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A state-of-the-art review of the application of nanotechnology in the oil and gas

industry with a focus on drilling engineering

Jagar A. Ali, Abdullah M. Kalhury, Ayub N. Sabir, Rawezh N. Ahmed, Nali H. Ali,
Abdullah D. Abdullah

PII: S0920-4105(20)30208-4
DOI: https://doi.org/10.1016/j.petrol.2020.107118
Reference: PETROL 107118

To appear in: Journal of Petroleum Science and Engineering

Received Date: 20 August 2019

Revised Date: 21 February 2020
Accepted Date: 22 February 2020

Please cite this article as: Ali, J.A., Kalhury, A.M., Sabir, A.N., Ahmed, R.N., Ali, N.H., Abdullah, A.D.,
A state-of-the-art review of the application of nanotechnology in the oil and gas industry with a focus on
drilling engineering, Journal of Petroleum Science and Engineering (2020), doi: https://doi.org/10.1016/
j.petrol.2020.107118.

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CRediT author statement

Jagar A. Ali: Supervisor. Abdullah M. Kalhury, Ayub N. Sabir, Rawezh N. Ahmed, Nali H.
Ali, Abdullah D. Abdullah: BSc Students.

.
A state-of-the-art review of the application of nanotechnology in the oil and
gas industry with a focus on drilling engineering
Jagar A. Ali*, Abdullah M. Kalhury, Ayub N. Sabir, Rawezh N. Ahmed, Nali H. Ali,
Abdullah D. Abdullah
Department of Petroleum Engineering, Faculty of Engineering, Soran University, Kurdistan
Region, Iraq.

*Corresponding Author: jagar.pet@gmail.com

Contents
Abstract .......................................................................................................................................2
1. Introduction.............................................................................................................................2
2. Types of Nanomaterials Used in Petroleum Applications ......................................................4
2.1. Nanoparticles .................................................................................................................. 4
2.2. Nanosensors .................................................................................................................... 6
2.3. Nanocomposites .............................................................................................................. 8
2.4. Coatinged-Nanoparticles............................................................................................... 10
2.5. Nanofluid ...................................................................................................................... 11
3. Applications of Nanotechnology in Oil Industry ..................................................................13
3.1. Exploration and reservoir characterization ................................................................... 13
3.2. Production technology .................................................................................................. 15
3.3. Enhanced oil recovery................................................................................................... 17
3.4. Drilling Technology ...................................................................................................... 26
3.4.1. Cementing .............................................................................................................. 28
3.4.2. Drilling Tools ......................................................................................................... 31
3.4.3. Drilling Fluids ....................................................................................................... 32
4. Nanotoxicity ..........................................................................................................................36
5. Detailed Summary .................................................................................................................37
6. Conclusions ...........................................................................................................................38
List of Abbreviation...................................................................................................................39
References .................................................................................................................................40

1
Abstract
Hydrocarbons have been the primary resource of energy of civilizations for hundreds of years
historically and still play a vital role in accomplishing the daily life occupations in every
sector. With the upcoming dramatic rate increase of human population reaching to 9.8 billion
by 2030, the latter require uprising supply of goods and services that can be achieved through
the increased rate production of gas and oil globally. Nanotechnology is a General-Purpose
Technology (GPT) that can fulfil the needs of humanity in every industry sector with its
unique properties of a scale range between 1 to 100 nm and high surface area, adsorption
potential and heat conductivity. Therefore, nanoscale materials can impressively make major
advancements in the upstream and downstream sectors of the gas and oil industry.
In this study, the properties and mechanisms of modifying the different nanomaterials are
manifested which can be used in different segments of petroleum industry, such as
exploration, reservoir engineering, enhanced oil recovery, drilling technology and refining
processes. Our aim in this work is to provide a detailed elaboration on the drilling technology
including the application of nanomaterials as additives in drilling mud for manipulating the
rheological properties, pH and treat the fluid loss, such as iron oxide (Fe2O3), silica dioxide
(SiO2), multi walled carbon nanotubes (MWCNT), and polymerized acrylamide monomer
with the presence of TiO2. Moreover, the application of these nanomaterials in cementing and
drilling tools such as pipes and bits are covered. Pipes are are coated with MoS2
nanoparticles. Drill bits can be modified and kept safe in harsh conditions by Al2O3-TiO2
nano ceramics powder. Consequently, nanotechnology is considered as a promising field that
can meet the demands with great potential and satisfying results.

