNTs GC-MS 10 PAHs 0.05–0.42 μg L1 Lake water 80.5–110.2 Menezes et al.
samples (2015)
19. g-C3N4/Fe3O4 mSPE- 7 PAHs 0.05–0.1 ng mL1 Environmental 80.0–99.8 Wang et al.
HPLC-UV water samples (2015c)
20. Magnetic CN sheets mSPE- 8 PAHs 0.1–0.3 ng g1 Soybean oil 91.0–124.1 Zheng et al.
GC-MS samples (2016)
21. Graphene/ mSPE- Naph, acenaphthene, 0.009–0.02 μg L1 Seawater samples 83–107 Mehdinia et al.
Fe3O4@polythiophene GC-FID fluo, phen, and anth (2015)
22. Au-MNP-Silica mSPE- Fluo, phen, anth, 0.002–0.004 μg L1 Seawater samples 91.4–104.2 Mehdinia et al.
LLME-GC fluoranthene and (2014)
pyrene
S. Patra et al.
23. L-cysteine-capped PL Phen, anth, ~0.26 μg L1 – – Adegoke and
CdSeTe/ZnSe/ZnS pyrene and naph Forbes (2016)
QDs-GO
24. BTMSI-IL-GO SPME- 9 PAHs 0.015–0.025 μg L1 Potatoes and food- 89.1–101.3 Hou et al. (2016)
GC-FID wrap sample
25. GO-silica GC-MS 14 PAHs 0.05–0.36 ng/cig Mainstream ciga- – Shi et al. (2015)
rette smoke
26. CNTs SFE-GC- 15 PAHs 1–10 ng mL1 Soil samples 62.9–111.8 Han et al. (2015)
MS
27. MWCNT-MMM and MMMM- 8 PAHs 0.02–0.09 ng mL1 Sewage pond 99.0–100.5 Mukhtar and See
SLG-MMM, HPLC water samples (2016)
28. CD-silica microporous SPE- 8 PAHs 0.03–0.8 ng mL1 River, well, rain 50–160 Mauri-Aucejo
composite HPLC and salty water et al. (2016)
samples
29. Phenyl-functionalized SPME- naph, phen, 0.008–0.043 μg L1 Environmental 86.2–112.0 Guo et al. (2015)
TiO2 NS HPLC-UV fluoranthene and water samples
BaP
30. Bulk MIP SPE-GC- 16 PAHs 5.2–12.6 ng L1 Seawater samples 83–113 Song et al. (2012)
MS
31. Nano-MIP SPE- 1-HP, 2-HF, 9-HF, 0.33–2.6 ng mL1 Urine samples 78.22–95.41 Chauhan et al.
UHPLC 9-Phenanthrol, (2015)
1-Naphthol
LOD Limit of detection, Au NP Gold nanoparticles, GMA-EDMA glycidyl methacrylate-ethylene dimethacrylate, SERS Surface enhanced Raman scattering,
Anth Anthracene, Phen phenanthrene, Naph Naphthalene, BaP benzo[a]pyrene, BghiP benzo[g,h,i]perylene, IP indeno[1,2,3-cd]pyrene, CD cyclodextrin,
chry chrysene, tpy triphenylene, BbF benzo[b]fluoranthene, fluo fluoranthene, BaA benzo[a]anthracene, AgNPs Silver nanoparticles, UPLC ultraperformance
liquid chromatography, FLD fluorescence detection, MPS 3-(Trimethoxysilyl)propyl methacrylate, IL ionic liquid, HPLC High-performance liquid chroma-
tography, Flu Fluorenyl, Chol cholesterol chloroformate, mSPE magnetic solid-phase extraction, GC-MS Gas chromatography-Mass spectrometry, MNP
magnetic nanoparticles, APTES 3-aminopropyl triethoxy silane, PDA Polydopamine, ZIF 7 zinc benzimidazolate, Ppy Polypyrrole, PANI Polyaniline, mSBSE
magnetic stir-bar sorptive extraction, BbP benzo(b)pyrene, acenaph acenaphthylene, DVB Divinyl benzene, mCNTs magnetic carbon nanotubes, CN carbon
nitride, LLME liquid–liquid microextraction, PL photoluminescence, QD quantum dot, GO graphene oxide, BTMSI Bis(trifluoromethanesulfonyl)imide,
SPME solid-phase microextraction, MMMM Mixed Matrix Membrane Microextraction, MWCNT multiwalled carbon nanotube, SLG single layered graphene,
257
MIP molecularly imprinted polymers, 1-HP 1-Hydroxypyrene, 2-HF 2-hydroxyfluorene, 3-HF 3-hydroxyfluorene
258 S. Patra et al.
separation and concentration of hydrophobic PAHs. The prominent SERS enhance-

ment on the ring can be assigned to the electromagnetic mechanism. They have
used a mixture of six PAHs with different numbers of benzene rings, namely,
naphthalene, anthracene, pyrene, benzo[a]pyrene, benzo[g,h,i]perylene, and
indeno[1,2,3-cd]pyrene and identified them in river water. Previously Zhao et al.
and Sheng et al. have also reported the use of SERS technique towards PAH
determination with AuNP/nickel foam and AuNP-TiO2 nanocomposites. The
AuNPs/nickel foam nanocomposite was prepared by a galvanic replacement reac-
tion between nickel foam and auric chloride, followed by modification with long-
chain alkyl mercaptan molecules. According to Zhao et al. as-prepared 3-D AuNPs/
nickel foam nanocomposite have super-hydrophobic properties, which may be used
to detect PAHs via hydrophobic interactions (2015). The lowest detected concen-
tration of PAH using AuNPs/nickel foam nanocomposite was reported to be 108
M. In another work, AuNPs-TiO2 nanocomposite was prepared by
photocatalytically depositing AuNPs inside the titania nanotubes. The detection
limit was reported to be 12.6 nm with a recovery range of 89.97–116.2% for real
water samples analysis (Sheng et al. 2012). Similarly, a per-6-deoxy-
(6-thio)-β-cyclodextrin (CD-SH) modified AuNPs as a SERS sensor for PAH
detection have also been reported. Here the quantitative detection of the PAHs
was carried out using SERS technique on inclusion complexes with different
concentrations. The sensing of PAHs was based on the matching relationship
between the host and the guest, i.e., host–guest interaction mechanism (Xie et al.
2011). A bare AuNPs coupled film system for PAHs detection has been reported by
Gu et al. They have a self-assembled smooth gold film (Au-film) with a hydropho-
bic layer of the alkyl chain to capture the PAHs molecules from bulk solution to the
surface of Au-film. The lowest detection limits for the selected PAHs, i.e., benzo[b]
fluoranthene, fluoranthene, benzo[a]anthracene, and pyrene, were found as 1.2 108,
2.0 108, 5.5 108, and 6.3 108 M, respectively (Gu et al. 2016).
Like gold nanoparticles, silver has also been employed for the detection of
PAHs. Xie et al. have reported a beta-cyclodextrin (β-CD) inclusion complex on
AgNPs for the detection of PAHs by SERS. According to them, the designed
system has the ability to bind anthracene and pyrene into the hydrophobic cavity
of β-CD, which will cause the analytes to be closer to the surface of AgNPs, i.e., the
zone of electromagnetic enhancement (Fig. 9.3). This will enable to detect SERS of
PAHs and SERS spectra can easily distinguish the individual PAH compounds in a
mixture by their characteristic peaks. As β-CD was used for detection, it has the
feature of high selectivity due to its size of the cavity and will increase the
sensitivity, selectivity, and analytical importance of the proposed sensing device
(Xie et al. 2010). In another literature, Qu et al. have prepared humic acid decorated
AgNPs with an average diameter of 50 nm for the detection of anthracene,
fluoranthene, pyrene, and 3,4-benzopyrene. The adsorption of these aromatic mol-
ecules to the humic acid decorated AgNPs was explained by π–π stacking interac-
tions between the adsorbate and adsorbent (Qu et al. 2013). Previously, Guerrini
et al. have reported the preparation of dithiocarbamate-functionalized AgNPs for
the detection of PAHs. The SERS spectra can inform the existence of the pollutant
Fig. 9.3 Schematic representation of the procedure for detection of the PAHs using CD-Ag NPs
(Redraw with permission from Xie et al. 2010)
by measuring its characteristic fingerprint vibrational features. In their study, they

have used pyrene, benzo[c]phenanthrene, triphenylene, and coronene as model
PAHs (Guerrini et al. 2009). A similar calix[4]arene-functionalized Ag NPs
SERS sensor for PAHs has also been reported by Leyton et al. 2004). It was
found that host–guest interaction mechanism took place through a π–π stacking,
which leads to charge transfer between the complex and the metallic surface,
resulting in modification of surface charge of the metallic Ag nanoparticles and
enhanced SERS signals.
2.4.2 Magnetic Nanoparticles (MNPs) Based Extraction/Sensing

Techniques
Iron oxide is the most popular among all metal oxide nanoparticles due to their
excellent magnetic property, easy and bulk synthesis. They have become a useful
member in biomedical fields as a magnetic resonance imaging contrast enhance-
ment, in drug delivery, immunoassay, tissue repair, and hyperthermia, detoxifica-
tion of biological fluids in cell separation, etc. Besides their biomedical
applications, they are very popular for the fabrication of sensor or extraction
devices also. The extraction can be easily and economically achieved through
MNPs, just using the simple magnets.
Recently, Wang et al. have prepared a cetyltrimethyl ammonium bromide-
coated Fe3O4 MNPs for the analysis of 15 PAHs in the aquatic environment by
liquid chromatography in combination with fluorescence detection technique. They
have used a solid-phase extraction (SPE) method for the extraction of PAHs and
reached an enrichment factor of 800 within 5 min using 100 mg of Fe3O4 MNPs and
50 mg of CTAB. They have concluded that this SPE technique is more convenient,
efficient, time-saving, and cost-effective than the conventional liquid–liquid
260 S. Patra et al.
extraction technique or the C18 SPE cartridge. The LOD value for all the selected
PAHs was found within 0.4–10.3 ng L1. The recovery value was found in between
59.23 and 87.95% for rainwater, upstream and downstream river water, wastewater,
and tap water sample (Wang et al. 2015b). A magnetic SPE technique coupled with
HPLC-Fluorescence detection has been reported recently for the determination of
PAHs in coffee and tea samples. For this, they have synthesized a nano-adsorbent
by combining ionic liquid, MNPs, and vinyl silane (trimethoxysilyl propyl meth-
acrylate), i.e., Fe3O4@MPS@IL NPs, and applied it for the analysis of seven heavy
molecular weight PAHs from coffee and tea samples. The full procedure has been
discussed in Fig. 9.4. The material shows a good performance for the analysis of
PAHs with the detection limits in the range of 0.1–10 ng L1. The spiked recoveries
of the seven PAHs in coffee and tea samples were ranged in between 87.5 and
104.5%, with RSDs of less than 3.7% (Shi et al. 2016). A gas chromatography
technique in combination with mass spectrometry and magnetic SPE has been
reported for the analysis of 16 PAHs in drinking water samples. As a simple
synthesis approach, they have prepared fluorenyl-functionalized superparamagnetic
core/shell magnetic nanoparticles. The method was simple, fast, and environmen-
tally friendly, i.e., does not require any organic solvent and have LOD value
ranging from 0.4 to 4.0 ng L1 (Cai et al. 2015). The recovery values in real
water samples were found in the range of 96.0–106.7%. Later, the same group has
reported another modified version of the material to improve the detection limit.
Fig. 9.4 Schematic representation showing the magnetic solid-phase extraction technique
(Redraw with permission from Shi et al. 2016)
Here, they have coated the prepared MNPs with 3-aminopropyltriethoxysilane and
modified with cholesterol chloroformate. The detection limit was lower than that of
the previous one, ranging from 0.2 to 7.8 ng L1 (Cai et al. 2016). A zeolitic
imidazolate framework (ZIF) based magnetic SPE of polycyclic aromatic hydro-
carbons from the air–water environment was reported in a recent article, published
from Hangzhou Dianzi University, China. ZIF consists of metal nodes connected to
imidazolate linkers, with both the properties of metal-organic frameworks (MOFs)
and inorganic zeolites, known for their controlled pore sizes, high porosity, and
high surface area (Zhang et al. 2016a). The synthesis procedure was simpler and
was prepared by simply mixing ZIF-7 and polydopamine-coated Fe3O4
nanoparticles in solution phase. The functional groups like –OH and –NH2 present
at the surface of MNPs, get attracted and anchored to the ZIF-7 through
non-covalent adsorption and covalent cross-link interactions. This promotes the
complete magnetization of ZIFs and thereby enhances their stability and reusabil-
ity. GC-MS was used as the main detection technique and applied for the analysis of
PAHs from rainwater and air samples containing particulate matters. The detection
limit was found in the range of 0.71–5.79 ng L1 with limits of
quantification ¼ 2.50–19.2 ng L1. Similarly, Hong Kong University of Science
and Technology (HKUST-1) based MOFs have also been prepared for magnetic
SPE of eight heavy PAHs in waters and fruit tea infusions and analysis was
performed by a combination of HPLC and fluorescence detection techniques. The
method shows a new pathway for the preparation of adsorbent material (here simple
mixing is used) and shows fast extraction (within 10 min) with a minimum
amount of sorbent (20 mg of HKUST-1 and 5 mg of MNPs) and an organic solvent.
The method possesses a lower LOD value of 0.8 ng L1 with a recovery range of
75–94% in real sample analysis (Rocı́o-Bautista et al. 2016).
Nowadays, stir-bar sorptive extraction (SBSE) has become very popular in the
field of extraction and ultra-trace level analysis. Recently, Mollahosseini et al. have
reported the use of polypyrrole–polyaniline nanocomposite based conducting poly-
mers as extraction phase for the analysis of PAHs through coupling of SBSE and
GC. The method shows a good linear detection range in between 2 and 450 ng mL1
with a LOD of 0.02–1.10 ng mL1 for the selected PAHs. The recoveries of these
compounds in spiked water samples were found in the range of 86–100%
(Mollahosseini et al. 2016).
Xue et al. have reported the preparation of MNPs with both hydrophobicity and
hydrophilicity for the extraction of PAHs from environmental water samples.
MNPs with divinylbenzene (DVB) and sulfonate functionalities were prepared
via “thiol-ene” click chemistry. Here, the hydrophobic DVB moieties were dedi-
cated for extraction while the hydrophilic sulfonate groups were used for dispersing
the MNPs in the aqueous sample solution. The method has shown a much lower
LOD value of 1.1, 0.8, 1.1, 1.4, 0.6, 2.1, and 0.7 pg mL1 for naphthalene,
acenaphthene, fluorine, phenanthrene, anthracene, fluoranthene, and pyrene,
respectively. Therefore, possess great potential in the pre-concentration of trace
level analytes in the complex matrix (Xue et al. 2015).
262 S. Patra et al.
Fig. 9.5 Schematic diagram showing the SERS detection of PAHs using thiol-modified
Fe3O4@Ag (Redraw with permission from Du and Jing 2011)
Besides single magnetic nanoparticles, some PAH sensor or extraction method

has also reported the use of MNPs along with other nanostructures. Use of two
nanostructures can enhance the effect of MNPs, due to the synergistic effect and
employing the thought Du and Jing has reported the preparation of thiol-modified
Fe3O4@Ag core–shell magnetic SERS probe for PAHs detection and identification
(Fig. 9.5). The linear calibration range was obtained between 1 and 50 mg L1 and
the detection limit was in the order of 105–107 M (Du and Jing 2011). Further,
Du et al. have reported another SERS probe for the detection of 16 Environmental
Protection Agency (EPA) priority PAHs using AuNPs-grafted Fe3O4. The approach
does not require expensive instrumentation or large sample volumes and was very
useful for identification of hydrophobic molecules like PAHs. They have achieved a
LOD value of 100–5 nM and applied the approach for the rapid screening of PAHs
in river water samples. Moreover, they have used a portable Raman spectrometer,
which will be beneficial for the on-site monitoring of PAHs (Du et al. 2016).
A magnetic N-doped carbon nanotube (CNT) has been reported by another
group for the identification and detection of PAHs in environmental water samples.
The determination was done by GC-MS technique and according to authors, the
method is more efficient than the use of SPME with polydimethylsiloxane fiber
(Menezes et al. 2015). Wang et al. have recently reported the synthesis of g-C3N4/
Fe3O4 nanocomposite and applied it for the solid-phase extraction of PAHs in water
samples. g-C3N4 has a stacked two-dimensional sheet-like morphology and is made
from simple precursors under ambient conditions at a low cost. Moreover, this is
known to be the most stable allotrope of carbon nitride of a great potential to be
used in environmental applications. The method shows a LOD of 0.05–0.1 ng mL1
towards the detection of PAHs with a precision in the range of 1.8–5.3%. The
technique also gives a high recovery value of 80.0–99.8% from real sample analysis
(Wang et al. 2015c). A similar magnetic SPE method has been proposed by Zheng
et al. also, where low-cost carbon nitride nanosheets were prepared by urea and
applied for the magnetic SPE of PAHs from edible oil. The obtained recoveries of
PAHs for spiked soybean oil samples ranged from 91.0 to 124.1%, with RSDs of
less than 10.2% (Zheng et al. 2016).
Like g-C3N4, graphene is another carbonaceous material of a 2-D sheet-like
structure with a high adsorption and electronic property. Graphene has also been
clumped with MNPs to provide the magnetic graphene. The magnetic graphene
possesses high surface area, high adsorption capacity and also facilitates easy
magnetic separation after adsorption of any environmental pollutant. Mehdinia
has reported the use of polythiophene as a surface modifier of magnetic graphene.
The detection limits were in the range of 0.009–0.02 μg L1 in the real matrix with a
recovery value in the range of 83–107% (Mehdinia et al. 2015). AuNPs-based
magnetic mesoporous silica nanoparticle has been reported for the liquid–liquid
microextraction and determination of PAHs by Mehdinia et al. (2014). For the
incorporation of AuNPs, magnetic MCM-41 (mesoporous carbon) was
functionalized with 3-aminopropyltriethoxysilane, which then interacted with
AuNPs through the amine group. The π-system of PAHs and immobilized AuNPs
on the surface of the sorbent can cause the electron donor–acceptor interactions.
The detection was linear in the range of 0.01–50 μg L1 with the detection limit of
0.002–0.004 μg L1 for PAHs. The method was successfully applied for the
analysis of PAHs in seawater samples with recovery value ranging from 91.4 to
104.2%.
2.4.3 Carbonaceous Materials Based Extraction/Sensing Techniques
Carbonaceous nanomaterials are regarded as the most studied nanomaterials of this

era. Different forms of carbon nanomaterials (e.g., graphene, carbon nanotube,
carbon nanospheres, carbon dots) have been explored and applied in the various
field of analysis and extraction. Among them, graphene and CNTs are treated as the
revolutionary invention with potential usefulness in almost all research fields.
Sometimes to enhance their efficacy, they are being modified with some other
nanomaterials also. Like, for the detection of PAHs, Adegoke and Forbes reported a
simple procedure for the preparation of L-cysteine-capped core/shell/shell CdSeTe/
ZnSe/ZnS quantum dot–graphene oxide (GO) nanocomposite (Fig. 9.6). Phenan-
threne, anthracene, pyrene, and naphthalene were chosen as model PAHs and
technique shows the LOD of 0.19 μg L1 for phenanthrene under optimum condi-
tions, while the LOD of anthracene, pyrene, and naphthalene were estimated to be
0.26 μg L1 (Adegoke and Forbes 2016). Hou et al. have reported a bis
(trifluoromethanesulfonyl)imide-based ionic liquid-grafted GO-coated SPME
fiber for extraction and enrichment of PAHs from potatoes and phthalate esters
food wrap. The method was simple in application and shows the LOD value of
0.015–0.025 μg L1 for PAHs detection (Hou et al. 2016). In another literature, the
authors have reported the selective and sensitive determination of PAHs using
264 S. Patra et al.
Fig. 9.6 Proposed fluorescence detection mechanism of phenanthrene using the QD-GO
nanocomposite probe (Redraw with permission from Adegoke and Forbes 2016)
SPME and GC-MS technique in mainstream cigarette smoke. Graphene was used
as a coating material for the SPME fiber. The prepared fiber has also been compared
with commercially available 100-μm poly (dimethyl siloxane) (PDMS) fiber and
found that graphene-based SPME fiber was advantageous than PDMS fiber in terms
of their cleanup and pre-concentration efficiencies. The LODs and LOQs value of
the selected 16 PAHs lies in between 0.02–0.07 and 0.07–0.22 ng/cigarette, respec-
tively. The method was also advantageous in terms of their easy operation and good
validation results (Wang et al. 2015d). A similar SPME fiber has also been reported
for the extraction and detection of PAHs in cigarette smoke by Shi et al. (2015).
This time, the authors have used GO-bound silica as SPE platform. The LODs and
LOQs values were comparable as that of the previous one and were found in the
range of 0.05–0.36 ng/cig and 0.17–1.19 ng/cig, respectively.
Besides GO, carbon nanotubes (CNTs) were also used for the analysis of PAHs.
Han et al. have reported supercritical fluid extraction with CNTs as a solid collec-
tion trap for the analysis of PAHs. Fifteen typical PAH derivatives were selected for
analysis and it was found that the material was most efficient trapping sorbent for
the collection of PAHs and their nitro-, oxy- and alkyl-derivatives compared with
liquid trapping and C18 solid-phase trapping. The method exhibited a recovery
value of 62.9–111.8% for the real soil samples analysis with precisions [Relative
standard deviation (RSD), intra-day] ranged from 1.9 to 13.7% (Han et al. 2015).
Very recently, Mukhtar and See have reported the carbonaceous nanomaterials
immobilized mixed matrix membrane microextraction technique for the determi-
nation of PAHs in sewage pond water samples. For the fabrication of carbonaceous
materials, MWCNTs and single layered graphene nanoparticles were individually
incorporated through dispersion in a cellulose triacetate polymer matrix. For the
extraction, a small piece of the prepared membranes was dipped in the solution to
initiate the analyte adsorption. After that, the analytes were desorbed by methanol
and analyzed by HPLC. The LOD was in the range of 0.02–0.09 ng mL1 with a
pre-concentration factor of 54–100 for all PAHs (Mukhtar and See 2016).
2.4.4 Other Nano-sized Materials Based Extraction/Sensing

