SEMINAR 2016

SEMINAR

ON
“NANOCATALYSTS IN REFINING AND
PETROCHEMICAL PROCESSES”

Prepared By:
Samala Aravind (U13CH047)

Supervisor
Dr. Mausumi Mukhopadhyay

(2016 – 2017)

DEPARTMENT OF CHEMICAL ENGINEERING

S. V. NATIONAL INSTITUTE OF TECHNOLOGY
SURAT – 395 007

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Certificate
This is to certify that Seminar- entitled

“Nanocatalysts in refining and petrochemical processes”

Submitted by
SAMALA ARAVIND(U13CH047)
In partial fulfillment of the requirement for the award of
Bachelor in Chemical Engineering
From Sardar Vallabhbhai National Institute of Technology, Surat
is the record of their own work carried out by them under the
Guidance of Dr. Mausumi Mukhopadhyay (Associate Professor,
Chemical Department, SVNIT)

Dr . Mausumi Mukhopadhyay Dr. Z.V.P Murthy

(Supervisor) Head, Chemical Department.

Seal
Department

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S. V. National Institute of Technology, Surat

(Aravind Samala) registered in Chemical Engineering Department of S.V.N.I.T.

Surat having Roll No. U13CH047 has successfully presented his Seminar on -
06/12/2016. The seminar is presented before the following members of the
Committee.
Signature

1) Examiner-1 Dr. Mausumi Mukhopadhyay

(Associate professor)

2) Examiner-2 Dr. Meghal A. Desai

(Assistant Professor)

The Seminar entitled “NANOCATALYSTS IN REFINING AND

PETROCHEMICAL PROCESSES” is submitted to the Head (CHEMICAL) along
with this certificate.

Place: Surat
Date: 06/12/2016

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ACKNOWLEDGEMENT

I would like to make deepest appreciation and gratitude to Dr. Mausumi

Mukopadhayay for her invaluable guidance, constructive criticism and
encouragement during the course of this project.

Grateful acknowledgement is made to all the staff and faculty members of

Chemical Department, Sardar Vallabhbhai National Institute of Technology,
Surat for their encouragement. We would also like to extend our sincere thanks
to all our fellow graduate students for their time, invaluable suggestions and
help. In spite of numerous citations above, the author accepts full responsibility
for the content that follows.

Name of candidate
Samala Aravind
(U13CH047)

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ABSTRACT

This article sets out to survey the remarkable development that has taken
place in catalysis in the refining and petrochemical industries since the middle
of the 20th century, and more especially since the 1970s, highlighting what
appears to be the most significant progress. It then attempts to outline the
energy and environmental context for the coming decades which will govern
the trend in industrial catalysis in the 21st century. Although the reduction of
CO2 will eventually require the decarbonization of energy carriers, oil will still
remain the principal source of liquid motor fuels for a long time. However, the
share of gas will gradually increase and hydrogen is destined to play an
important part as an energy carrier. The use of biomass will develop, but at a
modest level. Within this framework, catalysis will still play a leading role in
technical and economic development in the 21st century, even though it is far
from being an emerging discipline. While the extensive use of nanocatalysts
refining and fossil fuel processing has already become the pioneering area for
nanotechnologies in the oil and gas industry.

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CONTENTS

I ACKNOWLEDGEMENT
II ABSTRACT
III CONTENTS

Sr. No TOPIC PAGE NO.

1 INRODUCTION 8
1.1 IN SEARCH OF OIL(BACKGROUND)
1.1.1 Fossils
1.1.2 Magnetometer
1.1.3 Gravtimeter
1.1.4 Sesmic Tests
1.2 DEVELOPMENTS IN REFINING AND 9
PETROCHEMICALS
1.3 BENEFITS OF NANOCATALYSTS IN 10
CHEMICAL INDUSTRY

2 LITERATURE REVIEW 13
2.1 PRINCIPLE OF CATALYSIS
2.2 NANOCATALYSTS PREPARATION METHODS
2.3 SYNTHESIS OF ACTIVE NANOCATALYSTS
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3 RESEARCH ACTIVITES ON ACTIVE 19