Keywords: Nanotechnology; Oil and gas industry; Nanofluids; Drilling; Exploration; EOR.

1. Introduction
Amongst the numerous energy sources, crude oil remains, or even can be thought of, as one
of the most treasured, valued and predominant natural resources in present human societies
on the planet of Earth (Rychlicki et al., 2006; Landa-Marbán et al., 2017; Talukdar et al.,
2018). According to the world energy reports, demand on crude oil is increasing worldwide
(Ali et al., 2019a,b). Discovering new oil reservoirs is difficult and 30-60% of oil remains
trapped in the currently-producing reservoirs. Thus, researchers and oil companies try to
extract the remained oil in the matured reservoirs using novel and efficient technologies;
nanotechnology as the current most attracted valuable technology (Ali et al., 2019a-c).
2
Nanotechnology was first introduced around half a century ago, and currently, it is the most
active research topic worldwide (Lu et al., 2012; El-Diasty and Ragab, 2013). It was first
proposed by a physicist, called Richard Feynman, in 1959 (Feynman, 1960). The term
nanotechnology was first used by Norio Taniguchi in 1974, who gave a speech elucidating
the development of dimensional accuracy with which things can be made easier over time
(Taniguchi, 1974). Additionally, Allhoff and Lin (2006) reported that the nanotechnology is a
new class of technology that encompasses the accurate engineering and use of materials at the
molecular level. This innovative technology has been acknowledged as an unruly technology
with a broad range of benefits in different applications (Leon, 2010; El-Diasty and Ragab,
2013). According to the current research trends, nanotechnology has a promising role in
different industries, such as material and surface treatment (Abdelrahman, 2013), medicine
(Santamaría-Aguirre et al., 2018), chemistry (Whitesides, 2005), environment (Hannah and
Thompson, 2008), heavy industry and food processing (Lu et al., 2012). Thus,
nanotechnology’s contribution has made these fields advance into a whole new level, and
nanomaterial is now regarded as a key material for a broad scope of applications (Esmaeili,
2011).
Peng et al., (2017) and Baoliang et al., (2017) claimed that although the nanotechnology has
not been put into use very much and often in oil and gas industry as in the other areas,
fortunately, in the last 5 years, the industry has successfully managed to get benefits from it
in drilling process (Krishnamoorti, 2006), cementing, enhanced oil recovery (EOR) (Ali et
al., 2018b), corrosion inhibition (Wang et al., 1997), well logging (Nikitin and Korjik, 2012),
reduction of heavy oil viscosity, hydrocarbon detection, petroleum refining (Saleh, 2017) and
drag reduction in porous media. As it is obvious, the oil and gas fields depend on the strength
and stability of the materials, nanomaterials with high thermal conductivity (Mokhatab et al.,
2006), improving downhole separation of oil and gas, and greatly corrosive resistance could
be used as a developed geothermal resource (Wang et al., 1997). Additionally,
nanotechnology can help in developing the drilling process equipment, so it can make better
resistance headed for water and corrosion, better durability, wear and shock-resistant, and
enhanced thermal conductivity by coating them with special types of nanoparticles
(Krishnamoorti, 2006).
The drilling process, as the name suggests, is creating a hole in the ground to reach the
desired depth which is the formation that has been considered to contain petroleum according
to the geological and exploration data (Fagan, 1991). During this process, the mud
circulation, as one of the most common systems of the rotary drilling, performs many
3
functions such as cooling the drill bit, suppressing the reservoir fluids, cleaning the wellbore
and controlling the stability of the wellbore (Van Dyke, 1998). Selecting a suitable type of
circulation fluid to drill a well with the minimum cost, less environmental risk and lowest
formation damage is one of the main aspects of the drilling process in oil and gas industry.
This fluid, also called drilling mud or simply, mud, is basically a combination of clays with
water or oil. Conventionally, chemical materials including acids, polyacrylamide, starch,
xanthan, and fibers are added to the drilling mud in order to modify its properties and
functions. The high cost of chemicals (Kasiralvalad, 2014), possible reservoir damage (Rad
and Mansouri, 2018), high consumption (Paydar and Ahmadi, 2017), and chemical loss
(Alizadeh et al., 2015) are the main challenges for this classic mud. Therefore, a new kind of
mud with low cost, high efficiency, and environmental friendliness needs to be developed.
The main mechanisms of drilling nanofluid highlighted in the literature are increasing the
wellbore stability (Taraghijah et al., 2015), better wellbore cleaning (Samsuri and Hamzah,
2011), fluid loss reduction (Zakaria et al., 2012) and improving the mud rheological
properties (Jung et al. 2011). Abdo and Haneef (2010) studied the effect of drilling nanofluid
to solve virtually all the usual and unusual problems that the drilling muds are likely to face
in the wellbore. They stated that using nanoparticles can improve the rheological and
filtration properties of the drilling mud in a way that the use of expensive chemicals can be
eliminated. The study of this paper is to demonstrate the application of nanotechnology in the
upstream oil and gas industry generally and particularly in drilling operations by presenting
the previous works of the researchers regarding this purpose.