Techniques
Besides noble metals, magnetic and carbonaceous nanomaterials, some other nano-
sized materials have also been applied for PAH analysis. Very recently, Mauri-
Aucejo et al. have reported the use of cyclodextrin-silica microporous composite
for the determination of PAHs in water samples. SPE coupled with HPLC was
chosen as the detection technique. Several parameters like amount of solid phase,
the nature and volume of the eluent, and the sample volume and concentration were
being evaluated, before their quantitative estimation. The quantification limits of
the method were reported in the range of 0.09–2.4 μg L1 (Mauri-Aucejo et al.
2016).
Titanium dioxide (TiO2) nanoparticles are very popular for their excellent
chemical and thermal stability, high corrosion-resistance, non-toxicity, low cost,
and good biocompatibility. Over the past years, various size and shaped TiO2
nanoparticles have been synthesized and applied in various research fields.
Recently, Guo et al. have reported the preparation of phenyl-functionalized tita-
nium dioxide-nanosheets for the analysis of PAHs in environmental water samples.
Prior to the analysis, titanium dioxide-nanosheets were coated on a titanium wire
for selective solid-phase microextraction of PAHs. The method exhibited high
extraction capability, good selectivity, and rapid mass transfer for PAHs. The
calibration graphs were linear over the range of 0.05–300 μg L1 with the LOD
of 0.008–0.043 μg L1 (Guo et al. 2015). Another titania-based microextraction
device was reported by Zhang et al. but here the analysis was performed by a
coated-pore sintered titanium disk. Polydimethylsiloxane was used as the extraction
phase and carcinogenic 16 types of polycyclic aromatic hydrocarbons were selected
266 S. Patra et al.
as model analytes. The LODs and RSDs were found in the range of 0.06–3.20 ng L1
and 0.57–7.08%, respectively (Zhang et al. 2016b).
2.4.5 Molecularly Imprinted Polymers (MIPs) Based Extraction/

Sensing Techniques
MIPs are known to be a special class of polymers with a predetermined selectivity

towards their target molecule (Patra et al. 2015). This phenomenon makes them
useful materials in various fields like sensing, separation, drug delivery, etc. For the
synthesis of MIPs, the monomer and templates (analytes) were taken simulta-
neously and after polymerization, the template molecules were extracted from the
polymer matrix to leave a cavity selective and specific to that of the template
molecule. For the synthesis of MIPs, selection of monomers, cross-linker, and the
porogenic solvent is very important. For the polymerization, bulk polymerization,
suspension polymerization, two-stage swelling, precipitation polymerization, and
atom transfer radical polymerization techniques have been applied, in general. Due
to the associated advantages, MIPs have also been applied for the extraction and
determination of PAHs. Song et al. have reported the selective determination of
16 PAHs in seawater using MIP-based SPME technique and GC-MS was applied as
the main detection technique. They have prepared the MIPs through non-covalent
polymerization technique by using the 16 PAHs mixture as a template based on
sol-gel surface imprinting process. They have also prepared same polymer matrix
but with the absence of template molecules, termed as non-imprinted polymers
(NIPs). Their as-prepared MIPs show a higher binding affinity (111.0–195.0 μg g1)
than the NIPs with an imprinting factor of 1.50–3.12. With the high extraction
efficiency of the MIPs, they can remove 93.2% PAHs from natural seawater. As a
detection platform, they have achieved a LOD value of 5.2–12.6 ng L1 (Song et al.
2012). An extraction technique by coupling GC-MS and MIPs together has also
been reported for the sensitive determination of PAHs in ambient air dust. For their
study, Chrysene (CHR), benzo[a]pyrene (BAP), benzo[b]fluoranthene (BBF),
indeno[1,2,3-c,d]pyrene (ICP), and dibenzo[a,h]anthracene (DBA) were used as
template molecules, 4-vinylpyridine as the functional monomer, ethylene glycol
dimethacrylate (EGDMA) as the cross-linker, and 2,20 -azobis (2-isobutyronitrile)
(AIBN) as the initiator. The recovery of PAHs from air dust was in the range of
85–97% with a detection limit of 0.15 ng L1 (Krupadam et al. 2010). A similar
extraction and determination method has been reported by Dravoba et al. for
vegetable oil and tea samples (2012, 2013). In the first case, they have reached a
recovery value of 70–99% with an LOQ of 0.1–0.3 μg kg1 (Drabova et al. 2013).
In the second case, they have reached a recovery value of 73–103% with an LOQ of
0.05–0.2 μg kg1 (Drabova et al. 2012).
In bulk MIP, there is a general problem of template extraction, sometimes
templates were not easily extracted from the polymer matrix. But in nano-sized
MIPs, the surface-to-volume ratio increases, which overcome the problem associ-
ated with bulk MIP. Therefore, besides this bulk polymer matrix, some nano-sized
MIPs have also been fabricated to overcome the problem associated with bulk MIP.
Chauhan et al. reported the preparation of nano-sized multi-template imprinted
polymer for simultaneous extraction of PAHs using HPLC. For polymerization,
they have used 1-naphthol, 9-phenanthrol, and 9-hydroxyfluorene as templates,
methacrylic acid (MAA) as a monomer, EGDMA as a cross-linker, and AIBN as
an initiator. The limit of detection (LOD) and limit of quantification (LOQ) value
was much lower and was in the range of 0.33–2.6 and 0.99–8 ng mL1 (Chauhan
et al. 2015). Tiu et al. have reported the preparation of pyrene-imprinted
polythiophene nanofilm by an electrochemical deposition method and used it for
highly sensitive detection of pyrene and its analogues. The method shows good
stability and reproducibility with a detected linear concentration range of
0.01–10 μM (Tiu et al. 2016). A molecularly imprinted titania microbead for the
extraction of 1-hydroxy pyrene from urine using HPLC as detection technique has
also been fabricated. As a typical synthesis process, they have prepared molecularly
imprinted TiO2 by polycondensation of titanium (IV) butoxide in the presence of
the template, i.e., 1-hydroxy pyrene, and the resulting imprinted gel was deposited
in the form of a thin film on a quartz support for the extraction and analysis of
1-hydroxy pyrene (Yang et al. 2016).
3 Volatile Organic Compounds (VOCs)
3.1 Source, Toxicity, Cause Behind Their Detection/

Extraction
In a simple definition, VOC can be defined as the organic chemicals with high vapor
pressure at room temperature. Different kinds of VOCs can be found in the air, viz.,
alkanes, alkenes, alkynes, aromatic hydrocarbons, halogenated hydrocarbons, alde-
hydes, ketones terpenes, and alcohols (Kim et al. 2016). Maximum of them are
toxic or carcinogenic, and therefore all of them have tolerance limit for their
concentrations in the air. Because of their participation in photochemical reaction,
especially the more reactive non-methane compounds are often regarded as pre-
cursors of ozone. They have a great influence on the tropospheric chemistry and can
affect ozone formation (Chang and Chen 2008). Besides PAH, VOC can also be
known as highly toxic materials mainly originated from the exhaust gas. Anthro-
pogenic VOC sources include the combustion processes, the use of fossil fuels,
solvents, industrial production processes, and biological processes. Robert
Guicherit has previously carried out an extensive study to prove traffic as a source
of VOCs in air (Guicherit 1997). Besides this, in residential or industrial areas,
some other sources have been reported. The combustion of wood for cooking is
known to emit several different VOCs (like halogenated hydrocarbons and oxy-
genated hydrocarbons) and other air pollutants. Pulp and paper manufacturing,
biomass burning, industrial sources, and water treatment are the main global
268 S. Patra et al.
anthropogenic sources of VOCs, while oceans, soil, termites, and microalgae are
the main natural sources of these types of compounds. VOCs have been found to
have serious toxic effects to the human body as that of PAHs. They may cause acute
toxic effects (primarily neurological), cancer (such as leukemia), neurobehavioral
effects, and adverse effects on the kidney (Mirzaei et al. 2016). The acute health
effects associated with exposure to VOCs like benzene include muscle weakness,
confusion dizziness, and incoordination. These effects mostly occur when their
high concentration is present. In addition, they have also reported with the oph-
thalmic effects. The optic nerves may have been injured resulted from toluene as a
metabolite. Toluene is the main cause behind the polyneuropathy in shoe factory
workers. It is being reported that toluene in vapor phase has the ability to be
absorbed rapidly from the lungs, and liquid toluene is taken up readily from the
gastrointestinal tract, but poorly through the skin. Another VOC, xylene is respon-
sible for the irritation to eyes, mucous membranes, and skin. These VOCs may
cause sick building syndrome (SBS) also, which reported being associated with
certain health issues like headaches, eye irritation, nausea, cough, etc. The concen-
tration of toxic VOCs is low in motorcycle exhausted waste gas but it might affect
the human health seriously due to long-term exposure and/or bioaccumulation
(Mirzaei et al. 2016). Due to their high toxicity and adverse effects on health,
major environmental safety agencies, like Environmental Protection Agency
(EPA), National Institute of Occupational Safety and Health (NIOSH), and
European Agency for Safety and Health at Work (EU-OSHA), have customized
some guidelines regarding the limit of their exposure to human body in indoor and
workplace. Therefore, from the perspective of air pollution control, the determina-
tion of these toxic VOCs is extremely crucial for taking actions that would be
beneficial for our health. The effective methods to monitor VOCs in the complex
matrix are in high demand for atmospheric environmental measurement and control
as well as human well-being and health monitoring (Mirzaei et al. 2016).
3.2 Detection/Extraction of VOCs
Due to their widely reported heath hazardous effects, the detection of VOCs
becomes a popular field. Numerous literatures have been reported towards their
detection. Spectrophotometry, GC, and HPLC have been popularly applied for the
quantification of VOCs. Initially, Xu et al. have reported a GC-MS-based method
for the analysis of selected VOCs in Canada both in indoor and outdoor condition.
The examined samples were collected in between September 2009 and December
2011 (Xu et al. 2016b). In another report, Vinci et al. have reported a headspace GC
coupled to MS technique to study the occurrence of VOCs in foods purchased from
the Belgian market and dietary exposure assessment. They have screened 377 food
samples from the Belgian market and found the presence of 21 VOCs. The
compounds with their respective percentages of occurrence were: chloroform
(97%), toluene (95%), ethyl benzene (80%), o-xylene (79%), and benzene (58%)
(Vinci et al. 2015). Similarly, Cincinelli et al. have reported the analysis of VOCs in
the libraries and archives in Florence (Italy). Among the detected VOCs, BTEXs
(Benzene, Toluene, Ethylbenzene, Xylenes) being the most abundant, followed by
cyclic volatile methylsiloxanes, aldehydes, terpenes, and organic acids (Cincinelli
et al. 2016). An HPLC method was used for the determination of VOCs and others
in mainstream cigarette smoke using a glass filter and a sorbent cartridge was
reported recently. The sorbent cartridge was packed with Carboxen 572 (CX-572)
and a Cambridge filter pad (CFP). For the determination, gaseous compounds
collected with the CX-572 cartridge and total particulate matter (TPM) collected
with the CFP are coeluted in the same vial and then analyzed by HPLC, GC-MS,
and gas chromatograph–thermal conductivity detector (GC/TCD) (Uchiyama et al.
2015). These conventional methods and standard techniques have good accuracy
and precision but suffer from some drawbacks like their cost, high power demand,
lack of portability, and low throughput. Moreover, the use of such techniques
sometime requires complex and time-consuming pretreatment steps and highly
skilled operators also. The conventional method for monitoring the indoor VOCs
is generally time-consuming and expensive because it requires on-site sampling of
indoor air. This clearly suggests that this type of methods cannot be useful for the
quantification of VOCs on a real-time basis. As we have discussed earlier,
nanomaterials-based approach will be more advantageous and possess the oppor-
tunity for their real-time application in near future. Among the various
nanomaterials used for sensing of VOCs, the metal oxide semiconductor materials
are very popular in this field, which can be used to fabricate conductometric or
resistive type devices. Here, the variation of electrical conductivity or resistivity of
the sensitive element shows change or variation with a concentration of VOCs
species, resulting in rapid and sensitive detection of these compounds (Table 9.2).
3.2.1 Noble Metal Nanoparticles Based Analysis
Some literatures have reported the use of noble metal-based nanoparticles in VOCs
sensing. Like, Wang et al. have reported the preparation of unique Au@In2O3 core–
shell nanostructure through a simple sol-gel method and applied for the selective
detection of ethanol (Wang et al. 2015e). Another Au-loaded In2O3 nanofiber has
also been reported for the sensing of ethanol. Here, electrospinning technique was
applied for the fiber preparation. They have also changed the amount of Au during
the fiber formation and compared their property for ethanol sensing. It was found
that 0.2 wt.% Au-loaded In2O3 nanofiber shows the highest ethanol sensing prop-
erty (Xu et al. 2011). Santhaveesuk et al. have also used AuNPs for VOCs sensing
in combination with ZnO tetrapod sensor. They have also studied the enhancement
of sensing performances after mixing of TiO2. The synthesis was based on a simple
thermal oxidation technique. The operating temperature was 260–360 C with the
ethanol concentration of 50, 100, 200, 500, and 1000 ppm (Santhaveesuk et al.
2010). Zhang et al. have reported the synthesis of Au-supported ZnO nanoplates
and its applicability as ethanol sensor. They have also carried out a comparative gas
Table 9.2 List of nanosensors reported for the detection of VOCs
270
Response Recovery
S.N. Materials VOCs Concentration (ppm) Temperature ( C) time (s) time (s) Reference
1 Au@In2O3 Ethanol 100 160 4 2 Wang et al. (2015e)
2 Au-In2O3 nanofiber Ethanol 500 140 12 24 Xu et al. (2011)
3 Au/TiZnO Ethanol 50 240–340 – – Santhaveesuk et al.
(2010)
4 Au/ZnO Ethanol 5 300 13 – Zhang et al. (2012)
5 Au/ZnO NW Ethanol 100 380 5 6 Guo et al. (2014)
6 Au/ZnO NW Ethanol 50 325 5 20 Ramgir et al. (2013)
7 AuPd-WO3 Acetone 200 300 101 96 Kim et al. (2015)
8 In2O3/Au NRs Acetone 50 250 10 18 Xing et al. (2015)
9 Au@SnO2 Formaldehyde 50 RT 80 69 Chung et al. (2014)
10 Ag@SnO2 Ethanol 200 RT 34 68 Wu et al. (2013)
11 Ag@TiO2 Ethanol <5 RT 52 63 Zhu et al. (2014)
12 Ag-TiO2 nanobelts Ethanol 500 200 1 2 Hu et al. (2010)
13 Ag@α-Fe2O3 Ethanol 100 250 5.5 16 Mirzaei et al. (2015)
14 CoFe2O4 NPs Ethanol 50 150 50 60 Xiangfeng et al. (2006)
15 Ce-CoFe2O4 NPs Acetone 2000 200 38 – Khandekar et al. (2014)
16 Au-ZnO-Fe2O3 Acetone and 100 225 57 and 113 – Kaneti et al. (2015)
n-butanol
17 Hollow Fe2O3@SnO2 Toluene 10 250 – – Zhang et al. (2013)
18 α-Fe2O3-Au Acetone 100 300 – – Zhang et al. (2011)
nanospindles
19 Nano-Fe2O3 films Formaldehyde 100 320 – – Huang et al. (2013)
20 SnO2/α-Fe2O3 Ethanol 10 250 1 – Sun et al. (2014)
21 Fe3O4–NiO core–shell Toluene 100 280 27 – Qu et al. (2014)
22 SmFeO3 NPs Toluene 3 400 – – Mori et al. (2014)
S. Patra et al.
23 3-D aloe-like SnO2 Ethanol 50 285 1.2 76 Mei et al. (2012)
24 ZnO NW Ethanol 1500 300 – – Hsueh et al. (2007)
25 PdO-decorated ZnO Ethanol 100 320 1 7 Lou et al. (2013)
26 Pd-Ce-SnO2 Ethanol 100 250 6 20 Bagal et al. (2015)
27 SnO2@ZnO Ethanol 400 400 – – Singh and Singh (2012)
28 MWCNTs-doped Formaldehyde 50 250 – – Wang et al. (2008)
SnO2
29 Wormlike SnO2 n-butanol 5 150 – – Wang et al. (2014)
30 Flower-shaped SnO2 n-butanol 100 240 – – Huang et al. (2010)
31 ZnO-Graphene Acetylene 100 250 100 24 Uddin and Chung
(2014)
32 V2O5 NW microyarns Ethanol 1000 330 – – Jin et al. (2015)
33 Sparked In2O3 films Acetone 20,000 350 – – Inyawilert et al. (2014)
271
272 S. Patra et al.
sensing studies between pristine ZnO and Au/ZnO nanoplates in order to investi-
gate the effect of Au nanoparticles on the sensor performance. The results demon-
strated that the Au/ZnO nanoplate sensor has the faster response and recovery
compared to the pristine ZnO sensor. The response time was 13 s for Au/ZnO
nanoplates, whereas, for pristine ZnO, it was 135 s (Zhang et al. 2012). ZnO
nanowires functionalized by AuNPs have been reported as a high-performance
ethanol sensor. In a typical synthesis procedure, AuNPs were successfully
immobilized onto the surface of ZnO nanorods by a facile solution reduction
process to serve as a sensitizer. The material was able to detect ethanol in a wide
concentration range and a high response, fast recovery time with good selectivity
and repeatability (Guo et al. 2014). A similar ethanol sensor has also been reported
by Ramgir et al. using Au and ZnO nanowire nanocomposites. For the synthesis of
desired material, they have modified the hydrothermally grown zinc oxide (ZnO)
nanowires network with thin Au layer (10 nm). The reported response and
recovery times for Au-modified sensor films at 325 C towards 50 ppm of ethanol
were found to be 5 and 20 s, respectively. This faster reaction kinetics was mainly
due to the role of Au in improving the sensing properties as per the electronic
sensitization mechanism and its nano-Schottky barriers type junction with ZnO
(Ramgir et al. 2013). Besides the ethanol, AuNPs have also been applied for
acetone sensing. Au- and Pd-decorated WO3 nanorods have been employed as an
efficient acetone sensor. In a typical synthesis procedure, they have immersed the
prepared WO3 nanorods in the mixture of acetone (25 mM), HAuCl4 (25 mM) and
PdCl2 solution followed by UV irradiation and annealing. The material exhibited a
far stronger response to acetone gas (Kim et al. 2015). Xing et al. have prepared a
series of In2O3/Au nanorods (AuNRs) and studied their gas sensing property. The
morphology of the prepared In2O3/Au nanorods has been shown in Fig. 9.7a, b, and
c with the selected area electron diffraction pattern (SAED) in the inset. All the
images suggested a rod-like morphology. The detection limit was found as 0.1 ppm
for acetone and 0.05 ppm for ethanol. In Fig. 9.7d, e, In2O3/Au NRs and pure In2O3
gas sensors response curves have been shown. For acetone, the concentrations were
0.1–50 ppm at 250 C and for ethanol concentrations 0.05–650 ppm at 400 C,
respectively. In the plot, the dots represent the experimental data and the straight
lines are representing the linear fitting functions. As an interesting study, In2O3/
AuNRs gas sensor can clearly distinguish the acetone and ethanol biomarkers in
human breath by humidity compensation method (Xing et al. 2015). Chung et al.
have prepared Au@SnO2 core–shell nanostructure by sol-gel method and applied it
for the detection of formaldehyde at room temperature. The response and the
recovery times were reported as the 80 s and 62 s, respectively (Chung et al. 2014).
Besides gold, silver has also been used for the detection of VOCs by coupling
with metal oxides nanoparticles. Here we will discuss some earlier reported
approaches using silver-based metal oxide nanostructures for VOCs detection.
Wu et al. have prepared a nanocomposite core–shell Ag@SnO2 material using
chemical reduction and carried out a comparative study to prove that core–shell
nanostructure is superior sensing material than normal nanohybrid. The material
Fig. 9.7 (a) FE-TEM, (b) STEM, (c) HR-TEM image and SAED (inset of c) of In2O3/Au NRs
sample, In2O3/Au NRs and pure In2O3 gas sensors response curves to different (d) acetone
concentrations (0.1–50 ppm) at 250 C and (e) ethanol concentrations (0.05–650 ppm) at
400 C. The dots are experimental data and the straight lines are the linear fitting functions
(Reproduced with permission from Xing et al. 2015)
shows a better sensor response towards ethanol detection with shortening response
time (38 s) and recovery time (68 s). According to the authors, the sensing
mechanism is based on its effective adsorption, the reaction on the surface and its
fast desorption (Wu et al. 2013). Similarly, an Ag@TiO2 core–shell nanoparticles
based ethanol sensor has also been reported. The ethanol detection laboratory
equipment diagram with its various parts is shown in Fig. 9.8. The sensor was
reported to detect ethanol in the concentration range of 0.15–5 ppm. The sensor was
reported to have very good selectivity and stability for ethanol gas (Zhu et al. 2014).
Similarly, TiO2 nanobelts based Ag-TiO2 heterostructure has also been reported as
ethanol sensor. For this, first TiO2 nanobelt was prepared by hydrothermal method
and was conjugated with silver by photo-reduction. The sensor performance
towards ethanol vapor was examined and compared to electrical conductivity
measurements at varied temperatures. The sensing mechanism was interpreted by
surface depletion model (Hu et al. 2010).
274 S. Patra et al.
Fig. 9.8 Schematic representation showing the ethanol detection laboratory equipment diagram:
(1) computer, (2) data acquisition system, (3) liquid injection, (4) heater, (5) fan, (6) sensing film,
(7) power supply, (8) drying tube, (9) gas control valve, and (10) gas pump (Reproduced with
permission from Zhu et al. 2014)
3.2.2 Magnetic Metal Oxide Nanostructures Based Analysis
The popular among all metal oxide nanostructure, the magnetic nanoparticles are very
useful material in sensing and extraction of any compound. Several literatures have
been reported to exhibit the use of magnetic nanohybrids for the analysis of VOCs.
Recently, silver and iron oxide nanoparticles based core–shell structures have been
reported as a gas sensing platform. The synthesis was based on two-step reduction
sol-gel approach, where first AgNPs were synthesized using sodium borohydride as
reducing agent and subsequently mixed with a Fe (III) sol for α-Fe2O3 coating. The
material shows a better sensing performance than pristine α-Fe2O3 (Mirzaei et al.
2015). It is well known that spinel magnetic nanostructures are being prepared to
improve the property of normal Fe3O4 nanostructure. Xiangfeng et al. have reported a
hydrothermal technique for the preparation of CoFe2O4 nano-crystallines and applied
for the ethanol sensing. The sensor was very useful for a trace amount of ethanol
sensing and was also applied for the detection of triethylamine, when no ethanol was
present in the atmosphere (Xiangfeng et al. 2006).
As we know, doping has a great ability to improve the performance of any
nanostructure. Some literature has also reported the use of doped spinel structure
for VOCs sensing. Very recently, Khandekar et al. have reported the preparation of
Ce-doped CoFe2O4 nano-crystallines structure and study their gas sensing property
towards reducing gases like liquefied petroleum gas (LPG), acetone, ethanol, and
ammonia at 200–450 C. As a research finding, they have reported that the material
was sensitive and selective towards acetone as compared to other reducing gases
(Khandekar et al. 2014). Besides this spinel structure, ZnO, SnO2, and AuNPs
modified MNPs for acetone sensing have also been reported extensively in the
literature. Among them, recently Kaneti et al. have reported Au, ZnO, and Fe2O3
based magnetic nanocomposite for the detection of acetone and n-butanol. The
synthesis procedure was based on the hydrothermal approach and further surface
coating by Au and ZnO. The comparative study also demonstrated that the ternary
nanocomposite has the highest sensing ability than the binary and single α-Fe2O3.
Higher sensitivity/response in ternary nanocomposite was observed towards the
detection of acetone and n-butanol. The optimum temperature was also found very
lower, i.e., ~225 C, compared to the earlier reported methods. Chemical sensiti-
zation effect induced by the AuNPs is the main cause of their enhanced sensitivity,
and the existence of conjugated depletion layers in the nanocomposites promotes a
greater drop in resistance upon exposure to the gas (Kaneti et al. 2015). Similarly,
Zhang et al. have reported the controlled synthesis of recyclable core–shell
γ-Fe2O3@SnO2 hollow nanoparticles of a high photocatalytic and gas sensing
property. The synthesis technique was based on a low-cost and environmentally
friendly seed-mediated hydrothermal method. First γ-Fe2O3 hollow NPs were
synthesized by a template-free method and then they were used as a core for the
growth of SnO2 shells. By controlling the reaction time, the thickness of the shell
can also be monitored. From the combination of a magnetic semiconductor like
γ-Fe2O3 and wide band-gap semiconductor like SnO2, it can be expected that the
material will show an enhanced sensing performance. They demonstrated fast
response and recovery rates, which imply their applicability as promising materials
for gas sensors (Zhang et al. 2013). AuNPs-functionalized α-Fe2O3 nanospindles
were prepared for enhanced gas sensing property and catalytic activity. The sensing
property was much higher than pristine α-Fe2O3, which proves the effect of AuNPs
on sensing ability once again (Zhang et al. 2011). Another literature has reported
the use of Au, α-Fe2O3 and SnO2 hybrid structures as an enhanced gas sensing
material. The hybrid structure was made of α-Fe2O3 nanospindles as the core and
Au-decorated SnO2 coating as the shell. The higher gas sensing performances by
means of their higher sensitivity and faster response-recovery were mainly due to
special architectures and multiple compositions (Liu et al. 2012). Similarly, to
increase the gas sensing property, nanocomposite of α-Fe2O3 and SnO2 has also
been reported in the literature. It was found that the ethanol sensing property was
much higher in SnO2/α-Fe2O3 than normal SnO2 nanoparticles. Their study further
demonstrated that the double shell structure was superior as a sensor than the single
shell structure. At an ethanol concentration of 100 ppm, the response of
nanocomposite was reported as 16 s, which is almost two times higher than normal
SnO2 nanoparticles. The response time for 10 ppm ethanol was reported to as low as
1 s at a temperature of 250 C (Sun et al. 2014).
Besides the applicability of nanocomposite for ethanol and acetone sensor, they
have also been applied as a potential sensing platform for formaldehyde, toluene,
benzene, methanol, propanol, and butanol. In the year 2013, an in situ diffuse
reflectance infrared Fourier transform spectroscopic study for the formaldehyde
adsorption and reactions on nano-Fe2O3 films was reported by Huang et al. The
method was simple in operation and the sensor fabrication was based on screen-
printing technology (Huang et al. 2013). Another core–shell nanocomposite based
on magnetic nanoparticles and NiO was prepared by a facile hydrothermal method
in water-ethanol-butanol solvent without any templates. The morphological study
276 S. Patra et al.
demonstrated that the porous architectures were assembled from Fe3O4 sphere core
and NiO flower-like shells. The nanocomposite was applied as a chemical gas
sensor for toluene detection. The sensor shows a high response, superior selectivity,
and rapid response recovery towards toluene determination (Qu et al. 2014). Mori
et al. have reported a perovskite-type SmFeO3 oxide, a p-type semiconductor as a
chemoresistive sensor material for VOC detection. For sensor fabrication, the
SmFeO3 particles were deposited on a comb-type Pt electrode printed on an
alumina substrate. They have studied 15 kinds of VOCs (namely, methanol,
ethanol, propanol, butanol, acetic acid, propionic acid, methyl acetate, ethyl ace-
tate, acetone, methylethylketone, benzene, toluene, xylene, ethyl benzene, and
chlorobenzene) using a single format sensing device. The concentrations were
below 10 ppm and operating temperature was in the range of 350–500 C. It was
reported that the resistance of the sensor increased after the contamination of
referenced air with the selected VOCs, which is used as sensing platform (Mori
et al. 2014).
3.2.3 Other Metal Oxide Nanostructures Based Analysis
It can be found that among all the metal oxide nanostructures, SnO2- and
ZnO-based nanostructures have shown the most promising sensing performances
towards the detection of VOCs. The shape is a useful characteristic towards the
sensing property of a material. With the change in shape, an enormous change can
be observed within a material. In addition to their combination with MNPs, their
other 3-D structures and nanocomposites were also employed for VOCs sensing.
Mei et al. have reported the synthesis of 3-D aloe-like SnO2 nanostructures using a
simple hydrothermal method. The aloe-like FESEM images are shown in Fig. 9.9.
The developed sensor from this 3-D aloe-like SnO2 can detect ethanol, even if the
concentration is as low as 50 ppb at 285 C with high sensitivity. The low ethanol
concentration can be explained by the less agglomerative and thinner structure of
aloe-like SnO2 nanoparticles, together with the modulation of the conductance by
the small nanosheets (Mei et al. 2012). Mesoporous wormlike SnO2 nanostructure
was employed as a highly selective sensor for n-butanol. The nanostructure was
prepared using a simple combination of hydrothermal and annealing process, in the
presence of various amount of soluble starch. The pore diameter of as-prepared
SnO2 nanostructure was reported as 6–15 nm and the modified sensor shows a
linear detection limit in the range of 5–100 ppm (Wang et al. 2014). Huang et al.
reported a flower shape SnO2 nanostructure and applied as ethanol and 2-butanol
sensor. The flower-like structures exhibited a good response and reversibility
towards both the analytes. The sensor response at a concentration of 100 ppm
ethanol and n-butanol was reported to be 42.6 s and 77.2 s, respectively, at a
working temperature of 240 C (Huang et al. 2010).
As that of SnO2, laterally grown ZnO nanowires were also employed as ethanol
sensor. According to their research findings, the growth direction of the ZnO
nanowires was strongly depends on growth parameters and as an ethanol sensing
Fig. 9.9 FESEM images

