F04 – New Technologies In Production And Development

22nd World Petroleum Congress, Istanbul 2017

ENHANCİNG RECOVERY OF OİL USING NANO PARTICLES-AN OVERVIEW

Shuna Sharma, Engineer, ONGC, India

ABSTRACT
Nanotechnology has become the buzz word of the decade! The precise manipulation and
control of matter at dimensions of (1-100) nanometres have revolutionized many industries
including the Oil and Gas industry. Its broad impact on more than one discipline is making it
of increasing interest to concerned parties. The Nanotechnology applications have pierced
through different Petroleum disciplines from Exploration, to Reservoir, Drilling, Completion,
Production and Processing & Refinery. Nanotechnology also strikes the stage of production
enormously to enhance the oil recovery via molecular modification and manipulate the
interfacial characteristics. Moreover, in a very similar fashion, it provides novel approaches
to improved post production processes. The present paper provides an overview of the
various types of nanoparticle which enhance the recovery of oil. “Polysilicon” nanoparticle
can alter the reservoir wettability and reduces interfacial tension resulting in additional
recovery of entrapped oil from pores. Nanoparticles derived from transition metal oxides
namely NiO, Co3O4 and Fe3O4 adsorbs asphaltenes from heavy oil which reduces the
viscosity of heavy oil and enhances oil recovery.

22nd WPC preprint paper. ©World Petroleum Council

 F04 – New Technologies In Production And Development
22nd World Petroleum Congress, Istanbul 2017

INTRODUCTION
Nanotechnology is the use of very small particles having dimensions between 1-100 nm.
Nanotechnology (sometimes shortened to "nanotech") is the manipulation of
matter on an atomic, molecular, and supra-molecular scale. Or in other words it
can be said “Nanotechnology is science, engineering and technology conducted at Nano
scale”.

New advancement in nanotechnology have led us to develop new materials, device with
enhanced features, tools and special characteristic of the systems that cannot be match
with conventional technologies. Nanotechnology offers advantage over conventional
technologies because they are cost effective, more efficient and environment friendly.
Nano particles also offer unique combinations in the properties such as mechanical,
thermal, electrical, optical, magnetic and chemical properties at nanoscale length.

Richard Feynman-The Physict, was the first man who discussed the possibility of synthesis
via direct manipulation of atoms. Inspired by Feynman's concepts, K. Eric Drexler
independently used the term "nanotechnology" in his 1986 book Engines of Creation:
The Coming Era of Nanotechnology, which proposed the idea of a nanoscale "assembler"
which would be able to build a copy of itself and of other items of arbitrary complexity with
atomic control.

Fig no.1: The Scale of things referenced to Nanometer (Source: http://www.diss.fu-berlin.de)

Properties of Nanoparticles in Context of Oil and Gas Industry

Enhanced Oil Recovery (abbreviated EOR) is a generic term for techniques for increasing
the amount of crude oil that can be extracted from an oil field. Enhanced oil recovery
is also called improved oil recovery or tertiary recovery. Using EOR, 30 to 60 percent or
22nd WPC preprint paper. ©World Petroleum Council
 F04 – New Technologies In Production And Development
22nd World Petroleum Congress, Istanbul 2017

more of the reservoir's original oil can be extracted compared with 20 to 40 percent using
primary and secondary recovery.

Enhanced properties brought about in the Nano size range which can be of interest in
production engineering can be:
1) Large surface to volume ratio: enhanced activity and contact area
2) Confinements of electrons or positive charge changing the material structure: changing
dielectric constant, conductivity, optical properties, chemical, electronic, etc
3) Chemically modified surfaces (wettability alteration at nano-scale)

The incredibly small size of the nano-scale materials creates opportunities for them to be
injected into oil and gas reservoirs. Geoscientists have analyzed enough of the oil-bearing
sandstones to establish that the pore throat openings commonly range between 100
and 10,000 nanometers in width. That’s large enough for fluids like water, brines, and oil
and gas to flow through relatively freely. So if we could put nano-scale tracers or
sensors down a hole, they would be small enough to flow through these pores, and we
could gain a bunch of valuable information about the rock and the fluid environment
where the oil and gas is found.

Different Nano Particles Used in EOR Techniques

1. Using Silica Nano Particles:

A nanoparticle has size typically less than 100 nm. It is composed of two entities: the
core and a thin shell. Generally a molecular shell has three separate regions; a tail group,
hydrocarbon chain and active head group. The chemical nature of shell determine
the solubility of nanoparticles such as lipophobic and hydrophilic nanoparticles (LHP)
dissolved in polar solvents like water and hydrophobic and lipophilic nanoparticles (HLP)
dissolved in non-polar solvents like xylene. Based on studies (Hendraningrat et al, 2012 a,
2012 b, 2013 a, 2013b) hydrophilic nanoparticles have great potential for a future.