2. Types of Nanomaterials Used in Petroleum Applications

2.1. Nanoparticles

In the view of literature, nanoparticles possess an astonishing lengthy history (Heiligtag and
Niederberger, 2013). Vollath (2013) declared that nanoparticles had already been used a long
time ago by the Sumerians before the recent desire for the development and use of these tiny
particles. In other words, after lots of years of intense and deep research, work, struggle and
efforts, it turned out that nanoparticles were not the sole invention of humans even though
there are many man-made and synthesized nanoparticles (Heiligtag and Niederberger, 2013).
Nanoparticles which is a wide class of materials are substances, solid, or colloidal particles
whose sizes range in between 1-100 nm in diameter (Rizvi and Salah, 2018; Khan et al.,
2017; Subbenaik, 2016; Hendraningrat and Zhang, 2015; Abhilash, 2010; Fakoya and Salah,

4
2017). Vollath (2013) and Khan et al., (2017) stated that considering the overall shape,
nanoparticles can be divided into zero-dimensional., which are the nanoparticles per se, one-
dimensional., i.e., nanotubes or nanorods, two-dimensional., e.g., nanoplates (Vollath, 2013),
or three-dimensional ones (Khan et al., 2017). Heiligtag and Niederberger, 2013 proclaimed
that there are two types of naturally occurring nanoparticles: organic, such as viruses,
proteins, polysaccharides and many others; and inorganic compounds, i.e., metals,
aluminosilicates, iron oxyhydroxides etc., which are formed through wildfires, volcano
eruptions, weathering or microbial processes. Researchers and scholars recognized the
important and significant role that nanoparticles play in affecting and changing a substance’s
physiochemical properties, i.e., the optical properties, owing to their nano-scale size
(Abhilash, 2010; Khan et al., 2017).
Nanoparticles exhibit distinctive, unique and exceptional properties and features, which are
tremendously different from others, due to their minute size, larger surface area per unit
volume and special higher chemical reactivity than that of other particles (Abhilash, 2010;
Kamal et al., 2017; Fakoya and Salah, 2017; Kazemzadeh et al., 2018). It is worth
mentioning nanoparticles are not, indeed, as simple as one might have thought of; rather they
are comprised of three layers: (i) the core (the nanoparticle’s principal part), (ii) the shell layer
(iii)
(unlike the core, it is a different material chemically in all features), and the surface layer
(a layer which may have small molecules, surfactants, metal ions and/or polymers stuck to
them) (Khan et al., 2017). A large number of methods have been devised by the scientists to
synthesize a wide diversity of nanoparticles (nanoparticles of different shape, size and
chemical and/or physical properties) (Abou El-Nour et al., 2010; Heiligtag and Niederberger,
2013; Kango et al., 2013; Subbenaik, 2016).
In the past years, several methods were used for preparation of nanoparticles, including
solvent evaporation (Desgouilles et al., 2003), nanoprecipitation (Yadav et al., 2010), salting
out (Galindo-Rodriguez et al., 2004), emulsion and mini-emulsion polymerization
(Landfester, 2009), electrohydrodynamic atomization (Gomez-Estaca et al., 2012), using
supercritical fluid technology (Byrappa et al., 2008), and the generation of nanoparticles
using the nano-emulsion template (Anton et al., 2008). Solvent evaporation was the most
common method for preparation of nanoparticles (Murakami et al., 1999; Desgouilles et al.,
2003), and it is the first method which was used for preparing nanoparticles (Murakami et al.,