NANOCATALYSTS

4 NANOCATALYSIS IN PETROLEUM 21
REFINING AND PETROCHEMICAL
INDUSTRIES

4.1 NANOMATERIALS AS CATALYSTS

4.2 PRODUCTION OF PETROCHEMICALS WITH
CATALYSTS(OIL REFINING)
4.2.1 CRACKING
4.2.1.1 Catalytic Cracking
4.2.1.2 Hydro Cracking

5 APPLICATIONS OF NANOCATALYS 24

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CHAPTER 1
INTRODUCTION
1.1 IN SEARCH OF OIL (BACKGROUND)

Oil began to form deep under the earth millions of years ago when plants and animals died and
their skeletons settled at the bottom of seas and lakes. The remains were slowly buried under
layers of sediment and in the course of time became crude oil. The oil usually lies trapped
between domes of solid rock. Often there is a layer of salt water beneath it. In many cases the
richest deposits of oil lie beneath a great amount of rock and can be reached only by expensive
drilling operations. Geologists know which rock strata (layers) oil is most likely to be trapped in.
They start with experimental data of areas likely to be oil-bearing. Then they begin to gather their
evidence.

1.1.1 Fossils
Fossils help to date and identify rocks. Radioisotopes are used to obtain more accurate
measurements of their age.

1.1.2 Magnetometer
A special instrument called a magnetometer trails behind an airplane as it flies at an even height a
long a pattern of flight lines. As different types of rocks are magnetic to different degrees, the
results from the magnetometer give a picture of the magnetic structure and thickness of the rocks
deep underground.

1.1.3 Gravtimeter
The earth’s gravity also changes from place to place. A gravimeter carried across land or
mounted on a ship measures the different gravities of the rocks below dense rocks give a higher
gravity reading.

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1.1.4 Seismic Tests

Then there are seismic tests. These are more exact. They measure the time it takes for shock
waves from controlled explosions to reflect upward from rocks underground. The time it takes

the shock waves to reach an underground layer and return to the surface shows how deep the
layer is. It also gives clues about the type of rock from which the shock waves were reflected.

When all these tests are complete and if they show a good chance of oil being in a certain area, a
test well is driven down into the rock. It is at this point that large amounts of money are needed
to set up the drilling operation. It may cost billions of Rupees to develop a major oilfield before
any oil is gotten out of it. Therefore, the exploration be as thorough as possible before any
drilling starts. These days the computers are used to gather the information from all tests, but the
sure presence of oil is still not known. If there is oil, it probably lies 3000 meters below the
surface.

* Catalysts systematically have been used at least since the beginning of he industrial age.
* In a sense, all catalysis is nanoscale, since it involves chemical reactions at the nanoscale, and
today their use is widespread in industries such as petroleum refining, petrochemicals and other
chemical industries.
* The focus on principle of catalyst, cleaner fuels, and lower cost petrochemicals has driven the
refining and petrochemical industries towards improvement in conventional catalysts and, in
several cases, to the introduction of new nanocatalysts.
* Growth in the worldwide nanocatalysts market is driven by the ever-increasing demand from
polymer manufacturers, refining and petrochemical industries.
* Nanomaterials offer many possibilities as catalysts to meet future demands in catalytic
process technologies in petroleum refining, petrochemical, and synthetic fuels production of the
future.

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1.2 DEVELOPMENTS IN REFINING AND PETROCHEMICALS

Catalysis undoubtedly played a very important part during the second half of the 20th century in
the development of the refining and petrochemical industries. Figure indicates some of the
important dates that marked their history. With the exception of steam cracking, which has
always played a leading role in petrochemicals, the importance of the purely thermal processes
has declined steadily over more than 40 years, in favour of the higher performance catalytic,
processes. Apart from base catalysis, which is not much used, the refining and petrochemical
industries currently use almost all the main categories of catalysts, and the latter are often
indebted to these two industries for their initial applications and the significant progress achieved
over half a century. The main categories of catalysts mostly belong to heterogeneous catalysis,
which involves acid, metal, sulfur, and bifunctional catalysts and, to a lesser degree, oxide
phases (other than supports). Nevertheless, some important applications belong to homogeneous
catalysis, particularly where olefin conversion is concerned. This development in catalysis in
refining and petrochemicals will be briefly examined by main types of processes, starting with
the conventional processes used before 1970.