showing the morphological
images of 3-D aloe-like
SnO2 nanostructures at (a)
low and (b and c) high
magnifications (Reproduced
with permission from Mei
et al. 2012)
278 S. Patra et al.
Fig. 9.10 FESEM images of flower-like ZnO and PdO-ZnO structures: (a and c) lower magni-
fication; (b and d) higher magnification (Reproduced with permission from Lou et al. 2013)
platform, the resistivity of the reported sensor decreased upon ethanol gas injection
(Hsueh et al. 2007). Similarly, flower-like pristine ZnO and PdO-decorated ZnO
was prepared by a surfactant-free hydrothermal route and subsequent heat treat-
ment. They have reported that PdO-ZnO based sensor displays the response for
100 ppm for heptane and ethanol. The FESEM and TEM images have been shown
in Figs. 9.10 and 9.11, which clearly represent the flower-like morphology. The
schematic diagram of the gas sensing mechanism has been shown in Fig. 9.12. The
response was about 4–5 times higher than that of pristine ZnO at the optimal
operating temperature of 240 and 320 C (Lou et al. 2013). Bagal et al. have
reported the effect of Pd and Ce doping on SnO2 nanostructure for the sensing of
ethanol. The amount of Pd and Ce was optimized and the prepared nano-crystalline
powders were screen printed on the alumina substrates to form thick films, which
were further used as a gas sensing platform. The material shows a quick response
(6 s) and recovery (20 s) towards ethanol detection at an operating temperature of
250 C (Bagal et al. 2015).
To increase the ethanol sensing response, combination of ZnO and SnO2 was
also employed. For this, first zinc oxide was synthesized by a chemical route and
then deposited on an alumina substrate and lastly activated by tin dioxide (obtained
by on-site oxidation of tin chloride) (Singh and Singh 2012). Similarly, a
multiwalled carbon nanotube-doped SnO2 sensor was also reported for the detec-
tion of low concentration of formaldehydes. For this type of low-level detection,
they have employed an enrichment method with active carbon. The as-prepared
nanocomposite was able to detect 0.03 ppm of formaldehyde (Wang et al. 2008).
ZnO nanoparticles in combination with graphene oxide were used as acetylene
Fig. 9.11 TEM images of flower-like ZnO and PdO-ZnO structures: (a and c) low magnification
and (b and d) high magnification (Reproduced with permission from Lou et al. 2013)
Fig. 9.12 Schematic diagrams on the gas sensing mechanism of (b) flower-like ZnO and (c)
PdO-decorated ZnO structures (Reproduced with permission from Lou et al. 2013)
280 S. Patra et al.
sensor. The material shows a maximum sensor response value of 143 for 1000 ppm
acetylene at 250 C with an optimized material ratio of ZnO and rGO (4:1). It was
also concluded that improvement in sensor ability is mainly due to the incorpora-
tion of graphene (Uddin and Chung 2014). Besides ZnO and SnO2 nanostructure,
TiO2 is equally useful material for gas sensing, therefore, also applied for VOCs
detection, either individually or in combination with other nanoparticles. Recently,
TiO2 nanotubes have been synthesized and employed as a sensing material for
ethanol (Kılınç et al. 2011). For the preparation of nanotubes, Ti thin films were
anodized in a mixture of aqueous hydrofluoric acid (HF) (0.5 wt. %) and polar
organic (0.5 wt.% NH4F + ethylene glycol) electrolytes. The anodization potential
was in between 5 and 20 V for HF and 20 and 60 V for polar organic electrolytes. As
a sensing material, TiO2 nanotubes show very high sensitivity towards VOCs in an
operating temperature of 200 C. Another report can be found in literature where
TiO2 nanotubular films were used as an improved VOC sensing material. It was
reported that the prepared nanomaterial shows an improvement in sensing response
and selectivity to toluene (50 ppm), after the ball-milling treatment for 3 h at the
operating temperature of 500 C. But, when the ball-milling treatment time was
increased, it was unable to further enhance the original sensor response, which may
cause a decrease in the porosity of the film (Seo et al. 2011).
One-dimensional vanadium oxide nanostructure is one of the potential gas
sensing oxides and has applied by many researchers. For example, Jin et al. have
reported the preparation of ordered V2O5 nanowire microyarns for the detection of
ethanol, methanol, ammonia, and toluene. The response of the yarns shows a
maximum value of 9.09–1000 ppm for ethanol at 330 C. The finding value was
around 3.5 times higher than that of other nanowires. On the contrary, the material
shows a very little response towards methanol, ammonia and toluene; conclude the
potential usefulness of V2O5 nanowire microyarns in selective sensing of ethanol
(Jin et al. 2015). It is reported that one-dimensional (1D) metal oxide semiconduc-
tors nanostructures based sensors could exhibit excellent sensitivity to the detected
gases. Among all the 1D metal oxides, much attention has been paid for the
preparation of 1D In2O3 nanostructures such as nanowires, nanorods, nanotubes,
and nanofiber mainly owing to their interesting optical and electrical properties.
Driven by their advantageous effects, Zheng et al. have reported the preparation of
In2O3 nanofibers with diameters of around 60 nm by electrospinning method. For
electrospinning, they have used a solution of polyvinyl pyrrolidone and indium
nitrate, which was further calcined at 700 C in air. The as-prepared In2O3
nanofibers showed selectivity, fast response and recovery time towards ethanol
gas (Zheng et al. 2009). In another report, sparked In2O3 sensing film was used for
the VOCs sensing. For the preparation of sparked In2O3, two indium wires were
sparked and scanned repeatedly above Al2O3 substrates. The Al2O3 substrates were
well equipped with Au interdigitated electrodes at a sparking voltage of 4.5 kV for
10–200 cycles. The material was applied for the detection of ethanol and acetone
within a concentration range of 50–1000 ppm and 100–2000 ppm, respectively, at
200–350 C. The material was very useful as ethanol and acetone detectors for
drunken driving detection and diabetes diagnosis (Inyawilert et al. 2014). Besides
the use of normal In2O3 nanostructures, other metal-based nanocomposites have

also been reported. Recently, Karmaouni et al. have reported Pt-decorated In2O3
nanoparticles and applied it for the detection of acetone. The material was found
very sensitive towards acetone and shows the LOD value of 10 ppb or less
(Karmaoui et al. 2016). Mixture of indium and tin oxide (i.e., indium tin oxide,
ITO) was also reported as an efficient toluene sensor in a current study (Vaishnav
et al. 2015). The sensing mechanism was based on the redox reaction on the surface
of ITO film. The sensor was very much sensitive and selective towards toluene with
a linear detection range of 10–1000 ppm.
3.2.4 Molecularly Imprinted Materials Based Analysis
As we discussed earlier, MIP-based sensing devices are most popular in terms of

their high selectivity. Due to their high selectivity, they are also termed as an
artificial antibody or plastic antibody. MIPs as sensing material for VOCs are
also reported in the literatures. Mostly ethanol, toluene, or acetone was used as
template or target analytes during the MIP synthesis. Tan et al. have used a SnO2-
based MIP for the detection of ethanol. As expected, the material was highly
selective towards ethanol (Tan et al. 2015a). Another SnO2-based gas sensor for
the detection of acetone was also reported, very recently. The method was opti-
mized for the smooth adsorption and desorption of acetone gas (Tan et al. 2015b).
In another report, ethanol sensing device was prepared by mixing MIP as recogni-
tion element, MWCNTs as conducting element, and poly(methyl methacrylate)
(PMMA) as an adhesive substance. The sensor was very much selective and shows
a good response towards ethanol with a response time ~1 min. The sensor was able
to detect ethanol within a concentration range of 0.65–45.00 ppm with a LOD value
of 0.5 ppm (signal to noise ratio ¼ 3) (Alizadeh and Rezaloo 2013). A polymer
membrane ion selective electrode based potentiometric sensing system for sensitive
and selective determination of neutral vapors in the gas phase using MIP as a
selective detection platform was also reported. For this, the MIP was incorporated
into the membrane for selective adsorption of the analyte vapor from the gas phase
into the sensing membrane phase. To study the change in MIP binding site, an
indicator was used, which will have a similar structure as that of the selected
analyte. In their report, they have used toluene as a model analyte and benzoic
acid as the indicator. The sensing setup has been shown in Fig. 9.13. They were able
to detect toluene up to parts per trillion level (Liang et al. 2015).
4 Conclusion and Future Scope
The sources, contamination, hazardous effects, various detection and extraction

techniques of hydrocarbons have been presented in this chapter. The chapter
comprises the efforts made by researchers in the past few years for the detection
282 S. Patra et al.
Fig. 9.13 Experimental setup for potentiometric detection of the toluene vapor (Reproduced with
permission from Liang et al. 2015)
and extraction of two major toxic hydrocarbons (i.e., polycyclic aromatic hydro-
carbons and volatile organic compounds) formulating the innovative and simpler
way. The growing contamination of air, soil, and water samples from these types of
hydrocarbons becomes major concern of these days. They are entering into the
human and animal body through breathing, food, and water samples. Much devel-
opment has been made so far for the preparation of nanosensor for their detection.
But still, there is a need for more research to extend these sensors at the level of
real-time applications in future. The reported techniques lack the feature of selec-
tivity and much research has to be carried out for improving their detection limit in
the range of parts per trillion or low. There is a high need for an efficient device for
their trace level on-field detection by which we can efficiently detect the amount of
atmospheric hydrocarbon level. In addition, some selective adsorbents with a high
efficiency are also needed for their removal from atmosphere, soil or water samples,
so that we can get a pollution-free earth in upcoming days.
Acknowledgments Authors are thankful to DST, BRNS, and ISM for sponsoring the research
projects to Dr. Rashmi Madhuri (Ref. No.: SERB/F/2798/2016-17; SB/FT/CS-155/2012; FRS/43/
2013-2014/AC; 34/14/21/2014-BRNS) and Dr. Prashant K. Sharma (Ref. No.: SR/FTP/PS-157/
2011; FRS/34/2012-2013/APH; 34/14/21/2014-BRNS).
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Chapter 10
Biogas Produced from Different Feedstocks
in Anaerobic Digesters
Grazia Leonzio
Abstract Anaerobic digestion is a useful method for producing clean fuel from
renewable feedstocks. It is a biological process where biodegradable matter is
degraded or decomposed by the activity of specific microorganisms in the absence
of oxygen, producing biogas used for electricity and heat generation. The anaerobic
digestion is affected by the type of raw materials. Co-digestion, the simultaneous
digestion of a mixture of two or more substrates, is a technique, by which the
bioconversion rate, as well as the methane yield, can be increased. The same effects
are produced by the pretreatment of the biomass as pretreatments make the organic
substance of smaller size more accessible to microorganisms and methane produc-
tion. An important parameter used to evaluate the efficiency of anaerobic digestion
is the bio-methane potential. Others are the gross energy yields, the cumulative
energy demand, the net energy yield, and the energy efficiency. In this chapter, a
literature analysis about the diet of anaerobic digestion and related methods to
improve the process is carried out. Works report that energy crop is the most used
substrate for the biogas production. Mechanical, chemical, thermal, thermochem-
ical, and biological pretreatments can be used. Also, the different configuration of
anaerobic digester can be developed to improve the efficiency of the process.
Keywords Biogas • Anaerobic digestion • Co-digestion • Pretreatment of

biomass • Bio-methane potential • Configuration of anaerobic digestion
1 Introduction
Policy makers from around the world show an increase in energy consumption, by
promoting the conversion from an economy based on fossil sources to renewable
sources (Richardson 2012). The agricultural sector participates in it, by providing
biomasses that must be transformed into various forms of energy.
G. Leonzio (*)
Department of Industrial and Information Engineering and Economics, University of L’Aquila,
Via Giovanni Gronchi 18, 67100 L’Aquila, Italy