Fig. 2 General wettability effect on residual oil saturation, oil remained after primary and secondary oil
recovery (Jadhunandan & Morrow, 1991; Owolabi & Watson, 1993)

Hydrophilic silica nanoparticles dispersed in synthetic saline water resulting in decreased

residual oil saturation after waterflooding and consequently ultimate oil recovery. Based
22nd WPC preprint paper. ©World Petroleum Council
 F04 – New Technologies In Production And Development
22nd World Petroleum Congress, Istanbul 2017

on studies done by Abbas Roustaei et.al, 2012 by using HLP nano particles more oil can be
recovered. Luky et al, 2013 observed that the possible oil recovery mechanism could be
interfacial tension (IFT) reduction, wettability alteration (which affects capillary pressure
and relative permeability) during the use of these nano particles. The general wettability
effects on the oil saturation, oil remained after primary and secondary oil recovery is
shown in fig. 2.

Presence of these nano particles in three-phase contact region has a tendency to

create a wedge structure. Chengara et.al, 2004 studied that Structural disjoining pressure
(Displacement mechanism) is correlated to the fluid ability to spread along the surface of
a substrate due to imbalance in interfacial forces among solid, oil phase and aqueous
phase. Interfacial forces will cause aqueous phase contact angle to decrease to 1 º and the
result is wedge film, this film act to separate oil from the formation surface (McElfresh et
al, 2012). Luky et.al, 2013 concluded that oil recovery is inversely proportional to size of
the silica nanoparticles and directly proportional to increase in temperature. Binshang
et.al, 2005 concluded that water wet formation is better than oil wet formation and
intermediately wet formations even produce better than the water wet formation (Dong
et. al, 2006)

2. Using Aluminum oxide Nano Particles in Brine Fluid.

Aluminum oxide (Al2O3) nano particles can be used to recover more oil from the
formation. Since Al2O3 has the ability to reduce the viscosity of oil which hinders oil's
recovery. Nano particles are solids and need a fluid to carry them into formation.
Fluids play a significant role in the displacement efficiency (Sweep efficiency of
displacing fluids in reservoir is very important. It depends on mobility ratio which
further depends on the viscosity of the displacing fluid and displaced fluid. If the
viscosity of the displacing fluid and that of the displaced fluid can be altered to improve
the mobility ratio, then sweep efficiency can be enhanced). N.A. Ogolo et.al,2012
conducted experiments using Al2O3 nano particles and various fluids such as diesel,
ethanol, brine, distilled water concluded that Al2O3 nano particles dispersed in brine
and distilled water have tendency to improve oil recovery. Silane treated Silica oxide;
NiO can also improve sweep efficiency other than Al2O3.

3. Using Nano Particles of Oxides of d-block Elements

Asphaltenes are aromatic macromolecules containing heteroatoms. They are present
to different extents in heavy oils. Asphaltenes contribute to the increased viscosity of
heavy oils and make them difficult to recover and process. Removal of asphaltenes
from crude oil is considered a significant upgrading target.
Nanoparticles are small in size but have large surface area which helps in adsorption.
The catalytic activity and/or sorption capabilities of the NPs formed depend primarily
on the surface area/L of the oil matrix, which is dictated by particle size, colloidal
concentration and stability. The differences in adsorption capacities were attributed to
the effect of particle size distribution, surface area, morphology and surface
properties. Adsorption isotherms were also nano-particle specific. For some metal
oxides, the adsorption isotherms followed the Langmuir model, suggesting monolayer
coverage. For other metal and metal oxides, adsorption decreased at high
concentrations due to changes in the colloidal state of asphaltenes at high
concentration, i.e. association and further formation of hemimicelles and micelles.
22nd WPC preprint paper. ©World Petroleum Council
 F04 – New Technologies In Production And Development
22nd World Petroleum Congress, Istanbul 2017

Nashaat N. Nassar et.al in their work employed nanoparticles of Co3O4, Fe3O4, and
NiO for the adsorptive removal of asphaltenes from heavy oil model solution followed
by asphaltene catalytic steam gasification/cracking. The nanoparticles tested showed
high catalytic activity for asphaltene gasification/cracking. A correlation appears to
exist between the affinity constant (The affinity constant is a measure of the
interaction between the adsorbate and absorbent). Higher the value, greater is the
strength of interaction and catalytic activity of nano-particles. Among the tested
nanoparticles, NiO nanoparticles showed the highest absorption affinity and catalytic
activity for asphaltenes.

Fig. 3 Percent correlation of asphaltenes in the presence and absence of different metal oxide nano particles (Nshaat N.
Nassar et al.)