Figure given below shows some important dates in the development of the refining and
petrochemical industries (Alkyl, alkylation; A8, C8 aromatics; Arom., aromatics; Bifunct.,
bifunctional; CCR, continuous catalyst regeneration; FCC, fluid catalytic cracking; HDC,
hydrocracking; HDS, hydrodesulfurisation; RCC, resid catalytic cracking).

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1.3 BENEFITS OF NANOCATALYSTS IN CHEMICAL INDUSTRY

* Increased selectivity and activity of catalysts by controlling pore size and particle
characteristics

* Replacement of precious metal catalysts by catalysts tailored at the nanoscale and use of base
metals, thus improving chemical reactivity and reducing process costs

* Catalytic membranes by design that can remove unwanted molecules from gases or liquids by
controlling the pore size and membrane characteristics
In view of the numerous potential benefits that can accrue through their use, nanostructured
catalysts have been the subject of considerable research attention in recent times.

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CHAPTER 2
LITERATURE REVIEW

2.1 PRINCIPLE OF CATALYSIS

CATALYSIS
Chemistry is the science of substances and their transformations. Chemistry makes many
wonderful substances from animals and vegetables as well as from crude oil as a raw material.
Some substances occur naturally, but many have to be chemically treated in some way to make
them suitable for our specific needs. . Thousands of substances have been produced that are not
easily found in nature but posses unique and useful properties. The list of chemistry’s good deeds
is practically inexhaustible. Chemistry feeds us, clothes us, shoes us, and gives us the things
without which modern civilized society cannot function. In order to get unique substances, two
or more chemicals must come together and react! After all we’ve all seen images of chemists
cooking things up. May be we’ve even turned up the flame a few times ourselves in the kitchen!
And so we know that in order to speed up chemical reactions, high temperature certainly helps.
If you wish to have an economical and ecofriendly approach towards your chemical
transformations then you should use an appropriate catalyst. Catalysts change the reaction rate of
chemical reactions favourably without undergoing any permanent change themselves.

Any chemical reaction that takes place with the aid of a catalyst is called a catalytic reaction. For
example, heating a mixture of potassium chlorate and manganese dioxide produces oxygen
quicker than heating potassium chlorate on its own. The manganese dioxide acts as a catalyst to
speed up the reaction, and is left unchanged at the end. For this reason, the manganese dioxide
does not appear in the chemical equation that shows the reaction.
A contact catalyst is one that has a large porous surface to which other substances adhere by a
process called adsorption. Atoms or molecules of different substances collect on the surface of
the catalyst. While on the surface they react together and are released in a different form. An
example of such a reaction is the formation of ammonia from nitrogen and hydrogen. The
catalyst used in this example is the iron ore magnetite.
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Catalytic converters are used to clean-up exhaust gases in automobiles. It reduces the toxicity of
emissions from the internal combustion engines. They are fitted in the motor vehicle exhaust
system. A catalytic converter provides an environment for a chemical reaction where in toxic
combustion by-products are converted to less toxic substances. The catalyst itself can be a
precious metal, like platinum, palladium or rhodium. Platinum-rhodium catalysts are used as
“reduction catalysts” and platinum palladium catalysts are used as “oxidizing catalysts”. Zeolites
are micro porous alumino silicate minerals, commonly used as commercial adsorbents. Synthetic
zeolites are widely used as catalysts in the petrochemical industry.

* Many experimental studies on nanocatalysts have focused on correlating catalytic activity with
particle size.
* While particle size is an important consideration, many other factors such as geometry,
composition , oxidation state, and chemical/physical environment can play a role in determining
NP reactivity.
* The exact relationship between these parameters and NP catalytic performance may be system
dependent, and is yet to be laid out for many nanoscale catalysts.
* Catalyst is a substance that increases the rate of a chemical reaction by reducing the required
activation energy, and alter the required reaction temperature.
* Catalyst provide a site for the reactants to be activated and interacted together while leaving the
catalyst surface unchanged after the reaction. Normally catalyst surface must have the high active
energy, right structure, and enough spaces.