292 G. Leonzio
In this context, the use of anaerobic digesters feed by biomasses for biogas
production and ultimately also for bio-methane production is increasing. These are
important strategies to reduce gaseous emissions produced by fossil fuels, in
compliance with the Kyoto Protocol and therefore with the EU Directive 209/28,
which considers the 20% of energy consumption deriving from renewable sources
by 2020. Within the European Union, biogas production is increased by about six
times from 1990 to 2005 (Murphy et al. 2011) reaching a value of 10.9 million tons
of oil equivalent in 2020. Anaerobic digestion is currently widely promoted by
businesses, research, and market policy (Callahan 2011).
At first, anaerobic digestion was used to handle sludge deriving from wastewater
treatment systems. Recently, this technique has been extended to an animal,
agricultural and industrial by-products, and sludge of wastewater treatment
(González-Fernández et al. 2008).
The advantages that can be gained are the reduction of volatile suspended solids
and odors, the destruction of pathogenic organisms, and the energy production from
renewable sources. Then, anaerobic digestion offers the possibility of giving to
biomass an added value by converting it into energy, as methane and organic soil
(digestate), that is rich in nutrients, water, and organic matter.
Furthermore, it is a technologically process with low energy demand; it is
possible to obtain simultaneously an organic waste treatment and stabilization,
energy production, emissions reduction (including natural carbon), and liquid
fertilizers production (Müller 2007). It is also possible to obtain the recirculation
of nutrients and organic materials, by minimizing the need for external input.
However, the CO2 released in the digestion process cannot be considered a green-
house gas emission because carbon is used by plants for photosynthesis and is
released into the atmosphere, as part of the carbon cycle.
In waste management, anaerobic digestion is more favorable than aerobic
treatment, due to a better emission control and the energy recovery in the form of
biogas. Variations in the net energy consumption and in energy efficiency are
related to raw material properties and design of anaerobic digester.
To achieve an excellent biogas yield, it is necessary to provide an accurate
nutritional target and a suitable feeding.
Biogas plants treat different kinds of organic compounds that include wastewa-
ter, food industry and agricultural residues, sewage and energy crops. Although
sewage allows having more energy enhancement through anaerobic digestion
(Mara~ nón et al. 2012), biogas plants are mainly fed by energy crops.
In the literature, there are several works related to biogas production from energy
crops. Only a few works combine the specific methane yield and the crop yield, by
assigning a methane yield per hectare (Bauer et al. 2010).
Multiannual crops are Arundo donax L. (Arundo, also known as Giant Reed),
Panicum virgatum L. (switchgrass) cv. Alamo, the inter-specific hybrid Sorghum
arundinaceous Stapf (Sorghum halepense Pers. Sorghum roxburghii Stapf),
known as Silk Sorghum (S. Silk). Among these, switchgrass (Panicum virgatum)
has been recently reassessed for methane production (Frigon et al. 2012), while
Arundo is subject to most recent experimentations (Di Girolamo et al. 2013).
10 Biogas Produced from Different Feedstocks in Anaerobic Digesters 293
Annual energy crops are: sorghum [Sorghum bicolor (L.) Moench] genotypes,
namely fiber (Biomass 133; B 133), sweet (SUCROS 506; S506) and forage hybrid
(Trudan Headless; Trudan H.), a hybrid corn (Klips, FAO 700 maturity).
Among multiannual species, Arundo is a promising crop in Southern Europe
from the point of view of energy (Lewandowski et al. 2003); switchgrass is used
overall in the USA (Monti et al. 2011); Sorghum Silk should combine the better
forage sorghum characteristics (thin-stemmed “Sudan” genotypes) with its
multiannual production (Corleto et al. 2009). Barbanti et al. (2014) evaluate crop
diversity in quantity (biomass yield) and in quality (analytical characteristics),
reflecting on their performance in the specific methane yield and in gross energy
efficiency. Corn is the most important energy crop for biogas production with the
highest yield in central Europe. Silage cereals are mainly used in Italy and in other
parts of Europe.
In addition to corn, that is the main contact among energy crops, different
varieties of sorghum (Sorghum bicolor) are used, hybrids including fiber, sweet
and forage genotypes, for which methane production is evaluated (Jerger et al.
1987; Bauer et al. 2010; Sambusiti et al. 2013). The comparison between the
velocity of the recirculated and measured liquid phase and the experimental is
shown in Fig. 10.1.
2 Parameters Related to Diet of Anaerobic Digester

to Evaluate the Efficiency of the Biogas Production
In processes of anaerobic digester, different parameters are used to evaluate the

efficiency of biogas production.
The methane yields are in general evaluated in batch reactors under mesophilic
conditions (35 C), with an inoculum that has the following characteristics: TS of
36 mg g1, VS of 22.6 mg g1, TOC of 11.2 mg g1, TKN of 3.5 mg N g1, low
C/N ratio equal to 3.2, total alkalinity of 28.2 g CaCO3 l1. The content of NH+4–N
is high enough (2.77 mg g1). Biogas is measured at each sampling time and it is
aggregated as ml g1 VS. CH4 production is calculated based on volume displace-
ment and percent methane content at each current and previous reading as the
following equation (Lou et al. 2012) (Eq. 10.1).

ðA þ BÞ ∙ %CH4t B ∙ %CH4ðt1Þ
CH4 ðmlÞ ¼ ð10:1Þ
100 100
where A is the displaced gas volume, B is the headspace gas volume, t is the current
sampling time; t1 is the previous sampling time. The specific methane yield is
accumulated over time by adding up the amount of methane produced at each date
at the net of the inoculum, expressed as ml CH4 g1 VS as in the following equation
(10.2):
294 G. Leonzio
Gas bag for gas

collection
Gas composition
sampling
Air pump for biogas

Wet test meter for recirculation
periodic gas production
measurements Valve for feed
152 mm
344 mm
194 mm 140 Draft tube (38 mm dia)

mm
26 mm
Valve for effluent
Fig. 10.1 Schematic diagram of the experimental setup of the anaerobic digester (Karim et al.
2005)

V biogas sample ∙ CH4, sample V biogas inoculum ∙ CH4, inoculum
specific yield ¼
VS
ð10:2Þ
where Vbiogas sample and Vbiogas inoculum are biogas volume in sampling and in the
inoculum, CH4,samples and CH4,inoculum are the methane percentages contained in the
sample and in the inoculum. Energy crops have different specific methane yields
and they are different from corn. The specific methane yields are evaluated in
58 days of incubation, and it is observed that they follow three different fields. Corn
is characterized by a greater nation destination, so that it reaches greater methane
potential yields equal to 316 ml g1 VS. The three hybrid sorghums and S. Silk
show an intermediate response with a median value of 262 ml CH4 g1 VS.
The difference in the potential methane yield, among energy crops and maize,
are reported in the literature. As concerns sorghum, the highest values are often
observed, with +16% as mean value (Sambusiti et al. 2013) in forage fiber
genotypes (251 ml CH4 g1 VS in Trudan Headless), or +15% as mean value
(Jerger et al. 1987), but also +35% (Bauer et al. 2010). Yields of 400 g ml1 VS are
evaluated for the 506 SUCROS sorghum (Jerger et al. 1987), but also of 303 ml g1
VS (Sambusiti et al. 2013) and 345 ml g1 VS. For these experiments, the
incubation period varies from a minimum of 21 days (Mahmood and Honermeier
2012) to a maximum of 60 days (Jerger et al. 1987).
Switchgrass is collected mostly still green in the summer and therefore with
lower lignification, specific methane yield and a low fiber content. Massé et al.
(2011) find methane yield values between 169 and 252 ml CH4 g1 VS according to
the climatic season. Frigon et al. (2012) identify wider range: 95–152 ml CH4 g1
VS, according to the climatic season and to the pretreatment used in feeding.
Barbanati et al. (2014) find values of 216 ml CH4 g1 VS despite having been
raised in senescence with an advanced stage of lignification. Arundo has
methane yield values of 260 ml CH4 g1 VS (Ragaglini et al. 2014). Values of
273 ml CH4 g1 VS are achieved with experiments without pretreatment
(Di Girolamo et al. 2013). The difference can be attributed to the different condi-
tions in which the experiments are conducted: thermophilic and mesophilic at
53 and 35 C in the first and in the second experiment.
Some evaluations about potential methane yields, with regard to the methane
yield at the end of incubation, can be predicted through the Gompertz function. A
first-order kinetics is particularly used to fix data, by leading the methane cumula-
tive yield to a slight overestimation at the end of incubation, as the following
equation (10.3):
CH4 ¼ CH4 O ∙ e
xxo
b ð10:3Þ
where CH4 is the specific methane yield at t time (ml g1 VS), CH4O is the potential
methane yield that is the asymptote, x is the speed of substrate degradation, xo is the
inflection point, and b the speed of substrate degradation. Some differences in the
behavior of seven energy crops can be observed in the speed of substrate degrada-
tion (b parameter) and in the inflection point xo: the shortest time indicating the
easiest substrate degradation is recorded by corn (b and xo, 5.6 and 5.9 days). The
three hybrid sorghums S. Silk and Arundo, exhibit a slight decrease in both
parameters (b between 8.2 and 9.5 days; xo between 8.7 and 9.4 days) (Barbanati
et al. 2014). Switchgrass shows slower kinetics (b and xo, 11.4 and 11 days). Corn
reaches the highest peak in the daily methane yield after 6 days of incubation
(20.4 ml CH4 g1 VS d1). Three annual hybrids sorghums and S. Silk obtain an
intermediate peak (with a mean value of 11.4 ml CH4 g1 VS d1) in a longer time,
after 10 days of incubation. Arundo and switchgrass receive the lowest peaks (8.3
and 7 ml CH4 g1 VS d1) at the same time of sorghums variety, Fig. 10.2.
The gross energy yields per unit crops area (GE) measured in GJ ha1 can be
calculated as follows (Eq. 10.4):
GE ¼ DBY ∙ VS ∙ CH4 O ∙ 0:03402 ð10:4Þ
with 0.03402 GJ Nm3 that is equal to the lower heat of methane (CTI 2009). The
amount of consumed energy per unit crops area is evaluated by the Cumulative
296 G. Leonzio
Fig. 10.2 Cumulative methane yield during the anaerobic digestion of seven crop samples
(symbols) and fitted functions (lines) (a), and daily methane yield (b) estimated as the first
derivative of fitted functions (Barbanti et al. 2014)
Energy Demand (CDE) through an analysis based on life cycle (Frischknecht and
Jungbluth 2003). It briefly takes into account the amount of energy of the products
used in the agricultural process (fertilizers, fuel, etc.) or small fractions attributed to
the process (farms or equipment).
Other indicators to assess the energy efficiency of energy crops are net energy
yield NE, as the difference between produced and consumed energy GE–CED, the
energy efficiency EE as report GE/CED.
The GE values have a range between 286 GJ ha1 for maize and 158 GJ ha1 for
switchgrass and S. Silk. This value corresponds to a methane production between
4600 and 8400 Nm3 ha1. The two varieties of B133 and S 506 hybrid sorghum are
lower than maize by 10% and 20%. The Cumulative Energy Demand varies
between 39 GJ ha1 for corn and 15 GJ ha1 for the three multiannual species.
The three hybrid sorghums show intermediate values of CED of 21 GJ ha1.
Net energy yield describes the same pattern as gross energy yield. The two
aforementioned sorghum hybrids are not significantly different from maize. From
experimental results, NE values encompass a range of net methane output between
4200 and 7000 Nm3 ha1.
Unlike GE and NE, maize shows lower values of energy efficiency. The three
heterogeneous energy crops, switchgrass, S. Silk, and S 506, show intermediate
values of energy efficiency of 10.3 GJGJ1. Arundo and B133 have the highest
energy efficiency, an average of 10.3 GJGJ1, due to the lower value of CED.
Significant differences are reported in the literature about the gross energy yield
and the methane yield per hectare, as reported in Fig. 10.3. A methane yield of
7288 Nm3 ha1 which corresponds to values of GE 248 GJ ha1 is measured for the
sorghum silage, presumably a hybrid biomass (fibers or sweet), in Austria (Bauer
et al. 2010); this value is very close to that obtained for the B133 sorghum and for
SUCROS 506, an average equal to 237 GJ ha1 (Barbanati et al. 2014). In other
experiments, forage sorghum (genotype fibers) reaches a value of 175 GJ ha1
(Mahmood and Honermeier 2012). As regards switchgrass, the GE values vary in
the range between 20 and 46 GJ ha1 (Massé et al. 2011) and between 34 and
85 GJ ha1 (Frigon et al. 2012), depending on the harvest time and on the used
pretreatment. For switchgrass that has not received a pretreatment, there are values
of 158 GJ ha1, which largely exceed the values indicated above, thanks to a higher
biomass yield per hectare. No data on the energy yield or on the methane yield per
hectare are present for Silk Sorghum.
Arundo has a value of methane yield equal to 9500 Nm3 ha1 (Ragaglini et al.
2014). Arundo suffers a wide gap from maize in both gross and net energy yield.
The perspective of replacing corn with Arundo is associated with the possibility of
its cultivation with the use of a few inputs (water, fuels, etc.). So pretreatments are
an efficient method to improve the modest biodegradability of Arundo and to fill the
gap with maize. Also, energy efficiency emphasizes a good chance for energy crops
to be used. The multiannual energy crops and particularly Arundo seem to be the
best candidates (EE average + 48% above the corn). As regards maize, the energy
demand for irrigation (4.5 GJ ha1) and the N additional supply (8.6 GJ ha1)
represents a constraint that energy crop cannot exceed. For these reasons, it is better
to choose energy crops for biogas production.
Energy crops that require little energy can be a source of more sustainable
energy than corn in areas where there is a greater surplus of land. Especially
multiannual species are a viable alternative to corn (Lewandowski et al. 2003).
298 G. Leonzio
a
300 NE
GE a
ab a
250
a
b
ab
GJ ha–1
200
c
bc c
c c
150 c c c
100
0
b
14 EE
a
12 a
ab ab ab
10
GJ GJ–1
8 b
b
0
s lk . 3 6
un
do ras Si nH 13 50 ize
Ar tch
g S.
ud
a B S Ma
i
Sw Tr
Fig. 10.3 Gross energy yield (GE) and net energy yield (NE) (a) and energy efficiency (EE) (b) in
the seven biomass crops. ANOVA analysis significant at P 0.01. In each trait, different letters
indicate statistically different means (SNK test; P 0.05) (Barbanti et al. 2014)
For the sorghum silage, a hybrid biomass (fibers or sweet), it is possible to have a
methane yield of 7288 Nm ha1 which corresponds to GE to 248 GJ ha1 (Bauer
et al. 2010).
These values are similar to other types of sorghum: 237 GJ ha1 for B133 and
SUCROS 506 in average. For the forage sorghum genotype fibers, there are values
of 129 GJ ha1, whereas genotype fibers scored 175 GJ ha1 (Mahmood and
Honermeier 2012). Two varieties of hybrid sorghum, B 133 and S 506, have yields
of about 10% and 20% that are lower if compared to corn.
There are open issues concerning the feeding of biogas plants: the required
quality, the minimizing of the environmental impact, and the maximizing of the
energy yield. The content and the availability of substrates that are capable of
producing biogas are affected by variety, cultivation, and maturation stage.
Chandler et al. (1983) find different correlations between the biodegradability
stage and the substrate composition. An esteem of the potential to produce methane
from manure and energy crops is essential. The maximum methane yield requires
adequate and effective nutrients that are supplied to microorganisms in the digester.
Literature reports studies on the digesters diet, analyzing how this can affect the
amount of produced biogas and methane. The knowledge of potential biogas is
important for decisions about size, design, and economic management of biogas
plants.
A first-order kinetics model is used to evaluate the performance of biogas and
methane production in different conditions (Sánchez et al. 1996; Pagés et al. 2011)
(Eq. 10.5):

yðtÞ ¼ ymax ∙ 1 ek ∙ t ð10:5Þ
where y(t) is the cumulative methane curve (CH4 ml g1 VS1), ymax is the final
methane yield in an infinite residence time, k is the kinetic constant (d1), and t is
time (days). Productivity is modeled in accordance with the following equation
(10.6):
b ∙ cb ∙ tb1
r ðstÞ ¼ ymax ∙ ð10:6Þ
ðcb þ tb Þ2
where ymax is the final methane yield (ml CH4 g1 VS1), t is time (days), and b and
c are the equation coefficients. The experimental data are fixed by a nonlinear
regression analysis. The theoretical methane yield from untreated sludge is calcu-
lated by using Busswel equation. When the experimental value is known, the total
efficiency of the anaerobic digestion process is calculated by the following equation
(10.7):
exp
ymethane
η¼ theo
∙ 100 ð10:7Þ
ymethane
300 G. Leonzio
3 Bio-methane Potentials for Anaerobic Digestion
Different methods are used to evaluate the effectiveness of a digester’s diet,

especially for expensive dedicated crops. One of them, as reported in the literature,
is the bio-methane potentials (BMP), that is used to measure the potential produc-
tion of methane from the substrate, under optimal conditions using laboratory scale
tests (Hansen et al. 2004).
In particular, the bio-methane potential is a method, initially developed by Owen
et al. (1979), to determine the conversion rate of organic waste into methane and to
evaluate the maximum anaerobic biodegradability of an organic substrate. Through
this parameter, it is possible to assess a given substrate and optimize an anaerobic
digestion process (Raposo et al. 2011). Recently, there is a relative increase about
BMP studies on different substrates, including agricultural crop straws, urban solid
waste, and raw manures (Angelidaki et al. 2009). Many studies are conducted to
evaluate the anaerobic biodegradability of a lignocellulosic substance by its chem-
ical composition.
The features that influence the degradation degree of a lignocellulosic material
are lignin content, hemicellulose, mannose, cellulose, cellulose crystallinity, and
the association degree between lignin and carbohydrates (Chandler et al. 1980;
Gunaseelan 1997; Tong et al. 1990). Some researchers try to define a mathematical
model to estimate anaerobic biodegradability according to the lignocellulosic
content of the substrate.
BMP is used for decades, however, researchers are considering further simpli-
fications for further optimizations of the process (Colleran and Pender 2002; Rozzi
and Remigi 2004a). Colleran and Pender (2002) evaluate the necessity to harmo-
nize the anaerobic biodegradation, the activity, and inhibition assay, especially in
the standardization of the test inoculum, test conditions, and the duration of the
biodegradability tests.
Other researchers measure the pH influence, the temperature, the type, and
concentration of biomass hydrolysis on BMP (Gunaseelan 1997; Rozzi and Remigi
2004a).
The inoculum source may have different bacterial populations, substrate adap-
tion, and remains of substrates that are anaerobically biodegradable. Different
inocula include sludge coming from industrial treatment plants, granular sludge
from anaerobic digesters that treat brewery wastewater, animal manure, and sludge
from municipal water treatment plants.
For the influence of the substrate/inoculum (S/I) ratio of the BMP value, results
suggest an increase of the biodegradability, with the decrease of the S/I ratio, as
reported by Hashimoto (1989). The first author reports a reduction of biodegrad-
ability when the S/I ratio increases, digesting ball-milled straw using a cattle
manure inoculum. At an alkalinity level of 37 mg NaHCO3 g COD1, they find
that biodegradability and the speed of biodegradability decrease when the S/I ratio
increases from 0.5 to 1 although there are strong influences on the performances of
a granular inoculum. The decrease of BMP with the increase of S/I could be
attributed to luxury substrate uptake or storage under conditions of the high

substrate (Chudoba et al. 1992). A further explanation about the decrease of BMP
with the increase of S/I is due to the pH value for the VFA release.
In literature, a formula to estimate the value of BMP is present.
BMP expressed in liters of methane at standard conditions for amounts of added
volatile solid substrate is calculated from the maximum methane production
through the “sample bottle” and it is corrected by the maximum methane produc-
tion through the “empty bottle.” The biggest quantities of produced methane are
calculated using the equation of state for gases at the increase of pressure and by
multiplying the amounts of biogas with methane percentage in the headspace. The
quantity is converted into liters, according to the following equation (10.8):
h i
Ps þPatm ∙ V s %CH4s Pbl þPatm
%CH4bl
RT ∙ 100 RT ∙ V bl ∙ 100
BMP ¼ ∙ 22:4 ð10:8Þ
So
where Ps is the pressure in the sample (in Pa), Patm is the atmospheric pressure
(in Pa), Pbl is the pressure in the headspace, Vs is the headspace volume of the test
bottle (in m3), Vbl the headspace volume of the blank bottle (in m3), T is the
temperature of 308.16 K, R is the universal gas constant equal to 8.3114 (in Pam3
mol1 K1), CH4s is the methane percentage in the sample, CH4bl is the methane
percentage in the bottle blank, and So is the amount of added substrate (in GVS).
BMP underestimations can take place in the presence of inhibitors with pH values
outside the optimal value. In fact, the stable pH maintenance is the greatest problem
for the digestion of the lignocellulosic material, due to its buffer capacity and
volatile fatty acids accumulation (Banks and Humpreys 1998).
The biodegradability (Bo), as a maximum percentage of COD that is added and
converted to methane, is calculated as the ratio between the maximum COD of
methane, added as methane, and the biggest amount of COD, added in the sample
(Eq. 10.9):
CH4, max 2:86