4. Using Magnesium oxide nano particles

Formation damage due to fine migration is one of the destructive side-effect of some
EOR techniques which may also find solutions from nano-technological viewpoints. Fines
loosely attached to the pore surface are in the equilibrium with the pore fluids. These
particles start to flow when the equilibrium state is distributed by the EOR agent which,
may end up in permeability reduction in porous media. Different solutions have been
suggested to prevent detachment of fines from surface such as ionic clay stabilizer,
polymers and resins. Nano fluids that contain MgO nano particles show specific
properties such as high tendency for adsorption.
The study of interactions between fines and pore surfaces and investigating the
governing forces are important issue to describe the mechanism of this process. The
main type of these forces is electric double layer repulsion and London-Vanderwalls
attraction. These forces can be altered by the use of nano particles surface coatings.
MgO nano-particles increase the effect of attraction forces in comparison with repulsion
forces which results in fine fixation (Ahmadi et al., 2011). Al2O3 and SiO2 can also be
used for fine migration control other than MgO.

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 F04 – New Technologies In Production And Development
22nd World Petroleum Congress, Istanbul 2017

Fig. 4 SEM images of glass bed coated with MgO nanoparticles with adsorbed fines(Habibi et al.,
2011)

4. Using Ni-Fe Nano Particles

Gas hydrates is an ice- like crystalline solid formed from a mixture of water and natural
gas, usually methane. Hydrate can produce 160 times volume of methane which is an
infinite source of energy to be trapped. Bhatia and Chacko, 2011, suggested the injection
of air suspended self – heating Ni-Fe nanoparticles in the hydrate formation through
horizontal well. These particles will penetrate into the hydrate reservoir by passing
through the cavities. The self-heating of Ni-Fe particles in a magnetic field is caused by
hysteresis loss and relaxation losses. These particles cause a temperature rise up to 42°
in the formation leading to disturbance in thermodynamic equilibrium and causing the
water cage to decompose and release methane. In this technique, the pressure of
the fluids in contact with hydrate is lowered, pushing the hydrate out of its stability
region and leading to its decomposition. The main advantage of this technique is the
very low dosage requirements and these nano particles are non-poisonous and
environmental friendly.

Conclusion:
The following are the main points can be made after the study:
1. Nanotechnology could be break through to some of the bottlenecks in the field of
EOR. The size of nano particles and their very different characteristics, especially surface
properties, are the main keys of this improvement.
2. HLP silica oxide nano particles can be used to alter the wettability and inter facial tension.
3. Aluminum oxide nano particles in brine fluid can be proved promising to increase sweep
efficiency.
4. More research and investigation is required on d block metal nano particles because they
show variable properties which can be proved beneficiary for oil sector
5. NiO nano particles can be used to decrease the viscosity of oil by removal of asphaltenes
contents.
6. MgO nano particles can be used to mitigate fines.
7. Ni_Fe nano particles can be used in recovery of hydrates which is an infinite source of
energy to be trapped.

Acknowledgement
22nd WPC preprint paper. ©World Petroleum Council
 F04 – New Technologies In Production And Development
22nd World Petroleum Congress, Istanbul 2017

The authors would like to thank management of Oil and Natural Gas Corporation Ltd. for
the permission to publish this paper. Authors would also like to thank Shri B.Sarkar,
General Manager, ONGC; Shri R.K. Singhal, General Manager, ONGC; Shri P.K.Saxena,
Group General Manager, ONGC, Shri Sachin Sain Executive Director, ONGC for their
constant guidance and valuable advises during the entire work.

References
1. Sergio Kapusta et. al. SPE 15152 “ Nanotechnology Applications in Oil and Gas Exploration and
Production”

2. N.A. Ogolo et. al. SPE 160487 “ Enhanced Oil Recovery Using Nanoparticles”

3. Nashaat N. Nassar et. al “Application of Nanotechnology for Heavy Oil Upgrading: Catalytic Steam
Gasification/Cracking of Asphaltenes”

4. Nashaat N Nassar et. al. “In Situ Prepared Nanoparticles in Support of the Oilsands Industry Meeting Future
Environmental Challenges”

5. Abbas Shahrabadi et. al. “Experimental Investigation of HLP Nanofluid Potential to Enhance Oil Recovery: A
Mechanistic Approach”

6. Luky et. al. SPE 165955 “ Effect of Some Parameters Influencing Enhanced Oil Recovery Process using Silica
Nanoparticles : An Experimental Investigation”

7. Abdelrahman et. al. SPE 164716 “ Applications of Nanotechnology in the Oil & Gas industry: Latest Trends
Worldwide & Future Challenges in Egypt”

22nd WPC preprint paper. ©World Petroleum Council