NANOTECHNOLOGY

What is Nano?
Nano: a prefix which means 1/1000,000,000
Nanometer = 1/1000,000,000 of a meter = 1/1000,1000 of a millimeter = 1/1000 of a micrometer

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Nanotechnology is the understanding and control of matter at dimensions between approximately

1 and 100 nanometers, where unique phenomena enable novel applications.
Encompassing nanoscale science, engineering, and technology, nanotechnology involves
imaging, measuring, modeling, and manipulating matter at this length scale.

Researchers describe the potential benefits of nanotechnology as:

• Enhanced material properties that provide strength and endurance to increase performance and
reliability in drilling, tubular goods, and rotating parts.
• Design properties to enhance hydro-phobic or hydrophilic behavior.
• Lightweight, rugged materials that reduce weight requirements on offshore platforms, and
more-reliable and more-energy-efficient transportation vessels.
• Nanosensors for improved temperature and pressure ratings in deep wells and hostile
environments.
• New imaging and computational techniques to allow better discovery, sizing, and
characterization of reservoirs.
• Small drill-hole evaluation instruments to reduce drilling costs and to provide greater
environmental sensitivity because of less drill waste.

2.2 NANOCATALYSTS PREPARATION METHODS

HOMOGENEOUS NANOCATALYST PREPARATION METHODS (FOR COLLOIDAL):

In homogeneous catalysis, transition metal nanoparticles in colloidal solutions are used as

catalysts. In this type of catalysis, the colloidal transition metal nanoparticles are finely dispersed
in an organic or aqueous solution, or a solvent mixture.
The colloidal nanoparticle solutions must be stabilized in order to prevent aggregation of the
nanoparticles and also to be good potential recyclable catalysts. Metal colloids are very efficient
catalysts because a large number of atoms are present on the surface of the nanoparticles. The
method that is used in synthesizing transition metal nanoparticles in colloidal solutions is very

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important for catalytic applications. The reduction method employed controls the size and the
shape of the transition metal nanoparticles that are formed, which are very important in catalytic
applications.

The different reduction methods that have been used to synthesize colloidal transition metal
nanoparticles for homogeneous catalysis are summeraized below. Chemical reduction of the
precursor transition metal salt is the most widely used method of synthesizing transition metal
nanocatalysts in colloidal solution. There are four other synthetic methods to prepare colloidal
transition metal nanocatalysts that are not as commonly used

These synthetic methods include

* thermal, photochemical, or sonochemical reduction of the precursor transition metal salts

* ligand reduction and displacement from organometallic precursors

* metal vapor synthesis and

* electrochemical reduction of transition metal precursor salts.

Stabilization of nanoparticles in the solution is necessary in order to prevent agglomeration and
aggregation. For catalytic applications, the choice of stabilizers plays an important role in
determining the reactivity of nanoparticles. The above figure shows a schematic of synthesis of n
Pt-clay nanocatalyst.

A good stabilizer is one that protects the nanoparticles during the catalytic process, but does not
neutralize the surface of nanoparticles resulting in loss of catalytic activity. The choice of a
stabilizer to be used for capping the nanoparticles is usually a balancing act between passivation
of the nanoparticle surface and the fraction of available sites for catalysis, and also affects the
size and shape of the nanoparticles formed.

* Chemical Reduction Method.

Reduction of transition metal salt in solution to form the nanoparticles. precursor transition
metal salts are reduced to form the transition metal nanoparticles.

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* Thermal, Photochemical and Sonchemical Reduction Method.

Decomposition of the precursor organometallic salt to the zerovalent form. Reduced of pressure
metal salt or degradation of an organometallic complex by radiation X-ray or gamma-ray and
also UV-visible radiation by use of xenon or mercury lamp. Reduction of the precursor metal salt
by an acoustic caviation phenomena and growth of colloids in the sonicated liquid medium.