Bo ¼ ∙ ∙ 100 ð10:9Þ
So CODs
where CH4,max is the maximum amount of methane produced in the digester in the
last phase, So is the quantity of added substrate (in GVS), 2.86 corresponds to COD,
that is the equivalent of 1 l of methane under standard temperature and pressure
conditions (in g COD l1) and CODS is referred to COD within a sample, (in g COD
GVS1). Although Bo refers to the substrate converted into methane, a portion of
the substrate that remains in the form of biomass is present: this quantity cannot be
measured directly but it must be estimated.
However, the materials are mainly composed of soluble substances and different
types of structural materials (lignin, cellulose, and hemicellulose). In the past,
lignin is considered as an indicator for estimating the biodegradability of the
material (Chandler et al. 1980; Tong et al. 1990). The impact of lignin on the
302 G. Leonzio
biodegradability of organic matter is associated with its role in the lignocellulosic

complex: it is reported to hamper the degree and the rate of degradation of
degradable hollocellulosic components (Selinger et al. 1996). The mechanism
according to that lignin influences the hollocellulosica decomposition can take
place by blocking the access to the microorganism in more biodegradable areas
or through inhibitory effects starting from lignocellulose-containing compounds or
by their hydrolysis.
It has been observed that lignin and cellulose can better describe the biodegrad-
ability of organic matter. Buffiere et al. (2006) find a relationship between the
amount of lignin and cellulose and the biodegradability of organic matter although
no statistical analysis is reported about it. The Bo value of different species of
energy crops can be approximated, using simple linear models. Sutaryo et al. (2012)
find a relationship between lignin and cellulose biodegradability (Eq. 10.10):
Bo ¼ 086 0:92 ∙ ðL þ CÞ ð10:10Þ
where L and C are lignin and cellulose measured in GVS g1. Some interactions
between lignin and cellulose can be statistically evaluated by considering an
additional term that takes the product between the two variables into account
(Eq. 10.11):
Bo ¼ 081 0:69 ∙ ðL þ CÞ 1:87 ∙ ðL ∙ CÞ ð10:11Þ
Considering cellulose, hemicellulose, and soluble cells, the biodegradability of an

organic substance can be found with the following relationship (Eq. 10.12):
Bo ¼ ðBoc ∙ C ∙ Cav Þ þ ðBoh ∙ H ∙ H av Þ þ ðBocs ∙ CSÞ Xb ð10:12Þ
where Boc is the biodegradability of cellulose, Boh is the biodegradability of

hemicellulose, Bocs refers to soluble cells, and Xb is the amount of converted
biomass. Other models are showed in Table 10.1.
The model I and II are considered as approximation into an individual quanti-
tative relation between the biodegradability of the fractions of cellulose and lignin,
and hemicellulose and lignin. Model III considers both cellulose and hemicellulose
to act as one entity. Model IV considers the relation between lignin and
hollocellulose availability (CHav) to be surface related (Conrad et al. 1985). The
table also reports four statistical performance models.
The maximum biodegradability of a substance is calculated by the following
equation (10.13):
CODmethane, t¼max þ CODs, t¼max CODs, t¼0

Bp ¼ ð10:13Þ
CODin CODs, t¼0
where CODmethane,t¼max is the COD concentration that is equivalent to the amount

of methane produced in the final digestion time, CODs,t¼max is soluble COD at the
Table 10.1 Equations, number of parameters ( p), coefficient of determinations (R2), and signif-
icance (t values) for the estimation of anaerobic biodegradability based on a deterministic
approach
Model Equation Assumption tested R2 RSS Fpr
I Bo ¼ [0.22∙Ci∙Cav) + (1.01∙ Cav ¼ (C L )/C 86 0.006 <0.001
(NDSi + Hi)] 0.17
II Bo ¼ (0.58∙Ci∙Cav) + (0.85∙(Hi)∙Hav)∙ Cav ¼ (C L )/C 81 0.016 <0.001
(1.14∙NDSi) 0.25 Hav ¼ (H L )/H
III Bo ¼ (0.74∙(Ci + Hi) CHav ¼ (C + H L )/ 73 0.011 <0.001
∙CHav) + (1.04∙NDSi) 0.25 (C + H )
IV Bo¼ (0.86∙(Ci + Hi) CHav ¼ [1 (L2/3/ 75 0.011 <0.001
∙CHav) + (1.07∙NDSi) 0.28 NDF2/3)]
C cellulose, H hemicellulose, L lignin, av available, NDS neutral detergent solubles
final digestion time (in g COD l1), CODs,t¼0 is the soluble COD concentration at
the zero digestion time (in g COD l1), and CODin is the initial total COD
concentration in the sample (Table 10.2).
The BS value, that is the portion of soluble COD converted into methane at the
end of digestion, can be calculated in the following way (Eq. 10.14):
CODs, t¼0 CODs, t¼max

Bs ¼ ð10:14Þ
CODs, t¼0
According to BMP, a simple stoichiometric calculation of the maximum poten-

tial is used for gas production: theoretical or stoichiometric methane potential,
TBMP (Møller et al. 2004; Raposo et al. 2011; Triolo et al. 2011). However, the
TBMP values obtained by stoichiometric calculations are greater than the methane
potential which is influenced by recalcitrant carbon (Triolo et al. 2011). So TBMP
is not used as a potential indicator of biogas production but as a parameter to
evaluate the biodegradability of a substrate.
A developed method to determine BMP is the near-infrared spectroscopy tech-
nology (NIRS). It allows the reduction of time measurement. In fact, the traditional
measurement systems are expensive and require too much time, so are not advan-
tageous for large-scale operating digesters. Triolo et al. (2014), in particular, test a
partial least square (PLS) model for a rapid determination of BMP by using NIRS.
A total of 88 plant biomass samples of a wide variety is used for model prediction.
The standard error of the best PLS model is 37 CH4NL kg1 VS, where the BMP of
the test set is between 136.2 and 477.9 CH4NL kg1 VS, the coefficient of
determination and residual prediction deviation is 0.84 and 2.49. This shows that
NIRS has some success in various applications and might be an alternative tool to
traditional measurement systems. In various experiments, BMP values are deter-
mined by VDI 4630 regulations: Lesteur et al. (2011) and Doublet et al. (2013)
apply this technology to municipal solid waste plants.
304 G. Leonzio
Table 10.2 BMP and biodegradability as assessed from batch digestion of 15 European species
BMP BMP Bo Bp Bs
Species (lCH4 g VS1) (lCH4 g COD1) (%COD) (%pCOD) (%sCOD)
Yellow lupin 0.26 0.01 0.16 0.01 47 36 92
Vetch 0.29 0.02 0.2 0.01 56 43 99
Carrot 0.31 0.01 0.23 0.02 66 31 100
Spartina 0.29 0.01 0.21 0.03 59 52 97
White lupin 0.26 0.01 0.18 0.04 52 35 100
Triticale 0.29 0.00 0.20 0.00 57 52 86
Braken 0.18 0.01 0.12 0.01 34 22 92
Sweet clover 0.29 0.01 0.18 0.01 53 42 88
Winter barley 0.30 0.01 0.21 0.01 60 51 93
Winter bea 0.35 0.02 0.23 0.02 66 55 89
Sweet pea 0.37 0.03 0.24 0.02 70 61 93
Oil seed rape 0.29 0.02 0.18 0.01 51 59 90
Buckwheat 0.32 0.02 0.22 0.01 63 54 98
Rosebay willow 0.20 0.01 0.13 0.01 37
Quinoa 0.33 0.02 0.24 0.01 70
Bo: Proportion of total COD converted into methane by the end of the digestion time; Bp:
Proportion of the particulate COD that was mechanized by the end of the digestion time; Bi:
Proportion of the soluble COD that was methanized by the end of the digestion time
4 Co-digestion Methods in Anaerobic Digesters to Produce

Biogas
The definition of co-digestion is a treatment that combines different types of sub-

strates with the aim of improving methane production (Cuetos et al. 2011). This
strategy may increase the methane production by balancing the content of nutrients
for substrate and by reducing the negative effects of substrate inhibitors in the
anaerobic digestion process (Cuetos et al. 2011).
Co-digestion of organic residues can ensure the feasibility of the process and in
many cases, biogas yields are increased due to the synergistic effect of the use of
co-substrates that provides any missing nutrients (Mata-Alvarez et al. 2000). An
economic balance of anaerobic digesters shows that substrate must have a methane
yield greater than 20 m3CH4t1 as biomass to be cheap. For examples, sewage has a
methane yield included in a range between 10 and 20 m3CH4t1, while for
industrial organic by-products the range varies from 30 to 500 m3CH4t1. Besides
the increase of methane production, the addition of by-products can stabilize the
process, if added in a controlled manner. For example, co-digestion of sewage and
industrial by-products appears to be an attractive method to make biogas plants
economically feasible. However, in Denmark, the availability of organic
by-products is limited if compared to the amount of slurry and the high prices of
this biomass made co-digestion not economically attractive (Ward et al. 2010). For
this reason, Hamelin et al. (2011) propose some strategies to overcome this
problem: a carbon external source in the form of energy crop as co-substratum,
by using a digester with a larger residence time to compensate for lower methane
yields of animal sewage.
Co-digestion has several other advantages: the dilution of toxic substances
which come from used substrates, the synergistic effects of microorganisms, a
greater speed of digestion, a possible detoxification based on the co-metabolism
process (Montusiewicz and Lebiocka 2011). However, both the supplied load and
the hydraulic residence time increase (Cecchi et al. 1996).
Trying to get a co-substrates mixture as optimal conditions that allow the
maximum biogas yield without compromising the stability of the process is critical.
Generally, co-digestion of sewage sludge takes place with organic substrates
such as the organic fraction of municipal solid waste (Bolzonella et al. 2006), food
waste (Iacovidou et al. 2012), agricultural waste (Mara~nón et al. 2012), and
wastewater from butchery activities (Cuetos et al. 2008).
Anaerobic co-digestion of agricultural waste and energy crops, in particular, can
be one of the main alternatives in this sector, as stated by the United Nations
Development Programme (UNDP), which considers this technology as one of the
most useful decentralized sources of energy supply, especially when used with
energy crops and with all substrates that can be easily found on many farms
(Cavinato et al. 2010).
Sewage is a readily available source on farms, but the reduced biogas yield does
not justify the capital costs of plants. So the biogas yield can be increased by
placing co-substrates that are rich in energy such as corn, grass, fruit, and bread.
Different experiences show that in co-digestion thermophilic temperatures are
preferred to mesophilic (Mladenovska and Ahring 2000; Van Lier et al. 2001;
Angelidaki et al. 2006). However, in co-digestion systems, the addition of the
organic load radically alters the process management. In fact, the stability of the
process becomes much more difficult to keep, due to the greater variability of the
characteristics of the process and the balance that must be maintained between acid
hydrolysis reactions and methanogenesis. The maintenance of the fed composition,
the pH value control, and a possible recirculation are important.
Other studies in the literature report that silage can increase the biogas yield
through co-digestion of corn and clover (Amon et al. 2007). Vinasse biomass is
co-digested with pigs manure in laboratory scale and in five mesophilic digesters
that work almost continuously for 640 days. The performances of the process are
monitored by using chemical parameters and quantitative analyzes on acidogenesis
populations and methane genesis. Through vinasse utilization, the process shows
instability after 120 operating days. However, anaerobic digestion of sewage sludge
has a low solids content, lower than 10%, so there are low methane yields compared
to other organic substrates such as energy crops. To overcome this limitation and to
increase methane production from the slurry, co-digestion of slurry is carried out
with different substrates (Ward et al. 2008). Co-digestion of animals slurry clearly
shows improvements in biogas production, in process stability and an increase in
306 G. Leonzio
methane yield compared to theoretical values. The methane yield at an organic

loading rate (OLR) of 2.8 g VS/(lxg) and at a residence time of 45 days with a
substrate mixture formed by 85% of vinasse and 15% of liquid manure is equal to
0.31 NlCH4/g VS.
Bułkowska et al. (2012) study co-digestion of corn silage (Zea mays L. and
Miscanthus sacchariflorus) with 0%, 7.5%, 12.5%, 25% of PS used as co-substrate
in a perfect mixing reactor, with a hydraulic residence time of 45 days and an
organic loading rate of 2.1 g l1 d1. A correlation matrix between produced
biogas/methane and the parameters that describe anaerobic digestion is created to
study the stability of the process. The values of the correlation coefficients indicate
that the greater anaerobic digestion stability is achieved with the 7.5% and 12.5% of
slurry. A positive correlation between ammoniacal nitrogen and volatile fatty acids
concentration, composed by 25% of sewage sludge, shows the instability of the
process.
PCR results show clear changes in the quantitative composition of bacterial
consortia for each fermenter.
Co-digestion is a method for the optimization of biogas production in Zimbabwe
and in rural areas where the amount of liquid manure produced is not sufficient to
satisfy the annual biogas production (Raphael et al. 2009). The advantages are as
follows:
• It provides a better balance of nutrients from a variety of substrates which helps
to maintain the performance of a digester at stable levels and therefore to
produce a good quality fertilizer.
• It enables the optimization of rheological qualities when wastewater with bad
properties are mixed with sewage or sewage sludge.
• Biogas production from the slurry is not profitable according to current oil prices
(it has a low gas yield) so the addition of co-digested with a high methane
potential intensifies the gas yields.
Fountoulakis et al. (2008) study biogas production from co-digestion of olive oil
mills wastes (SW), marc (WGR), and from meat by-products (OMW). Olive oil
mills wastes are taken from Stavrakia, Crete, and Greece after a three-phase
centrifugation process. The experiments are conducted in continuous digesters at
two different temperatures: 35 and 55 C. The addition of SW to anaerobic
digestion to OMW or WGR increases the methane yield and stabilizes the internal
process. Results indicate that co-digestion with 50% of OMW and 50% of SW, with
50% of OMW and 50% of WGR, and with 50% of WGR and 50% SW give a
methane yield of 170, 163, and 191 kg lCH41 per kg of COD added. This increases
the methane yield by 23–36%, compared to that obtained by digestion of only
OMW and WGR. The final methane yield of OMW, from co-digestion of OMW:
SW, OMW:WGR, and WGR:SW under mesophilic conditions is estimated at
184, 214, and 188 kg lCH41 per kg of COD added. Co-digestion of OMW:SW,
OMW:WGR, and WGR:SW under thermophilic conditions produces an increase of
34.5%, 28.9%, and 14.1%, respectively. The use of SW as co-substratum in
anaerobic digestion of OMW and WGR has many advantages: improves the
methane yields, provides to the system all the missing nutrients. The results of this
experiment suggest that co-digestion of these organic residues is very promising.
In general, anaerobic digesters for food waste are not very stable and efficient
due to the volatile fatty acids accumulation. Small fruit and vegetable wastes can be
found in the low value of the C/N ratio. So co-digestion of fruit and vegetable
wastes with other organic waste materials such as municipal sludge, sewage,
agricultural biomass become widespread (Bouallagui et al. 2009). Fruit and vege-
table wastes (FVW) and food wastes (FW) are two FORSU in China and their
lowest C/N ratio can cause a rapid acidification and release ammonia which can
create problems of methanogenesis inhibition in the digester. Co-digestion of FVW:
FW can be a solution to this problem although limited research has been conducted
on it.
Lin et al. (2011) calculate the biochemical methane potential for fruit and
vegetable wastes (FVW) and food waste (FW) from a northern city in China of
12.30, 0.56 m3CH4/kg VS (volatile solids) with a biodegradability of 59.3% and
83.6%. The experimental tests for anaerobic digesters in laboratory scale at a
temperature of 35 C are conducted with an organic loading (OLR) of 3 kg VS/(m3
day) for FVW and FW. For FVW, the process is stable with a 2.17 m3/(m3day)
biogas production rate and with a methane yield of 0.42 m3 CH4/kg VS. Anaerobic
digestion of FW fails due to the accumulation of fatty acids. The effects of the
FVW:FW ratio on the co-digestion stability and performances are analyzed with the
same value of OLR. For values of FVW:FW equal to 2:1 and 1:1, the performance
and operation of the digester are maintained stable, without volatile fatty acids
(VFA) and ammonia accumulation. An FVW:FW ratio equal to 1:2 causes an
increase in the concentration of VFA to 1100–1200 mg/l, while methanogenesis
is slightly inhibited. At the 1:1 ratio for co-digestion of FVW with FW, the methane
production yield is 0.49 m3CH4/kgVS and the efficiency in the removal of the
volatile solids and chemical demand for soluble oxygen are of 74, 9% and 96.1%.
Co-digestion of FVW and FW cannot only achieve the highest biogas yields, but
also high efficiency in the organic matter removal.
Chiu et al. (2013) carry out some studies with different organic loads that are
relative to anaerobic co-digestion of kitchen wastes and sludge from animals, fruit
and vegetable wastes. In kitchen wastes, the Total Chemical Oxygen Demand
(TCOD), oils and fats, and moisture content (MC) are calculated to be 101.5 g/l,
33.0 g/l, and 82.7%, respectively. In swine wastewater, TCOD/TKN is 4.56–43.9
and TCOD/TP is 2.02–31.8. Some biodegradability tests on fruit and vegetable
wastes show that COD removal exceeds 56% and methane recovery exceeds 80%.
Co-digestion of these three organic wastes proves that the system works steadily
until an OLR of 9.52 g COD/ld and at a hydraulic retention time (HRT) of 5 days.
When OLR increases to 12.54 g COD/ld, the efficiency in COD and volatile
suspended solids (VSS) removal decreases from 90% to 76.5% and from 93% to
76.5%. The analyzed ammoniacal nitrogen concentration is 28% lower than the
stoichiometry concentration planned. The discrepancy may be due to different
biodegradability of the substrate, to sampling and analysis procedures of TKN,
and to the parameters used for stoichiometric calculations.
308 G. Leonzio
Sewage is an abundant substrate for anaerobic digestion (Kaparaju and Rintala