* Ligand Displacement Method.

Displacement of ligand in the prganometallic complex.(e.g. amine ligands are displaced by thiol
ligands)

* Condensation of Metal Vapour Method.

Evaporation of transition metal vapours at reduced pressure and subsequent condensation of
these metals at low temperature with organic vapours. Nanoparticles are formed by the
nucleation and growth when the frozen metal/organic mixtures is warmed to the point of melting.
No precise control on size of the nanoparticles.

* Electrochemical Reduction Method.

Precursor metal ions are reduced at the cathode using anode as the metal source. The metal at
anode is oxidized in presence of a quaternary ammonium salt which acts as both the electrolyte
and the stabilizer.

HETEROGENEOUS NANOCATALYST PEPARATION METHOD

Heterogeneous metal nanocatalyst are prepared by adsorption of nanoparticles onto support

which involves functionlization of support to adsorb nanoparticle on to them.

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2.3 SYNTHESIS OF ACTIVE NANO CATALYSTS

METHODOLOGIES INVESTIGATED:
* Thermal evaporation in vacuum
* Electron-beam lithography and pulsed laser deposition
* Buffer-layer assisted growth
* Chemical vapour deposition
* Gas condensation, ionized cluster beam deposition
* Electrochemical deposition methods
* Sol-Gel or colloidal techniques
* Deposition-preparation and impregnation methods
* Molecular cluster precursors

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CHAPTER 3
RESEARCH ACTIVITIES ON NANOCATALYSTS

Indian catalysis research

Indian catalysis research and development today is geared to serve the needs of the country on
the one hand and the more challenging global requirements on the other. The research is focused,
on innovative solutions to the problems of environmental pollution, safety in industrial practice
and saving the energy requirement in chemical reactions. Catalysis R & D in Indian institutions
now looks forward to the development of competitive catalysts and processes that are required to
meet these challenges.

Indian per capita consumption of petroleum and petrochemical products was increased
considerably during 1970s. Due to this rapid growth most of the laboratories initiated projects on
the development of catalysis for petrochemicals and petroleum refinery processes with an
emphasis on self-sufficiency and indigenization rather than on innovation. Catalysis research is
expanded to cover topics such as synthesis and application of zeolites, molecular sieves, novel
materials and photocatalysis. The globalization has resulted in many partnerships between Indian
and foreign organizations. For example, a large amount of catalysis research carried out in
CSIR’s (Council of Scientific & Industrial Research) laboratories. Mention must be made of
NCL (National Chemical Laboratory, Pune), IIP (Indian Institute of Petroleum, Dehradun) and
IICT (Indian institute of Chemical Technology, Hyderabad) in this regard. These laboratories
have collaborations with multinational R & D Centres. Based on these activities, many catalysts/
processes developed in India are expected to go global in coming years. IPCL (Indian
Petrochemical Ltd), PDIL (Projects & Development India Ltd.), IIT (Indian Institute of
Technology, Mumbai/Kanpur), CFRI (Central Fuel Research Institute, Dhanbad) have also
contributed substantially t the area of catalysts.

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GBHE Research Activities on Nanocatalysts

Factors that are presently believed to play a significant role in the catalytic reactivity of
supported metal clusters:
the structure(size and shape)
* chemical composition
* oxidation state
* inter particle interactions
* reactivity of nanocatalysts.

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CHAPTER 4
NANOCATALYSTS IN REFINING AND PETROCHEMICAL PROCESSES

4.1 NANOMATERIALS AS CATALYSTS

* Objective of Nanocatalysis Research is to produce catalysts with 100% selectivity, extremely
high activity, low energy consumption, and long lifetime.
* The approaches: Precisely controlling the size, shape, spatial disturbution surface composition,
electronic structure, and thermal and chemical stability of the individual nanocomponents.
* Nanoparticles have a large surface to volume ratio compared to bulk materials, a few
billionths of a meters in dimension to speed up chemical reactions, they are attractive candidates
for use as catalysts.
* Key point for the nanomaterials lies in that it has high surface area of the crystal, thus to give
higher atomic utilization ratios, the surface electronic and steric properties all changes. Doping
heteroatoms over the nano-materials surface would give much large effect.

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4.2 PRODUCTION OF PETROCHEMICALS WITH CATALYSTS

(OIL REFINING)
The oil we used to make “Petrol” (gasoline, or motor spirit) and other products, start out as raw
black petroleum. It cannot be used as it is, straight from underground. It must be changed into the
specific chemicals that people use. This process of changing petroleum into useful products is
called refining. The modern oil refinery is a large and complicated factory. Automatic control of
the various stages is efficient and safe. Teams of workers are needed to keep the refinery
machinery “running” smoothly.

The crude oil consists of many different chemicals with various chemical and physical
properties. Distillation or fractionation is the first stage in petroleum refining. This separates out
the various constituents) of the crude oil. Different hydrocarbons vaporize at different
temperatures. Here, tall distillation columns are necessary. There are many separate trays that are
fitted for collecting various chemicals. As the heating starts, partly vaporized oil is fed into the
column part of the way up. The lightest fractions are gases. The gases gather at the top of the
tower. Heavier fractions that are slower to evaporate gather at each lower stage. Usually,
fractions from several stages are drawn off for further processing. The residue, which is left at
the bottom of the tower, contains a wide range of petroleum parts. It can be used for fuel oil
without any more processing. It can be further distilled to give bitumen or lubricating oils.

4.2.1 Cracking
A process known as “cracking” breaks down large molecules into smaller ones. This is done
either by thermal cracking, using high levels of heat and pressure, or by using less heat and
pressure and a catalyst. Catalytic cracking is done by the fluid technique. In this, a catalyst in the
form of a fine powder is poured like a liquid through the petroleum and out to a regenerator. In
the regenerator, carbon that has become attached to the catalyst is removed. The catalyst is then
returned to the refining cycle.

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4.2.1.1 Catalytic Cracking

Catalytic cracking is normally used to make gasoline. The gasoline produced by this process has
a higher octane number than gasoline produced by straight distillation. The octane number is a
measure of the tendency of fuels to “knock” (make a knocking noise) when used in automobile
engines. The higher the number, the less is knock.

4.2.1.2 Hydro Cracking

In this method, hydrogen and catalysts are used under high pressure. The process results in
greater amounts of gasoline and less waste than catalytic cracking. During the cracking operation
some gases are always formed. These gases are collected and then put under high temperatures
and pressures in the presence of a catalyst. This process is called polymerization, joins molecules
together to make larger molecules. These larger molecules (polymers) are used in the production
of gasoline.

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CHAPTER 5
APPLICATIONS OF NANOCATALYSTS
Nanomaterials offer many possibilities as catalysts to meet future global demands in the
following catalytic process technology:
* Petroleum refining
* Petrochemical industry
* Synthetic fuels production
* Polymer manufacturing
* Pharmaceutical, chemical and food processing

INDUSTRIAL APPLICATIONS OF NANOCATALYSTS

* Biomass gasification to produce high syn gas and biomass pyrolysis for bio-oil
* Production of biodiesel from waste cooking oil
* Green Diesel production using Fischer-Tropsch
* Improved economic catalytic combustion of JP-10 aviation fuel
* Hydrogen production by steam reforming of ethanol over nanostructured catalyst
* Adsorptive desulfurization and bio desulfurization of fossil ooils
* Hydrodesulfurization of diesel

Sector:Biomass

Application: Biomass gasification to produce high syn gas and biomass pyrolysis for production
of bio-oil
Process Improvements: • Novel Al2O3 supported NiO catalyst reduces tar yield significantly
and increases tar removal efficiency to 99% • Significant increase in gas yield • Lighter fractions
of H2 & CO are increased in the syn gas composition while heavier fractions of CH4 & CO are
reduced, thus improving syn gas quality
Catalyst: Nano NiO catalyst supported on γ- Al2O3 microspheres of 3 mm size (Johnson
Mathey Company, greater than 99% purity)

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Application: Production of biodiesel from waste cooking oil