2005; Nasir et al. 2012). In Denmark, the methane potential energy, annually
generated through anaerobic digester is equal to 30 petjoule (PJ) and sewage
contributes 80% to this potential.
It is estimated that liquid manure production in the future will continue to
increase. This phenomenon is inevitable since the improvement in well-being and
in standard social life is followed by a dietary change from carbohydrate sources to
protein sources. The consequence of this is a strong demand for animal products,
especially in developed countries. For example, sewage handling, through anaero-
bic digesters, particularly in Denmark is in line with the objective of using 50% of
the produced slurry as a substrate for anaerobic digesters and therefore producing
renewable energy in the form of biogas by 2020 (Aftale om Grøn Vækst 2009).
Sewage is an advantageous substrate for anaerobic digestion processes since it
has a high water content that ensures dilution and it allows to avoid problems with
the pumping; it contains a wide range of nutrients that promote the growth of
microorganisms. However, there are also some limitations to its use. High water
content means that there is little easily biodegradable carbon to produce sufficient
methane per unit volume (Hamelin et al. 2011); therefore, much more energy is
required to maintain the temperature inside the digester, and there are further costs
related to sewage transportation in the biogas plant (Asam et al. 2011).
Methane production from sewage in terms of volatile solids (VS) is about
290 l kg1 for slurry and 210 l kg1 for cow manure (Burton and Turner 2003).
Since the concentration of VS is lower than 5–7% for PS and then 7–9% for cow
manure, methane production is low. This makes anaerobic digestion uneconomical.
The main problems occurring with digestion of sewage in an anaerobic digestion
process are the high water content and the low biodegradability of slurry due to the
high content of fibers that are constituted mainly by lignocellulosic material
(Hamelin et al. 2011). The biodegradability of the slurry is about 32%, 69%, and
52% for cow manure, and sow slurry. The presence of fibers hinders the hydrolysis
processes (González-Fernández et al. 2008).
However, slurry is considered a very good substrate for anaerobic digestion due
to its buffering capacity and its high content of a wide range of nutrients. But it has a
low biogas yield, 20–30 m3/ton (Angelidaki et al. 2003) and a high concentration of
ammonia nitrogen (2–3 gN–NH4+/l). For this reason, co-digestion of wastewater
with a high content of carbon is preferable, not only to increase the C/N ratio but
also to increase biogas production by making the process economic.
Co-digestion of pig slurry (PS) with fish waste (FW) and biodiesel waste (BWs)
is evaluated by Regueiro et al. (2012) and compared with the sole digestion of
PS. The results demonstrate that co-digestion of PM with FW and/or BWs is
possible only if the concentration of ammonia nitrogen and fatty acids remain
below the inhibition level, by modifying some operating parameters such as feeding
composition, the organic loading rate (OLR), and the hydraulic residence time.
Co-digestion of PM and FW is possible with an OLR of 1–1.5 g COD/ld, in a biogas
production of 0.4–0.6 L/L with a COD removal efficiency of 65–70%. As regards
BW, good results (biogas production of 0.9 L/L d and COD elimination of 85%) are
achieved with a feeding concentration lower than 5%. However, if we operate at the
same OLR, biogas production and methane content in co-digestion are increased if
compared to the sole digestion.
Ogunwande et al. (2013) conduct studies about co-digestion of swine manure
(SM) and chicken manure (CM) to optimize biogas production. Five different
mixtures are considered with the SM/CM ratio of 0:1, 3:1, 7:1, 7:3, and 1:0, and
they are digested in batch reactors for 63 days. The results show that co-digestion
has a significant effect on the temperature of the substrate, on pH, and on the
produced biogas. The average temperature of the substrate and the pH value during
the digestion are 28.5 2.5 C and 6.8 0.55. The biogas obtained from the
mixture ratio 0:1 and 1:0, produce 0.52 and 0.38 l kg1 VSfedday1 on average per
day. A value of ratio equal to 1:1 allows to obtain a biogas production higher than
69.2% and 131.6% if compared to ratio equal to 0:1 and 1:0.
Gomec and Ozturk (2013) evaluate biogas production from co-digestion of two
different slurries (pork and chicken) in an anaerobic digester under mesophilic
conditions. To increase biogas production, silage corn is added and the total
produced energy (heat and electricity) is 1.2 times increased by a cogeneration
system. The amount of produced methane is calculated as 5800 and 6580 m3/day,
while total energy is equal to 45.05103 and 51.05103 kWh, without or with the
addition of corn silage.
Miao et al. (2014) observe as that co-digestion of blue algae with PS allows
having the highest methane content equal to 212.7 ml g1 with a ratio between the
two substrates (blue algae/liquid manure) equal to 2. However, pH values, ammonia
nitrogen, ammoniacal nitrogen, and volatile-free fatty acids do not show a signif-
icant difference between the single digestion and co-digestion. This confirms the
stability of the process. The results demonstrate that this system is promising for
energy production from renewable sources and for solid waste treatment.
Cavinato et al. (2010) study co-digestion of manure and other organic waste. If
the temperature rises to 55 C, biogas production is increased from 0.45 to 0.62 m3/
kg VS, compared to normal thermophilic conditions of 47 C (typical of European
co-digesters). Also methane content increases from 52% to 61%. With a higher
stability of the parameters (pH, ammonia, VFA content), a general improvement of
the digester is obtained. They also study the economic feasibility of such plant,
considering the use of a co-generator of 1 MW for electricity and heat generation
and a system for nitrogen removal. The simulations show PB values of 2.5 years,
and 3 and 5 years, in a biogas plant with or without the nitrogen removal process.
Nges et al. (2012) show that the co-digestion of industrial and energy crops
wastewater allows an increase in the produced methane yield per ton of power. The
system also avoids the need for micronutrients that digestion of energy crops
normally requires. Batch co-digestion is used to predict some results which can
be obtained on a large scale, using a CSTR digester: the C/N ratio increases while
the concentration of fatty acids decreases. Moreover, the economic feasibility of the
system improves under these conditions.
Pastor et al. (2012) study the co-digestion of mud and oil used for a
semicontinuous digester, in a pilot plant and under mesophilic conditions (38 C).
310 G. Leonzio
They find that the addition of 0.5% of oil allows doubling the biogas production.
The optimum percentage of oil in the mixture is 19%. The process of co-digestion
improves the volatile substance removal (greater than 11%, if compared to the case
where co-digestion is not used) and also the biogas production (greater than 23.5%,
if compared to the case where co-digestion is not used). The efficiency of the
produced biogas is the same in the presence or absence of co-digestion because the
same kilowatts of energy per m3 of biogas are produced by means of cogeneration.
Thy et al. (2005) conduct experimental tests in a farm in Cambodia that last
150 days and consist of five treatments with proportions between pig and cattle
liquid manure equal to 100:0, 75:25, 50:50, and 25:75. Plug flow digesters, with a
volume of 640 l and a residence time of 20 days, using a polyethylene tubular film
are used. They verify that when the proportion of PS increases, the amount of
produced gas increases more than 50%. The proportion of N in N total ammonia is
also increased. The N experimental measurements are conducted with the Kjeldahl
method. Instead, ANOVA analysis is used to describe the gas production trends, the
characteristics of slurry, sludge, and effluents. They conclude that cattle manure
produces less biogas and less valuable fertilizers if compared to manure.
Agricultural substrates such as fruits and easily biodegradable vegetables with a
low nitrogen content are appropriate for co-digestion, and they can ensure a good
methane production with animal organic waste. (Bouallagui et al. 2009; Dinuccio
et al. 2010). Moreover, the use of agricultural substrates in co-digestion is a viable
solution for its disposal in areas of high agricultural production. So the combination
of PS and carbon-rich substrates can lead to better performance than digestion of PS
only. Furthermore, co-digestion can lead to a reduction in the concentration of some
compounds (such as ammonia and volatile fatty acids) that are present in the slurry
and which may be toxic in the anaerobic digestion process (Murto et al. 2004).
Agricultural substrates may have a different effect in the presence of other sub-
strates (Fountoulakis et al. 2008).
Gelegenis et al. (2007) show that mills wastes may inhibit some microbial
groups in anaerobic reactors, during co-digestion with chicken manure. These
authors report that the presence of phenols and aromatic oils in agricultural sub-
strates could inhibit the development of the populations of Archea in methanogenic
consortia. Furthermore, methanogen populations and their domains are poorly
understood by adding a substrate for the co-digestion with PS (Yue et al. 2013).
Ferrer et al. (2014) evaluate the effect of four different agricultural substrates
(tomato, pepper, peach, and persimmon) on the biochemical methane potential
(BMP) in an anaerobic digester during co-digestion of PS. The study is focused
on optimizing the combination which improves the CH4 production, and it may be a
PS management in high livestock density areas. The experiments are conducted in
plastic bottles for 100 days, under mesophilic conditions (35 1 C). The bottles
are prepared to reach a certain homogeneity in volatile solids (1.3 g VS + manure
from agricultural substrates + inoculum) as well as the amount of the inoculum
(33.6 ml per bottle). On the basis of volatile solids, the inoculum-substrate ratio is
equal to 0.7 in all combinations; therefore, the variation of the volatile solids in the
composition is only attributed to the agricultural substrate. The concentration of
methane in the produced biogas is analyzed by using Focus Gas Chromatograph,

with a split/splitless injector and a flame ionization detector. From some experiment
they find that: vegetable substrates (pepper and tomato) show a higher content of
lipids, proteins, lignins, and cellulose compared to fruit substrates. However, the
latter have a higher carbohydrate content. The highest BMP values are achieved
with those substrates that have a protein content between 14 and 20 g 100 g1 VS,
lipids between 4 and 5 g 100 g1 VS, and carbohydrate between 74 and 78 g 100 g1
VSn of tomato and pepper.
Some differences, concerning BMP production and observed in the study, can be
explained by the composition of the substrate. BMP depends on the amount of the
following components: lipids, proteins, carbohydrates, and lignin. The CH4 poten-
tial of these components is equal to 1014 lCH4 kg VS1 (lipids), 496 lCH4 kg VS1
(proteins), and 415 lCH4 kg VS1 (carbohydrates).
Molinuevo-Salces et al. (2010) achieve an increase in BMP of 27%, by using PS
in co-digestion with fresh corn, carrots, peas, and leaks, at inclusion levels from
15% to 85%, measured in terms of percentage of TS of vegetable substrates in
relation to the TS of the initial PS.
Ria~no et al. (2011) raise the BMP value by 49% by adding winery wastewater to
wastewater during co-digestion at a level from 15% to 85%, measured in terms of
COD. The increase in BMP with increasing agricultural substrate inclusion level
can be explained by the adaptation of the co-substrate mixture to the optimum
characteristics for digestion as regards the biodegradable organic matter. This is
confirmed by the co-digestion of animal manure and agricultural substrates in
continuous experiments using a continuous flow stirred-tank reactor or similar
configurations (Callaghan et al. 2002).
Scano et al. (2014) carried out experimental studies on an anaerobic digester in a
pilot plant which uses fruit and vegetable wastes as substrates, coming from the
Fruit and Vegetable Wholesale Market of Sardinia (Italy). The experimental study
is conducted for a period of about 6 months to assess the most suitable operating
parameters of the process, according to the availability of different types of fruit
and vegetable wastes in different periods of the year. Overall, the optimal waste
loading rate is 35 kg/every day, with a corresponding hydraulic residence time of
27 days. The optimal organic loading rate ranges from 2.5 to 3.0 kg VS/m3 d, and
the average specific biogas production is approximately 0.78 Nm3/kg VS, with a
specific methane yield of about 0.43 Nm3/kg VS. The results of the experimental
study are used for preliminary evaluations of the performances of anaerobic
digestion plant, employed for the treatment of all wastes produced by fruits and
vegetables coming from the Wholesale Market of Sardinia. The estimation of daily
methane production (290 Nm3/d) is sent to a cogeneration unit with an output of
about 42 kW and an annual power generation of about 300 MW h/year (about 25%
of the Wholesale Market electricity consumption). The plant also shows interesting
economic features since the cost of energy production (about 150 €/MW h) is
slightly lower than the energy purchase cost of the wholesale market (about
200 €/MW h). A return time of 7.25 years can be made if electrical energy is sent
312 G. Leonzio
to the national network. PBT decreases by about 5.4 years if 50% of available
thermal energy is used to replace heat production from fossil fuel boilers.
Bouallagui et al. (2009) study anaerobic digesters fed with fruit and vegetable
wastes (FVW). These wastes are characterized by a content between 8 and 18% of
total solids (TS) and by 86 and 92% of total volatile solids (VS). The organic
fraction includes about 75% of biodegradable matter (sugars and hemicellulose),
9% of cellulose, and 5% of lignin. Anaerobic digestion of FVW is studied under
different operating conditions and using different types of bioreactors. The 70–95%
of organic matter conversion into methane is reached, with a volumetric organic
loading rate (OLR) from 1 to 6.8 g fed versatile solids (VS)/l day. There is an
important limitation, in this case, that is a rapid acidification of these wastes, with a
pH decrease in the reactor, and a higher volatile fatty acids (VFA) production,
which inhibits the methanogenic bacterial activity. Systems with two continuous
phases appear to be the most efficient technologies for anaerobic digestion of FVW:
more than 95% of volatile solids is converted to natural gas with a volumetric
loading rate of 5.65 g VS/l d. They find that the average methane production yield is
equal to 420 l/kg added VS.
Sitorus et al. (2013) carry out studies on anaerobic digestion of a mixture of fruit
and vegetable wastes, for 14 weeks and at room temperature. The mixed fruit and
vegetable wastes, collected in a city of Pontianak, are used as substrates in a single
batch phase for biogas production. The wastes are taken according to the sampling
method, with a composition of 78% of vegetable wastes, 4% of tuber wastes,
and 18% of the fruit wastes. Once manually mixed, the total waste weight is
160 kg. They find that the maximum content of methane in biogas is 65% with a
biogas flow of 20–40 ml/min.
As suggested by several authors, sewage produced by various kinds of livestock,
subjected to different diets are a source of gaseous emissions.
Methane emissions are generally reduced during slurry storage and the quality of
fertilizers obtained is high.
For example, the reduction of proteins and the addition of nutritional additives
and enzymes to formulated diets for pigs is found to be effective in reducing
nitrogen, phosphorus, calcium, and other nutrients excretion (Veum et al. 2006),
thus helping to reduce the environmental impact. Likewise, the reduction of protein
content, associated with an addition of amino acids or fiber to the diet allows the
reduction of excreted nitrogen and, consequently, of ammonia emissions. Dietary
modifications can also affect methane production from manure, but few studies
about it are conducted. Velthof et al. (2005) show that the decrease of protein in a
diet reduces methane production, while the addition of fibers increases it. The
increase of fiber in swine diets shifts nitrogen from urine to feces, increases the
excretion of a few fatty acids, and decreases the pH value of feces.
Amon et al. (2006) try to find a relationship between the dairy cattle diet, manure
composition, and methane yield. They also try to optimize anaerobic digestion of
PS with corn silage and with the addition of glycerin. The latter allows increasing
the methane yield of an anaerobic digester fed by protein-rich substrates (corn
silage, PS, rapeseed flour). As regards pig farms, protein, and fiber diets affect
ammonia and methane emissions (Dourmad and Jondreville 2007). High fiber and
low protein diets can reduce ammonia emissions. But this has an effect on methane
emissions, too. In fact, some studies show that the reduction of protein weakens the
maximum amount of methane that can be produced (Velthof et al. 2005), while this
potential is higher with high fiber diets (Velthof et al. 2005). The right content of
fiber and protein can be achieved by providing less soymeal, by adding amino acids
and by increasing the incorporation of protein and/or fiber-rich by-products (Jarret
et al. 2011a). At the same time, the recent increase of by-products such as biofuels,
wheat distiller’s dried grains with solubles, rapeseed flour, and sugar beet pulp,
could be an economic and ecological alternative resource for swine diet. In the last
10 years, thanks to the rapid growth of ethanol industry in Canada, North America,
and Europe, the amount of corn and wheat distiller’s dried grain with solubles
increase. So many studies are aimed at evaluating the effect of different by-products
(wheat DDGS, sugar beet, and rapeseed fatty meal) on the composition of sewage
and on methane emissions.
Jarret et al. (2011b) use five different swine diets, with a different content of fiber
and protein: two control diets, a control high protein (CHP), a diet with 17% of
crude protein (CP), a low-protein control (CLP) diet with 14% of CP, and three
experimental diets with 17.5% of CP, with 20% of (1) dried distillers grain with
soluble (DDGS), (2) sugar beet pulp (SBP), or (3) fatty rapeseed meal (FRM). They
use a CSTR digester with a 30-day residence time. They evaluate the Bo value
(ultimate methane potential) and the methane conversion factor, which reflects the
portion of Bo converted into methane, in the obtained slurry. They use two different
methods to measure methane. The first measures the amount of Bo in sewage sludge
through the bio-methanogenic potential (BMP) test. In particular, the quantity of
emitted methane expressed in liters is calculated on the basis of the organic content
(OM), the volatile solids content (VS), the methane conversion factor (MCF) that
reflects the amount of Bo really converted into methane and the ultimate methane
potential expressed in lCH4 kg1OM (Eq. 10.15).
CH4 ¼ Bo ∙ MCF ∙ OM ð10:15Þ
The values of Bo and of methane conversion factors are reported in the IIPCC.
The second type of measurement is based on different effluents: fresh mud, stored
mud, and a mixture of stools and water. They observe that the kind of diet and
effluents affect the methane production after 30, 50, and 100 days. The interaction
between the type of diet and manure is significant for methane emissions and for the
methane conversion factor. The BMP method registers a greater methane produc-
tion, while the average methane production is 77%, 58%, and 64% of the ultimate
methane potential for fresh mud, stored mud, and the mixture of stools and water.
The results of the experiments show that the type of diet has a significant effect but
that it is rather limited in the ultimate methane potential from the slurry. The effect
of diet is much more evident on the methane conversion factor, with low levels of
high protein diets and high levels for high fiber diets. The results obtained in the
experimental tests can be used to improve dietary characteristics to limit
314 G. Leonzio
uncontrolled methane emission in the environment and to maximize methane

production, when anaerobic digestion is used for energy production.
Jarret et al. (2011a) evaluate the effects of adding 25% of DDGS (dried distiller’s
grain soluble) to swine diet, on the excretion of organic matter, nitrogen, and carbon
and on the methane potential emitted by feces and urine. They conduct eleven
experiments: a control diet mainly based on cereals and soybean meal, and ten
experimental diets obtained by adding to the control diet 25% of one of the ten
samples of DDGS. The ultimate methane potential (Bo) of effluents is measured
with an increased digestion time of 100 days, for each type of diet. The addition of
DDGS increases the amount of the produced feces from 27% to 50% and that of
urine from 7% to 50%, if compared to the base case. The amount of organic matter
produced by feces and urine increases by 65% and 54%, if compared to the basic
case. The Bo values measured in feces and in urine vary in a range between 202–294
and 278–368 LCH4/kg OM. On average, these values are lower than those obtained
in the basic diet.
Sorghum production increases significantly in Brazil, so it can be used in animal
feeding since it has a good nutritional quality and can be a substitute for corn.
According to it, the author assesses the quality and the amount of produced biogas,
starting from a supply that consists in the initial, increasing and final decomposition
of PS, deriving from a corn- and sorghum-based diet. Experimental tests are
performed on 20 batch digesters with a 30-day residence time, a solids content
between 4% and 6% and a volatile solids content between 3.2% and 5.6%. They
also find that the average biogas production is greater in digester fed with feces.
Jarret et al. (2012) show that the addition of high fiber biofuel in diet causes a
displacement of nitrogen from urine to excreted feces, a decrease in slurry pH, and
an increase in C compounds, OM, VFA in the latter. This causes a decrease in the
speed of ammonia volatilization during storage and an increase of produced
methane. Results show that the addition of fibers and a lower content of proteins
have significantly reduced the amount of ammonia nitrogen accumulated and
volatilized, while the speed of ammonia volatilization rose from 12% to 32% if
compared to high protein diets. So diet composition and its effects on effluent
quantity and characteristics should be considered in a context of optimization of
wastewater treatment, by minimizing ammonia and methane emissions or, in other
situations, by maximizing the uncontrolled methane emissions from sewage.
M€oller et al. (2010) study the amount of produced biogas and greenhouse gas
emissions from dairy cattle manure, produced by different diets. The experimental
tests are carried out in CSTR digesters, with a volume of 7 l and under mesophilic
(35 C) and thermophilic (50 C) conditions. Instead, the experimental batch tests
are conducted without the inoculum at four different temperatures (10, 15,
20, 35 C). They also conduct some tests with the inoculum and under thermophilic
and mesophilic conditions to determine the final methane yield. The cows are fed
with low-fat corn silage, with corn silage and crushed rapeseed or with corn silage
and grass silage (low-fat clover). The amount of biogas produced from sewage is in
the following order: corn + fat > corn > grass. They analyze methane emissions
from untreated liquid manure at a low temperature and under anaerobic conditions,
in which it is possible to observe the bacterial degradation of organic matter.