Process Improvements: • Esterification of fatty acids (FFAs) and transesterification of
triglycerides to biodiesel in one pot • Solid acid nanocatalysis of Al0.9H0.3PW12O40 nanotubes
with double acid sites yield 96% of biodiesel from waste cooking oil as compared to 42.6% with
conventional H3PW12O40 catalyst
Catalyst: Aluminium dodeca-tungsto-phosphate (Al0.9H0.3PW12O40) nanotubes as solid
catalysts with surface area of 278 m2/g

Application: Green diesel production using Fischer-Tropsch Synthesis (FTS)

Process Improvements: • Improving the FTS technology for production of high molecular
weight waxes, followed by their hydrocracking to generate liquid fuels • Improved efficiency of
slurry and fixed-bed reactors, used in FTS from biosyngas • Produce long, linear-chain paraffin
waxes in fixed bed & slurry FTS reactors
Catalyst: • Nano Fe and Co powders (10-50 nm) are used as FTS catalysts in slurry reactors,
promoted by other metals like Mn, Cu & alkalis • Produced by thermal plasma chemical vapor
deposition (TPCVD) and cluster spray techniques • Minimize liquid-solid diffusion resistance •
Multi-walled carbon nanofilaments (MWCNF), produced by CO2 sequestration via dry
reforming for gas-to-liquid FTS, with the iron carbide content rendering catalytic activity

Sector: Oil, Gas & Fossil Fuels:

Paraffin Dehydrogenation • Naphtha Reforming • Selective Hydrogenation •

Hydrodesufurization

Application: Improved economic catalytic combustion of JP-10 aviation fuel using hydrocarbon
fuel soluble nano catalyst
Process Improvements: • 50 ppm addition of catalyst in JP-10 reduces the ignition temperature
required to initiate combustion by about 240°C
Catalyst: Hexanethiol monolayer protected Palladium clusters < 1.5 nm
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Application: Hydrogen production by steam reforming of ethanol over nanostructured indium

oxide catalysts
Process Improvements: • At 623K, 99% conversion with mesoporous In2O3/KIT-6 catalyst
exhibit high production rates from ethyl alcohol at low-temperatures and yield low concentration
of CO impurity in comparison with other reported catalysts
Catalyst: Mesoporous In2O3 prepared using Mobil Composition of Matter No. 41 (MCM-41)
silica catalyst as templates with particle size of 2-3 nm and surface area of 107 m2/g to 173 m2/g

Application: Adsorptive desulfurization and bio desulfurization of fossil oils

Process Improvements: In situ coupling desulfurization using assembly of nano adsorbents
(nano γ- Al2O3) onto surfaces of Pseudomonas de lafieldii
Catalyst: Nano γ- Al2O3 (10 nm in width and 100-200 nm in length) with specific surface area
of 339 m2/g

Application: Hydrodesulfurization of diesel

Process Improvements: Hydrodesulfurization of dibenzothiophene increased by 20% using
SDM NiMo/Al-HMS nanocatalyst at 330°C as compared to commercial catalysts.
Catalyst: Synthesis of new NiMo/Al hexagonal, mesoporous structured nanocomposite catalyst
by supercritical deposition method.

Sector: Fuel Cells

Application: Core-shell nanocatalysts for fuel cell applications

Process Improvements: • Pt atoms are placed at the surface of other metal nanoparticles • All
the Pt atoms are available for catalytic reactions at the surface • Pt clusters on ruthenium
nanoparticles produce high activity per unit of Pt mass
Catalyst: Smooth and compact Pt shell for better oxygen reduction reactions in fuel cell
applications

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Application: In situ hydrogen production by reaction of ammonia and nanocatalysts

Process Improvements: • Ammonia is stored as a coordination complex with a transition metal
compound in solid composition • It acts as the hydrogen fuel precursor for a vehicle internal
combustion engine that is operated to use hydrogen or a combination of hydrogen and gasoline
as fuel • Ammonia dissociation catalyst tube containing a catalyst bed and maintained at 750°C
is used to dissociate ammonia into nitrogen and hydrogen atoms
Catalyst: The dissociation catalyst is a mixture of nanometer size particles of Co-NiO-Cu-Zr
catalyst deposited on high surface area of TiO2 and 2% Pt deposited on alumina particles.

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CONCLUSIONS
* Nanomaterials offer many possibilities as catalyst to meet future demand in catalytic process
technology in petroleum refining, petrochemical industry, and synthetic fuels production of the
future.
* The higher activity and better selectivity of nanocatalysts over traditional catalysts are
attributed to their large specific surface area, high percentage of surface atoms and special crystal
structures.
* The development of nanocatalysts is increasingly supported by advances in prepartion,
characterization and testing of catalysts.
* While it is well known that nanotechnologies have significantly contributed and advanced in
a number of industries such as, refining, petrochemicals, medicine, electronics and clean tech,
they are also expected to present game changing improvements to the oil and gas industry. With
global energy demand projected to increase by 60% over the next 30 years, there is no way for
current energy supply rather than to become more efficient and environmentally sound and that
is exactly what nanotechnologies can enable. They offer tremendous potential to increase
recovery of new and existing reservoirs, make economically viable to exploit unconventional
hydrocarbons improve exploration efficiency and modernize infrastructure.

# There are numerous areas of the petroleum industry where nanotechnology can contribute to
more efficient, less expensive, and more environmentally technologies than those that are readily
available. The future possibilities for nanotechnology in the petroleum industry are identified as
follows

* Improved success of exploration by improving data gathering, recognizing shallow

hazards, and avoiding dry holes.

* Nanotechnology-enhanced materials that provide strength and endurance to increase

performance and reliability in drilling, tubular goods, and rotating parts.

* Improved elastomers, critical to deep drilling and drilling in high-temperature/high-

pressure environments.

* Production assurance in diagnostics, monitoring surveillance, and management

strategies.
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* Corrosion management for surface, subsurface, and facilities applications.

* Lightweight, rugged materials that reduce weight requirements on offshore platforms,

and more reliable and more energy-efficient transportation vessels.

* Selective filtration and waste management for water and carbon nanotube applications.

* Enhanced oil and gas recovery through reservoir property modification, facility
retrofitting, gas property modification, and water injection.

* Refining and petrochemicals technologies.

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Some notes
1. The largest refinery in the world is Jamnagar Refinery in Gujarat. Refining capacity per day
is 661000 barrels per day.
2. One Barrel is 42 gallons or approximately 160 litres
3. What one Barrel of crude oil makes?
Gasoline 74 lit
Distillate fuel oil 37 lit
Kerosene/Jet fuel 15 lit
Residual fuel oil 9 lit
Liquefied refinery gases 7 lit
Coke 7 lit
Asphalt &road oil 5 lit
Petrochemical Feed stock 5 lit

4. India has witnessed a spectacular growth in the refining sector. In 1947, there was only one
refinery located in Digboi, with a capacity of only 0.25 million (250,000) tones/year. Today
there are at least 20 refineries in India with an installed capacity of 60.4 millions/year. By the
year 2012, India’s oil refining capacity would be 65.3 million tones /year.
5. India has large reserve of trained and highly skilled manpower at a relatively much lower
cost compared with advanced countries.

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References:
1) Dr. Anil Lachke (Catalysts in Petrochemical Industries)
2) Kong, X., & Ohadi, M. 2010. Applications of Micro and Nano Technologies in the Oil and
Gas Industry - Overview of the Recent Progress. Society of Petroleum Engineers.
3) Esmaeili, Abdollah. 2009. Applications of Nanotechnology in Oil and Gas Industry.
4) Scott, S., Crudden, C.M., and Jones, C.W. (eds.). 2003. Nanostructured Catalysts.
Nanostructure Science and Technology Series. Springer, New York.
5) Ying, J.Y, and Sun, T. 1997. Research Needs Assessment on Nano-structured Catalysts.
6) Mokhatab, Saeid, Fresky, M.A, and Rafiqul Islam, M. 2006 Applications of Nanotechnology
in Oil and Gas E&P, Journal of Petroleum Technology 58 (4).

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