Thanks to the international IPPC method that is famous for methane emissions
calculation; they find that these are higher at all temperatures with a high-fat diet
and that there are much more benefits in biogas production with this diet if
compared with other diets. Therefore, fats have a positive effect on biogas
production.
Amon et al. (2007) optimize the biogas production in an anaerobic digester from
corn and cattle slurry. In fact, there is a growing demand for biogas production from
these substrates. The highest biogas yield is achieved by sewage deriving from
cattle fed with a well-balanced diet. Methane production is measured for 60 days in
a batch reactor and at a temperature of 38 C. The highest methane yield achieved is
of 166.3 NlCH4 kg VS1. Thirteen different varieties of corn are cultivated: the
methane yield decreases when crops approach ripeness and with late varieties, the
methane yield is between 312 and 365 NlCH4 kg VS1 for milk stage, and it is
between 268 and 286 NlCH4 kg VS1 for complete maturation. Corn silage can
increase the methane yield by 25% if compared with the natural one. Corn silage
yields are of 289 NlCH4 kg VS1, whereas the natural one is 25% lower,
225 NlCH4 kg VS1. During silage, lactic acid, acetic acid, alcohols, formic acid,
H+, and CO2, that are important precursors for methane formation, are produced.
Another reason may be the decomposition of fibers during the ensiling process that
increases the availability of fibers for methanogenesis.
The importance of nutrition in biogas plants is also studied by Piccinini et al.
(2008). They analyze some substrates such as manure, energy crops, and/or agro-
industrial residues. In both cases, it is necessary to consider the specific character-
istics of the used matrix to have a proper operation of the plant. For energy crops,
product uniformity makes the construction more reliable, even if it requires a lesser
complexity of the plant. The addition of agro-industrial residues determines issues
about the supply continuity and quality variability. These problems can be over-
come if the matrix undergoes a silage, or if the main load is energy crops.
The input energy of a digester also influences the energy efficiency of the
process. Anaerobic digesters are a valiant option in wastewater treatment, but the
use of biogas requires the maintenance of a positive life-cycle energy. Many studies
about energy balance are focused on the used raw materials, biogas systems,
different waste management strategies, and possible options for biogas use (P€oschl
et al. 2010).
P€
oschl et al. (2010) evaluate the food impact (single or co-digestion) of different
strategies for downstream waste management and the energy balance of plants. The
input data are obtained from biogas plants, knowledge on the anaerobic digestion
process, and technology management. The energy balance is assessed using the
Primary Energy Input to Output (PEIO) ratio. For single feeding, the Primary
Energy Input to Output (PEIO) ratio varies between 10.5% and 64% depending
on the energy required for the provision of raw materials. The energy balance
becomes negative when the distance for cattle manure transport is greater than
22 km and that for municipal waste is greater than 345 km. The input energy is
strongly influenced by raw materials characteristics. Agricultural wastes, for
316 G. Leonzio
example, in most cases do not require any pretreatment. The energy balance
depends on the biogas yield, the efficiency, and the energy value of fossil fuels
replaced by biogas. As concerns co-digestion with multiple feeding, the PEIO
varies between 45.6–48.6% and 34.1–55% for the small and large scale of biogas
plants. This suggests a greater stability in the co-digestion process. Results suggest
that the energy efficiency can be increased by 5.1–6.1% through the recovery of
biogas emitted from the stored digestate.
The energy and environmental efficiency of biogas plants, according to the
matrix, are analyzed by Bacenetti et al. (2013). They evaluate the energy and
environmental efficiency of three different biogas plants with different electrical
power and different feeding. They observe that sludge allows lower emissions but a
higher consumption of thermal energy for heating. The environmental impact and
energy efficiency are evaluated through LCA analysis, by using the amount of
produced biogas as a functional unit. Results suggest that biogas plants also require
that the anaerobic digestion process reaches the highest methane yield according to
the kind of feeding used and by ensuring the highest peak of produced energy. The
input power also affects the economy of the process. A mathematical model, that is
made to describe the stationary and temporary state of a digester, shows the
existence of a residence time and a quantity of substrate input flux that are able to
maximize methane production in the produced biogas (Balmant et al. 2014).
To keep the anaerobic process for biogas production stable and uniform, it is
necessary to feed it with a certain quantity of substrate with a stable quality or by
varying the quantity to obtain a specific quality. Fed quantities are manually
changed with biogas flow variations. Continuous information on the substrate
quality are not available and analyses on feeding are too much expensive. Jacobi
et al. (2012) evaluate the feasibility of near-infrared spectroscopic (NIRS) for an
online monitoring of the substrate quality to find a way to control biogas produc-
tion. An NIRS sensor is designed, built, and calibrated for continuous monitoring of
dry matter [0.75% fresh matter (FM)], volatile solids (0.74% FM), crude fat
(12.09% FM), crude protein (12.22% FM), crude fiber (1.50% DM), and
nitrogen-free extracts (0.93% FM) of maize silage.
Centralized anaerobic digesters are in general used, in co-digestion processes.
Many farms cooperate to feed a large centralized digestion plant, powered by
different substrates. It is a standard technology used in Europe, Asia, and in the
USA. Thorin et al. (2012) conduct studies to improve biogas production from
co-digesters in the Växtkraft plant in Vasteras. Organic waste coming from civilian
homes and restaurants are mixed with pasture crops and with the process water
which is recirculated and sent to the digester. Solid and liquid wastes are then
co-digested in a digester, with an extension of 4000 m3. Later, the produced biogas
is purified and used for vehicles operations, while plant residues are then used as
fertilizers. They evaluate that the pretreatment of feeding and the use of membranes
for filtering the recirculated water, allow an increase in biogas production up to
30%.
4.1 Inhibition of Microorganisms During The Co-digestion

Method of Anaerobic Digesters
To prevent the inhibition of microorganisms during the co-digestion process, sub-

strates with high biogas potential must be carefully added to avoid the suboptimal
digestion conditions caused by the inhibition of microbial activity.
Nielsen and Angelidaki (2008) report that in biogas plants used in Denmark, for
animal and industrial organic by-products sewage treatment, a high concentration
of ammonia and long-chain fatty acids are due to the inhibition of microorganisms.
This inhibition is indicated by a decrease in the speed of methane production and by
an accumulation of fatty acids in the digester. Some inhibitors and inhibitory
thresholds are reported in the Table 10.3.
The inhibition of microorganisms in the anaerobic digestion process can be
attributed to inadequate knowledge of the organic substance composition, insuffi-
ciency in the knowledge of the characteristics of substrate degradation, inadequate
supervision of the process, especially as regards the VFA concentration, insufficient
substrate storage, by causing an improper mixing and a lower degree of precision in
the substrate dosage (Nielsen and Angelidaki 2008).
Ammonia is a product of biological degradation of organic substances with a
nitrogen content, mainly in the form of proteins and urea (Kayhanian 1994).
Ammonia is essential for microbial growth, but if it is present in a high concentra-
tion in the substrate, it can cause the inhibition of the digestion process. The
inhibition threshold is reported in the table, and it is a combination of free ammonia
nitrogen and ionized ammonia nitrogen (Kayhanian 1994).
Angelidaki and Ahring (1993) observe the performance of a digester treating
cattle manure under thermophilic conditions when the concentration of free ammo-
nia exceeds 7 g l1. Whittmann et al. (1995) propose a change in the pH
intercellular value, an increase in the required energy demand, and the inhibition
of the specific enzymatic reaction as a mechanism of ammonia inhibition. The
ammonia inhibition experiments using urea as a source of ammonia are conducted
with five different TAN values and with some digesters maintained at 50 C for a
Table 10.3 Inhibitors and inhibition threshold in the AD process

No Inhibitors Inhibition threshold
1 Ammonia TAN 2.5 g l1 both mesophilic and thermophilic of AD processing cattle
manure that not previously acclimated to high ammonia concentration; 4 g l1
to previously acclimated with high ammonia concentration (Hashimoto 1989)
Increasing FA: 0.55–0.65 g l1 in thermophilic of AD causes decreasing
methane yield by 25% of digester processing cattle manure (Angelidaki and
Ahring 1993)
2 LCFAs Oleic acid and lauric acid IC50 ¼ 4.3 mM (Chen et al. 2008)
3 Sulfide 100–800 mg l1 as dissolved sulfide or approximately 50–430 mg l1 as
undissociated H2S (Parkin et al. 1990)
C/SO42 ¼ 1.6 corresponding to 1400 mg SO42 l1 (Siles et al. 2010)
318 G. Leonzio
residence time of 4 h. They find a negative correlation between the methane yield
obtained from cow manure and that with a concentration of TAN and VFA.
Methane yields with a TAN of 2.93 g l1 and an FA of 0.71 g l1 are less than
23.6% if compared to those with TAN values of 2.15 g l1 and FA of 0.48 g l1.
Isobutyric and isovaleric acid are accumulated during the experiments so that they
are indicators of ammonia inhibition.
Nakakubo et al. (2008) suggest that isobutyric, butyric, and isovaleric acid can
be used as indicators of ammonia inhibition. After a period of ammonia inhibition,
butyric and valeric acid gradually decrease and they suggest a conversion into
isobutyric acid and then in propionic acid (Nielsen and Ahring 2007).
In the case of ammonia inhibition, VFA concentration, isobutyric acid,
isovaleric acid, TAN values, and biogas production can be used as process indica-
tors. Kayhainan (1994) suggest that to prevent ammonia inhibition the C/N value of
the substrate must be kept between 22 and 35 and that the pH value inside the
digester must be controlled. Chen et al. (2008) propose a method to obstruct
ammonia inhibition by increasing the residence time of biomass in the digester,
by switching off the stirrer half an hour before the addition of the substrate and by
immobilizing microorganisms with inert material (clay, activated carbon, zeolite).
Slurry acidification with sulfuric acid can help to reduce ammonia emissions.
Kai et al. (2008) find that this method can help to reduce ammonia emissions by
70% for PS. However, a high acid concentration may cause the inhibition of
microorganisms in the anaerobic digestion process. The presence of sulfates in
the acidified manure may help the growth of the sulfate-reducing bacteria (SRB)
which compete with metanogeneci bacteria.
The ultimate methane yield of acidified cow manure is significantly less than
45%, compared to not acidified manure. Batch digestion that both raw and liquid-
manure acidified fraction shows sulfide inhibition, but this does not happen while
evaluating the solid fraction of acidified slurry. However, methane production from
a solid fraction of the slurry is greater than the not acidified one, whereby the
acidified solid fraction can be used for co-digestion to increase the methane yield
(Sutaryo et al. 2012). So co-digestion of cow manure with the solid fraction appears
a promising method to increase methane production. They show that there is not
any negative effect in the acidification process of the solid fraction of cattle manure
on the methane yield, but there is sulfide inhibition of the anaerobic digestion of
acidified manure. To avoid this, some substrates with high biogas potential must be
added carefully to prevent the suboptimal conditions of digestion that cause the
inhibition of microorganisms.
Siles et al. (2010) evaluate sulfate inhibition using continuous flow reactors that
process Na2SO4-fed glucose and they find that the inhibition ratio C/SO42 is 1.6,
which corresponds to 1400 mg l1SO42.
Moset et al. (2012) find a reduction in 18% of methane in an anaerobic digester,
starting from a substrate that consists of 20% of acidified PS and in 80% of not
acidified slurry. However, the concentration of sulfates in the substrate is of
730 mg l1.
Chen et al. (2008) propose a method to prevent and to reduce sulfide inhibition
by including the substrate dilution and by reducing the concentration of sulfide in
the substrate by means of stripping, coagulation, oxidation, precipitation, and
partial oxidation.
The solid fraction of manure has a high potential in methane production per unit
fresh weight, so it may be used as co-substrate for anaerobic digestion (Hjorth et al.
2010).
Sutaryo et al. (2012) assess co-digestion of not acidified cattle manure with its
acidified solid fraction. They use three different concentrations of acidified solid
fraction, that are equal to 10%, 20%, and 30%, in a thermophilic digester at a
temperature of 50 C. The acidified solid fraction of cow manure is obtained from a
Danish farm, by using an acidification technology developed by InFarm A/S,
Aalborg, Denmark. Solid-liquid manure separation is performed using the screw-
press solid-liquid separation method with 0.5 mm screen size. They find that
methane production per VS substrate gram decreases significantly as the concen-
tration of the solid fraction in acidified cow manure increases. This phenomenon
can be explained by the fact that the solid fraction of acidified cow manure is a
recalcitrant part of animal sewage with a lower biodegradability. This result is in
line with the reduction of the VS concentration as the solid fraction concentration of
acidified cow manure increases. However, methane production from a power
supply with 30% of acidified solids is about 50% greater than the base case
model. Furthermore, digestate has a residual methane potential that is three times
higher. So post-digestion of acidified digestate with a high concentration of solids is
necessary to prevent methane emissions from digestate.
Co-digestion of acidified solids also allows having a stable methane production
and a low concentration of VFA. Rasi et al. (2011) report that the H2S concentration
in biogas plants for common boilers and internal combustion engines should be
smaller and it does not exceed 1000 ppm.
Sutaryo et al. (2012) determine the methane production from different acidified
slurry fractions that are produced by different solid-liquid separation methods. The
experiments are conducted in batch digesters under mesophilic conditions and for
an incubation period of 90 days. The different substrates used in the experiments
are: a fraction of acidified sow slurry that is subjected to separation by a screw press
with four different screen sizes and two different dishes voltages, a fraction of
acidified PS that is subjected to drum/rotating screen, and acidified cow manure not
subjected to the separation process that is filtered press. The results show that the
ultimate methane yield of the solid fraction of acidified PS increases significantly
with a bigger screen size in screw press manure separation. The ultimate methane
yield from the solid fraction of acidified PS through a separation process with the
drum is higher compared to the solid fraction of acidified cow slurry, obtained from
the screw press separation method. This is due to the different substrate
composition.
320 G. Leonzio
4.2 C/N Parameter for Co-digestion Processes of Anaerobic

Digesters
The C/N parameter is important in the optimization of an anaerobic digester diet.

Zeshan et al. (2012) evaluate the effects of the C/N ratio and the associated
ammonia, in an anaerobic digester operating under thermophilic conditions. This
parameter has a certain influence on the global methane yield (Guendouz et al.
2010). The ammonia nitrogen concentration prevents the reduction of biomass
activities and avoids the inhibition of the anaerobic digestion process. In particular,
ammonia nitrogen has a much more significant inhibitory effect on methane genesis
that ionizes ammonium ion. This causes a considerable drop of pH and ammonia
production.
Li et al. (2013) report that the optimal C/N values are in the range 20–30: higher
values release a lower concentration of ammonia nitrogen in the digester. Different
amounts of organic loading rate (OLRs) and recirculated digestate are set to
improve the biogas recovery and to overcome the problem of ammonia nitrogen
accumulation within the system (Table 10.4).
Wang et al. (2012) evaluate the possibility of improving methane yield from an
anaerobic digester that is fed with a mixture of dairy slurry (DM), poultry manure
(CM), and wheat straw (WS) optimized according to the C/N ratio. They show that
as the C/N ratio increases, methane potential increases. Values equal to 25:1 and
30:1 allows to have the best digester performance with a stable pH and low
concentrations of total ammonia nitrogen. The maximum methane potential is
achieved with DM/CM equal to 40.3:59.7 and a C/N of 27.2:1, obtained through
the optimization of response surface methodology.
Table 10.4 Factors that influence the thermophile digestion

Factors Causes Effects
C/N Low C/N Accumulation of TAN and VFA
High C/N Rapid consumption of nitrogen by methanogens
and low gas production
Total ammonia With 30% TS fed Inhibition at 1200 mg TAN/l
nitrogen With 18% TS feed Inhibition at 3500 mg TAN/l
With 7% TS feed Inhibition at 4000–5000 mg TAN/l
With 20% TS feed No TAN inhibition, TAN: 2300 mg/l
17% loss in methane yield
Solid content Increase from 20% to 14.4% decrease in organic removal
30% of TS
Inoculation and Less inoculums Needs high retention time
retention time High inoculum Need less retention time, accelerated start-up
High gas production rate
Temperature and High temperature Free ammonia inhibition
retention time Needs low retention time
TAN Total ammonia-N, VFA Volatile fatty acid
Ye et al. (2013) study the optimal feeding for biogas production that consists of
rice straw, manure, and kitchen wastewater. They use batch digesters in series,
under mesophilic conditions. The optimal ratio, which is found for kitchen waste,
manure, and rice straw, is 0.4:1.6:1 with a C/N ratio equal to 21.7. The methane
yield of 674.4 l/kg VS is higher than the value equal to 71.67% and 10.41%
obtained from digestion of rice straw and PS.
5 Pretreatments of the Biomass to Produce Biogas

in Anaerobic Digesters
Different biomasses are used in the anaerobic digesters to produce biogas.

Low cost and low-value substrates that can be used in biogas plants in a
sustainable way are the agricultural by-products such as slurry, straw, and energy
crops. Unfortunately, these organic materials have a low biodegradability, so that
their treatment is not cheap (Møller et al. 2007). A common way to solve this
problem is to do a pretreatment to the substrate.
Currently, there are several pretreatments: mechanical, physical, thermal, chem-
ical (alkali, acid, oxidative), and organic or a combination of them (Hendriks and
Zeeman 2009).
An effective pretreatment may increase the area, by improving substrate acces-
sibility to enzymes, or may minimize the loss of substrate and the formation of
inhibitors.
For this reason, pretreatments make the organic substance of smaller size: it is
more accessible to microorganisms and methane production is increased. Speed and
degradation degree increase after size reduction especially for substrates with a
high fibers content (Palmowski and Müller 2003). In fact, there are several factors
that contribute to limit the enzymatic hydrolysis of biomass, like crystallinity, the
degree of polymerization of cellulose, the presence of lignin, the cellulose protec-
tion from hemicellulose, and fiber strength (Mosier et al. 2005).
Pretreatment with lime is most promising because the levels of inhibitors
(furfural, methyl furfural, and hydroxy soluble phenolic compounds) released
during or after alkali pretreatment are low and the pH value is increased, by
obstructing acid production in the reactor. Furthermore, this pretreatment dissolves
lignin and removes about 33% and almost 100% of acetal groups. In addition, lime
has reduced costs and a greater safety compared to other chemical compounds
(Wyman et al. 2005).
In the literature, there are several examples of the positive effect of pretreatment
on biogas production: the biogas yields of some substrates increase linearly with the
increase of the surface area (Jedrczak and Krolik 2007). However, the fiber size
cannot be directly correlated to the increase of biogas yield because there can be
many shearing effects from treatment which cannot be measured only by the fiber
size. Palmowski and Müller (2003) study the connection between the surface area
322 G. Leonzio
and the biogas yield through a kinetic model and they find a good relation between
the model and the experimental data.
Alkaline pretreatments are used too. Alkaline pretreatment of wheat plant (WP),
which includes grain and straw, is investigated under different conditions to ensure
bio-methane production under mesophilic condition (López-Jiménez et al. 2015).
Alkaline pretreatments are carried out using 8% of NaOH weight solution at
different temperatures (0, 25, 50, 75, and 100 C). The best performances are
reached by a pretreatment at 75 C for 60 min, giving a methane yield of 404 g ml1
VS. Cumulative methane yield for pretreated WP at 25, 50, and 75 C increases the
methane yield of about 47.5%, 40.8%, and 54.5%. These values are greater than
those obtained from untreated WP, whereas pretreatments at 0 and 100 C do not
guarantee an improvement in biogas production. Qualitative analysis obtained from
WP pretreatment, by using the Scanning Electron Microscopy and the Fourier
Transform Infrared show crystallinity reduction and surface layers of lignin and
hemicellulose removal (Taherdanak and Zilouei 2014). Alkaline pretreatments are
an effective method that can solubilize and also neutralize acids released by various
lignocellulosic complexes (Hendriks and Zeeman 2009; Chen et al. 2012). How-
ever, the presence of small amounts of alkaline residues that remain in treated solids
may be useful for preventing pH reduction during the subsequent phase of
acidogenesis. For these reasons, alkaline pretreatment is much more effective and
compatible when compared with other pretreatments, including the
thermochemical ones.
Dererie et al. (2011) conduct some experimental tests for methane batch fer-
mentation (at a mesophilic temperature of 37 C) with a rice straw substrate. A 3%
of NaOH solution as pretreatment is given to ground rice straw biomass for 120 h at
37 C, while hydrothermal pretreatment is given for 10 min at 200 C. It is observed
that the addition of NaOH is a mandatory requirement to keep a suitable range of
pH and for starting biogas production from pretreated rice straw slurry with the
hydrothermal method. The concentration of the substrate during feeding are
maintained at 5% TS (50 g TS/l). The study shows that 140.0 l/kg VSa biogas
and 59.8 l/kg VSa methane are obtained from untreated rice straw substrate.
However, substrate pretreatment with NaOH solutions results into 184.8 l/kg VSa
biogas and 74.1 l/kg VSa methane. Hydrothermal pretreatment followed by the
addition of 5% NaOH results into highest biogas and methane production yields as
315.9 l/kg VSa and 132.7 l/kg VSa. The pretreated substrate with NaOH shows an
increase of 132.0% in biogas production and 123.9% in methane production
relative to the untreated substrate. However, the hydrothermally pretreated sub-
strate results into an increase of 225.6% in biogas production and 222.0% in
methane production compared to untreated rice straw substrate.
Thermo alkaline pretreatments are usually conducted at temperatures between
100 and 150 C with a load of lime of about 0.1 Ca(OH)2 (Chang et al. 2011).
Gonzales et al. (2013) evaluate a thermos-alkaline pretreatment at 100 C to
ensure anaerobic digestion of press mud in terms of increased methane yield. The
effects of lime are evaluated on COD solubilization and on volatile fatty acids
production in different experimental conditions. BMP measurements are carried out
to evaluate the effect of alkaline pretreatment on methane yield during digestion of

press mud. The measurements are conducted in batch assay under mesophilic
conditions (37 1) according to VDI 4630 standards (2006).
A type of pretreatment that is available and that can be installed for large-scale
plants is mechanical pretreatment, which includes: milling, grinding, crushing, and
chopping.
Methane production from substrates such as food waste, sisal fibers, sludge from
wastewater treatment plants, paper, or tomatoes increased by 28%, 23%, 7%, 60%,
and 100%, after mechanical pretreatment. (Kouichi et al. 2010). Although the
positive effect of biogas production after the use of this pretreatment is evident, it
is necessary to determine whether the increase in the quantity of gas compensates
for the larger amount of input required energy.
Maibritt et al. (2011) study the use of an extruder to increase the methane yield in
produced biogas. They analyze five different types of agricultural biomasses. The
samples are analyzed at different temperatures, maximum particle sizes, biogas
potentials, and energy consumption. The extruder treatment increases biomass
temperature from 5 to 35 C. Furthermore, extrusion accelerates the organic
compounds degradation slowly and some organic compounds, that are not other-
wise degradable, are degraded. The methane yield increased significantly from 18%
to 70% after 28 days, and from 9% to 28% after 90 days. The additional electrical
energy for the increased methane production is of 6–68%. After 90 days, the
extrusion process of the analyzed biomass has an energy efficiency that is classified
as follows: grass ¼ straw ¼ flocculated solid manure < solids pressure screw
manure < littiera.
Two types of mechanical pretreatment, as Grubben deflaker (Gd) and a Krima
disperser (Kd), are tested on a large-scale plant to evaluate their effect on particle
size, methane potential, energy balance, and capacity. The results after 115 days of
incubation in a batch reactor show that methane production is increased by 59% and
43%, after the grinding with Gd and Kd. In both pretreatments, 90% of the ley crop
grow as particle sizes lower than 2 mm and more than 50% of the sample is reduced
to particles that are smaller than 0.125 mm. The energy balance is positive for Gd
and around the break-even point for Kd. Some analysis of the setup shows that Kd
has a capacity that is almost twice than Gd capacity (Lindmark et al. 2012).
Usually, a chemical pretreatment with a Fenton reactor, for a nonselective
degradation process of organic compounds is used (Karina et al. 2012). The greater
effectiveness of this method depends on the formation and release of OH radicals
generated during H2O2 degradation, in the presence of Fe2+ ions. The Fenton
processes advantages are availability, simplicity, and low cost (Deng 2007;
Torrades et al. 2008).
This process is studied by Karina et al. (2012) on Miscanthus giganteus biomass,
Sida Hermaphrodite, and Sorghum Moensch for two hours and under optimal
conditions (pH ¼ 3, the mass ratio [Fe2+]:[H2O2] equal to 1:25 for Miscanthus
and Sorghum and 1:15 for Sida). The delignification degrees are 30.3%, 62.3%, and
48.1% for these three species. The lignification levels are low due to the chemical
pretreatment and both cellulosic structure and hemicellulose are destroyed by
324 G. Leonzio
enzymes. Results show that this method has low ability to degrade cellulose which
results in a low glucose content. The volatile fatty acids concentration after
chemical pretreatment is high enough so that biogas has a high methane content
(from Sorghum Moensch biomass it is possible to have biogas with a methane
concentration of 75%). To have a high biogas concentration, there is no need for
Fe3+ ions coagulation. Some studies show that the produced biogas is characterized
by a higher energy level when Fenton process does not have a coagulation stage.
The oat straw is enriched with saccharine through enzymes and fermented to
ethanol by thermochemical pretreatments and after its removal, the remaining
material is subject to biogas digestion. A detailed calculation of the material
balance shows that for steam explosion pretreatment, the combination of ethanol
fermentation and biogas digestion converts the 85–87% of the higher heating value
(HHV) of holocellulose (cellulose and hemicellulose) in the oat straw and into
biofuel energy. The energy yields of ethanol and produced methane are of
9.5–9.8 MJ/(kg dry oat straw), which is 28–34% greater than the direct digestion
of biogas, which shows a yield of 7.3–7.4 MJ/(kg dry oat straw). The speed of
biogas formation from residues fermentation is even higher than that obtained from
the corresponding, but not fermented pretreatment; this means that biogas digestion
can be terminated only after 24 days and ethanol process acts as an additional
pretreatment for the biological process.
Biogas production can be increased through biomass pretreatment with micro-
wave irradiation, as studied by Zehra (2013), where electromagnetic energy is
converted into heat energy. The advantage is that microwaves penetrate biomass,
deposit energy, and generate heat through the treated material. Barley, corn, wheat,
and straw from agriculture in Norway are considered as biomass. These are divided
into two groups: the first contains minced straw while the second wet straw with
deionized water. Both are subjected to irradiation with microwaves at a temperature
between 200 and 300 C. A group of 66 batch digesters is tested under mesophilic
conditions for 60 days. Preliminary results show that the use of microwaves has no
effect on biogas production. An increase of the process temperature of 300 C leads
to a lower biogas production. The specific methane yield is not improved by
irradiation with microwaves and the author finds an inverse relationship between
thermochemical conversion efficiency and cumulative biogas production.
Pilli et al. (2011) evaluate the benefits obtained by pretreatment of sludge with
ultrasound, the effect of sonic parameters, the impact of the characteristics of mud
on its disintegration, and consequently the increase of the biogas production in the
anaerobic digester. The comparison between ultrasound and other pretreatments is
necessary to evaluate the best pretreatment of sludge from both the environmental
and economic point of view.
Braguglia et al. (2011) study how to maximize the biological digestion of sludge
to clarify the feasibility of a new treatment to recover good quality mud for
agricultural use. The combined effect of organic loading rates (from 0.7 to
2.8 g VS l1 d1) and of the degree of dehydration by anaerobic digestion of sludge
subjected to ultrasonic pretreatment are evaluated together with the thermal and
energy balance. Despite the use of low sonic parameters, the performances of mud
digestion improved in terms of solids degradation and biogas production which

depends on the organic load of soluble compounds. Biogas production from sludge
pretreated by ultrasound is higher (over 30%) compared to the basic case. The
improved filterability during digestion of sludge that is subjected to ultrasonic
pretreatment at an average value of OLR due to a significant purpose dejection.
Heat balances indicate that ultrasound could be a system to ensure the sustainability
of mesophilic digesters. However, thickening is a prerequisite to achieving a
positive energy balance.
Preliminary studies on the substrate for biogas production show that different
types of pretreatments make the matter much more accessible to biological degra-
dation after the breakdown of complex structures of organic materials, thereby their
potential for biogas production is increased.
The biological degradation of sludge by means of ultrasound is extensively
studied in full-scale laboratory experiments (Pilli et al. 2011). Kim et al. (2003)
observe that the use of ultrasound allows increasing methane production by 34%.
Ultrasound is an emerging method and an effective mechanical pretreatment to
ensure the biodegradability of sludge, and it could be useful in sewage and sludge
treatment plants. Ultrasound increases sludge digestibility through the destruction
of its physical, chemical, and biological properties. The degree of destruction
depends on sonic parameters and on the characteristics of mud: the optimal
evaluation of the parameters varies according to the type of sonic parameter used
and the type of mud. Results show that ultrasound usage increases biogas produc-
tion by 50% and some assessments on the energy balance show that the average
ratio of the net gain of electric energy consumed by the ultrasound device is 2.5.
Pretreatments are ozonation and sonolysis. During ozonation, ozone decom-
poses and the radicals react with organic matter by making it soluble and reducing
it in size: this makes it more biodegradable. Therefore, the final amount of mud and
the digestion time can be reduced while the biogas production increases (Bougrier
et al. 2006). The rate of digestion is increased by a factor equal to 2.2 by suggesting
the possibility to have smaller residence time. Remarkable results in sludge solu-
bilization are reported by Salsabil et al. (2010). Chu et al. (2008) find that ozone
allows having an efficiency in solubilization between 25% and 40%. While ozon-
ation and sonolysis are widely studied as pretreatment processes in anaerobic
digesters, their use for an organic fraction of municipal solid waste (OFMSW) is
not yet developed.
Cesaro and Belgiorno (2013) use sonolysis and ozonation to improve the
biodegradability of OFMSW in anaerobic digesters to ensure a greater biogas
production. The results show that both pretreatments may enhance the solubiliza-
tion of organic solid waste. However, during ozonation experiments, no correlation
is observed between increased solubilization and biogas production: the application
of higher ozone doses led to the formation of by-products less biodegradable than
untreated substrate. This evidence makes the ultrasound process more efficient than
ozonation and addresses further studies for sonolysis optimization.
The structure and physical properties of zeolite make it ideal for the use in
biological purification wastewater (Park et al. 2010). Therefore, the use of zeolite in
326 G. Leonzio
wastewater treatment is increased significantly in the past decade. The supports of

zeolites ensure that the anaerobic digester contains a high level of biomass and that
it can operate with a hydraulic retention time significantly reduced. Zeolites are
used as supports to immobilize microorganisms in different reactors (fixed bed,
fluidized bed, etc.) and consequently as ion exchangers for the removal of ammonia
in anaerobic digesters for the presence of Na+, Ca2+, and Mg2+ on its crystal
structure. These properties make them useful in improving the performance of
anaerobic digestion processes treating high nitrogen content wastewater, such as
cattle and chicken wastes. At the same time, zeolites show a great capacity for the
absorption of toxic metals that can inhibit the microorganisms responsible for
anaerobic digestion.
Montalvo et al. (2012) conduct a review on the use of zeolites in anaerobic
digestion processes evaluating the influence of size on mesophilic and thermophilic
digesters. They also consider the role of zeolites in granulation and anaerobic
oxidation processes and in sequential reactors such as hybrid moving bed biofilm
reactors.
For biological pretreatments, the breakage of organic compounds into simple
organic structures takes place through the action of enzymes that are produced by
microorganisms inside the digester. In the case of lignocellulosic materials, the
biodegradation process is facilitated by cellulose and hemicellulose (Parawira
2012). Three experiments are conducted:
• Thermophilic digester at 50 C: a mixture of enzymes is added to dairy cattle
manure and it is fed into the digester, both in the presence and absence of an
enzymatic pretreatment.
• Mesophilic digester at 35 C: a mixture of enzymes is added to dairy cattle
manure and it is fed into the digester, both in the presence and absence of an
enzymatic pretreatment.
• The mixture of enzymes is added to the solid fraction followed by a step of
incubation at 35 C for 20 h before being combined with the liquid fraction and
then it is fed into the thermophilic digester. A mixture of the inactive enzyme is
added for the control of the digester at 121 C and for 30 min.
They find that the addition of enzymes to cow manure does not produce any
significant effect on methane production in both mesophilic and thermophilic
digesters. This is attributed to microorganisms in the digester degrading the ME
since the substrate is fed into the digester immediately after mix with ME, and
extracellular enzymes produced by microorganisms already present in the digester
that are sufficient to facilitate the hydrolysis of the organic compounds in DCM
(Romano et al. 2009). The addition of microorganism mixture followed by an
incubation period at 50 C for 3 days has a significant effect on increasing the
methane yield. The addition of the enzyme mixture to solid fraction followed by an
incubation period at 35 C for 20 has a positive effect on methane yield produced by
a substrate mixture (30% liquid fraction of cow manure and 70% solid fraction of
cow manure treated with enzymes). However, compared to the previous case, there
are further costs for the application of enzymes and therefore it represents a limiting
factor for large-scale biogas plants.
Zieminski et al. (2012) use an enzymatic pretreatment on sugar beet pulp and
spent hops for their high fiber content. A 24-hour hydrolysis time with a mix of
enzymatic preparations Celustar XL and Agropect pomace (3:1, v/v) with
endoglucanase, xylanase, and pectinase activities prove to be the most efficient.
The highest biogas yields are obtained from the enzymatic hydrolysis of sugar beet
pulp (183.39 ml/d from 1 g COD at fermenter loading with organic matter of 5.43
gCOD/l-d). Methane fermentation of spent hops hydrolysate has a yield equal to
121.47 ml/d biogas from 1 g COD. These results show that enzymatic pretreatment
improves biogas production.
Hydrothermal pretreatment provides an accelerated pre-hydrolysis of biomass
that results in higher biogas and methane production yields. Energy analysis of the
complete conversion of biomass into biogas process (impregnation; steam explo-
sion; enzymatic hydrolysis; two-step anaerobic fermentation) is performed with an
optimization of the thermochemical and biological process by Santarelli et al.
(2012). The analyses are carried out on a pilot plant. They analyze the biogas-to-
electricity phase, considering two different types of CHP and SOFC. The results
show that the integration of the conversion process from biomass to electricity
allows a positive electrical balance, but there is a deficit in heat balance. Finally, the
comparisons show that the best performance is obtained from an integrated SOFT
plant.
Thermal pretreatments have a positive effect on energy balance (Hendriks and
Zeeman 2009). The substrates are heated and the composition of hemicellulose and
the branching groups determine the effectiveness of the treatment (Hendriks and
Zeeman 2009).
High-temperature thermal pretreatments in the range of 100–225 C at 25 C
intervals for 15 min are performed by evaluating the biochemical methane potential
(BMP) of cattle manure, dewatered manure, and chicken manure. Such
pretreatment on cow manure to 175 and 200 C for 15 min provides a significant
increase in methane production after an incubation period of 90 days. In the 27th
day, the improvements in methane production are 13% and 21% at 175 C and
200 C. For PS, methane production is increased at all temperatures between
125 and 200 C with the greatest increase of 29% at 200 C after 27 days.
A significant methane production of pretreated samples compared to not
pretreated ones, in cattle manure, and in dehydrated, shedding indicates a change
in the lignocellulosic structure of substrate by giving easier access to microbial
enzymes (Bruni et al. 2010).
There is no positive effect of high-temperature thermal pretreatment on methane
production from chicken manure. Even at 225 C thermal pretreatment led to
reducing methane by 18% compared to the basic case. The lack of a positive effect
could cause an increase in the biodegradability of chicken manure, since there is no
bedding material in the sample, thus providing limited potential for improving the
methane production in the pretreated sample (Raju 2012).
328 G. Leonzio
Sutaryo et al. (2012) evaluate the effect of low-temperature pretreatments on the

methane yield from PS and the solid fraction of PS in batch digesters. The use of
such pretreatment is an interesting method since the required energy can be used by
the surplus obtained from the cogeneration system.
Low-temperature thermal pretreatments are conducted from PS by Møller et al.
(2004). In particular, four different treatments are conducted (from 65 to 80 C with
intervals of 5 C) for 20 h and are applied to both raw and solid fraction manure.
They find that such pretreatments provide a slight increase in pH and a large
increase in VFA total concentration. Acetic acid and butyric acid in pretreated PS
at 65 C increase by 65% and 63%. For solid fraction of slurry, an increase of 63%
and for acetic acid and butyric acid an increase of 126% are recorded, compared to
non-pretreated specimens at a temperature of 80 C. The pH increase is due to the
solubilization of macromolecules (Carrère et al. 2010) or to the formation of some
substances such as ammonia nitrogen, whereas an increase in VFA concentration
can be determined by auto-hydrolysis (Bonmati et al. 2013). There is a significant
increase in methane production from PS within a range of 9.5% and 26.4% for
11 days of incubation. So low-temperature thermal pretreatments may increase the
reaction rate, but it has a little effect on the overall yield with an infinite residence
time, as represented by Bo parameter. The use of low-temperature thermal pre-
treatments provides a significant increase in methane production for a solid fraction
of the slurry. This happens in a linear fashion with pretreatment temperature.
Energy balances show that high- and low-temperature thermal pretreatment is a
useful method to increase methane production from liquid manure only when there
is thermal energy available that can be used in the thermal pretreatment processes.
In low-temperature thermal pretreatment, excess heat can be used by the cogene-
ration plant (Menardo et al. 2011).
6 Configuration of Anaerobic Digesters to Produce Biogas

from Different Biomasses
Biogas production efficiency can be optimized by the use of two cascade digesters
connected in series by using methane genesis microorganisms. Athanasoulia et al.
(2012) consider residence times included between 12.3 and 19.7 days for both
systems. For these two reactors that are in series, biogas production increases while
the volatile suspended solids concentration decreases. Biogas production is
increased from 9.5% to 40.1%; the biogas selectivity is estimated to be 0.49
0.06 m3 biogas/kg TVSdegradato for the reactor in series and 0.44 0.02 m3
biogas/kg TVSdegradato for the reactor at a single stage. As regards volatile
suspended solids reduction, values between 31.5% and 33.8% for a single digester
and values between 36.2% and 40.7% for a digester in series are obtained.
Ge et al. (2010) study two mesophilic digesters in series with a working volume
of 4.6 l, treating primary sludge with a residence time of 2 and 14 days. The system
allows a volatile solids reduction of 44%, this is a lower value than that of 54%,
which is reached under thermophilic-mesophilic conditions. The effects of resi-
dence time on the biogas yield and on volatile fatty acids concentration are
examined.
Kaparaju et al. (2009) evaluate the possibility of optimizing biogas production
from sewage through two methanogenesis CSTR digesters in series. They also
estimate a single digester which operates at 55 C with a residence time of 15 days
and a working volume of 5 l. For the digesters in series, the working volume is
distributed as 70/30%, 50/50%, 30/70%, and 13/78% between the methanogenesis
digesters in series. The reactors in series can increase the biogas production, and the
best results are obtained when the working volume is distributed as 70/30% and
50/50%; it is possible to have a biogas production that is 13–17.8% higher, a lesser
volatile fatty acids content, and a minor loss of methane compared to a single CSTR
digester. They estimate an increase in biogas production when the working volume
is distributed as 30/70%, but the process is unstable. With a working volume
distributed as 13/78%, differences in biogas production are not present and a
lower methane production, compared to a single digester is present. Some exper-
iments on laboratory scale show that with a distribution of working volume as
77/23%, biogas production can be increased by 1.9–6.1%, if compared to a single
digester. The temperature between the methane genesis reactors must be similar.
However, the highest biogas production must be economically evaluated together
with the extra installation costs and the complexity of the process.
Ramakrishnan and Surampalli (2013) study the configuration of a hybrid anaer-
obic reactor that uses supports for biomass immobilization and biogas recycling to
improve mixing. The reactor consists of sludge bed in the lower part and an
anaerobic filter in the upper part and is fed with wastewater containing complex
phenols. Four different biogas flow rates of 25.11, 16.87, 25.30, and 37.95 l1 are
recirculated for 100 days. Biogas recirculation ensures the residence time for solids
and biomass. The removal of COD and phenols improves with the increase in
biogas recirculation. With a residence time of 0.33 days, a removal of phenols and
COD of 95% and 92% are obtained.
Lee et al. (2013) use in three experimental studies a biogas with a methane
concentration of 73% produced at the Taiwan Sugar Swine Farm in Taichun. In the
first study, they investigate the effect of biogas flow rate on the performance of
generator at different excesses air. Then, the results of this study are compared to
the results obtained from studies on biogas with a methane concentration of 60%.
Finally, for biogas with a methane concentration of 73%, the effect on the perfor-
mance of the generator with a preheated gas input (using a waste heat recovery
system) at different temperatures is evaluated. Power generation increases with
increasing methane concentration in biogas, except when excess air is less than
0.85. However, thermal efficiency increases with increasing methane concentration
only when excess air is greater than 0.95. The best performance of the generator,
obtained by preheating the inlet gas, are evident when excess air is relatively high,
for example, 1.3.
330 G. Leonzio
Jung et al. (2013) develop a process for the conversion of solid organic waste
(food waste and sewage sludge) in H2 and CH4. The first stage is formed by a dark
fermentative hydrogen production (DFHP) without requiring the use of an inocu-
lum. The second stage is constituted by a sequence of anaerobic digesters and batch
reactors (ASBR) and an up-flow anaerobic sludge blanket reactor (UASBr) is used
to treat H2. The system (H2+CH4-ASBR) shows the best performance in terms of
total biogas conversion (78.6%), while a higher biogas flow is obtained with the
system (H2+CH4-UASBr). To reduce the addition of bases in DFHP process, the
produced methane is used for water dilution. Effluents of ASBR and UASBr are
effective to keep pH higher than 6 with no methane production.
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Topics in Mining, Metallurgy and Materials Engineering

Series Editor: Carlos P. Bergmann

Tawfik Abdo Saleh

More information about this series at http://www.springer.com/series/11054

ISSN 2364-3293 ISSN 2364-3307 (electronic)

Library of Congress Control Number: 2017951115

© Springer International Publishing AG 2018

Printed on acid-free paper

This Springer imprint is published by Springer Nature

Dharan, Saudi Arabia Tawfik Abdo Saleh

I would like to acknowledge the support provided by King Fahd University of

9 Role of Nanomaterials as an Emerging Trend Towards the Detection

Tawfik Abdo Saleh and Saddam A. AL-Hammadi

Keywords Crude oil • Nanotechnology • Oil and gas industry • Upstream •

T.A. Saleh (*)

© Springer International Publishing AG 2018 1

Oil and gas industry

Various facilities for

2 Upstream Exploration and Drilling Sectors

2.1 Oil Well Exploration

2.2 Wellheads and Drilling

Various nanotechnology techniques can be implemented to enhance the down-

2.3 Logging While Drilling

3 Upstream Production Sectors and Nanotechnology

3.3 Gas Compression

3.4 Oil and Gas Storage and Export

long pipelines, intermediate compressor stations and pump stations are

3.5 Midstream sectors

The midstream sectors involve

4 Introduction to Downstream Sectors

5 Oil Refinery Process

Fig. 1.2 A simplified block diagram of the refinery processes

5.1 Crude Distillation Unit

5.1.1 Atmospheric Crude Distillation Unit

Classification of Oil Refinery

Physical and thermal processes Chemical processes

Fluid Catalytic Cracking

Fig. 1.3 Classification of oil refinery processes based on their nature

column, called a fractionation column, side stripper columns, a furnace, a desalter,

Crude Distillation Units

Vacuum Crude Distillation Atmospheric Crude Distillation

Main operating conditions:

Fig. 1.5 The atmospheric crude distillation unit (ACDU)

Fig. 1.6 A tray in the

5.1.2 Vacuum Crude Distillation Unit

Vacuum distillation is a separation technique where the pressure is reduced above

5.2 Thermal Cracking Processes

5.2.1 Thermal Cracking Coking Processes

Fig. 1.8 Classification of the thermal cracking process

Delayed Coking Process

Fig. 1.9 A simplified diagram of the delayed coking process

Flexi-coking is an improved version of the conventional fluid coking process,

Fig. 1.10 A simplified flow diagram of the flexi-coking process

5.2.2 Visbreaking Thermal Cracking Process

Fig. 1.11 A flow diagram of the Soaker Visbreaker unit

Fig. 1.12 A flow diagram of the Coil Visbreaker unit

5.3 Fluid Catalytic Cracking Unit

5.3.1 Reaction and Regeneration Process

separated by fractionation and forwarded to either storage or for further treatment.

5.3.2 The Fractionation Process

reactor at a high temperature (on average 300–500 C) and at moderate pressures.

U.J. Etim • P. Bai () • Z. Yan ()