1999) (see Fig. 1). During this process, compound solutions were prepared in the emulsions,
and volatile solvents (Salager et al., 2004) were advanced by victimization of chloride and
chloroform. However, this has currently been replaced with the organic compound that
5
provides a higher pharmacological medicine profile and urges particles to be within the 500
nm in size. The prepared emulsion is born-again into a nanoparticle suspension on
evaporation of the solvent, then the solution is allowed to diffuse through the continual a part
of the emulsion to carry out customary mode of ways i.e. single emulsions e.g., oil-in-water
(Talele and Gudsoorkar, 2016), and double emulsions (Salager et al., 2004; Mendoza-Muñoz
et al., 2016). Such sort of ways utilize high-speed homogenizations or ultra-sonification,
followed by evaporation of the solvent, either by continuous magnetic stirring at elevated
temperatures or below reduced pressure resulting in the formation of coagulated nanosized
particle collected by activity followed by laundry to urge obviate surfactants and eventually
the merchandise is preserved (Talele and Gudsoorkar, 2016). ShamsiJazeyi et al. (2014)
enumerated some of the significant and noteworthy applications of nanoparticles, including
drug delivery (Khan et al., 2017), imaging, solar cells, drilling (Fakoya and Salah, 2017) and
enhanced oil recovery (Gbadamosi et al., 2018a). Nanoparticles can help in reducing
interfacial tension and surfactant adsorption on the surface of reservoir rock, stabilizing
foams and emulsion and altering wettability as well as reducing oil viscosity (ShamsiJazeyi et
al., 2014; Kamal et al., 2017; Gbadamosi et al., 2018a).

Fig. 1 Solvent evaporation technique for the preparation of nanoparticles.

2.2. Nanosensors
Generally speaking, nanosensors, as the most recent invention, are defined as those physical,
chemical or biological sensors, which are created at the nano-scale, in active elements and in
nanomaterials sizes (Lieber et al., 2006; Dahman, 2017). However, Scoville (2013) and
Rubel (2010) defined nanosensors as those devices that have the ability to sense and respond
to physical stimuli, as well as to convey data and information effectively with unique and
astonishing physical properties on the nano-scale. Developing this kind of nanomaterials

6
provide several benefits in sensitivity and specificity over traditional materials (Lieber et al.,
2006). Moreover, the composition of a nanosensor could include many additives, like
accelerants, fillers, fibers, plasticizers, nano-flakes and nano-platelets. The addition of these
additives is dependent on the field of their application (Bhavsar, 2009). Nanosensors can be
operated at the same scale of natural biological processes to allow function with both
chemical and biological particles. Thus, the stem sensitivity enhancement can form a high
surface area-to-volume ratio of nanomaterials with delivering unique physical properties of
nanomaterials (Juzgado et al., 2017). According to Yonzon et al. (2005) and Kim et al.
(i)
(2009), nanosensors can be classified based on the following bases as shown in Fig. 2:
classification based on nanosensors structure, and (ii) classification based on the application of
nanosensors. According to their structure, nanosensors are divided into optical and
electrochemical nanosensors. And they are sub-classified into four different types including
chemical, electrometer, deployable and biosensor based on their chemical composition. Each
can have different features and applications according to their structure and chemical
composition.

Fig. 2 The general classification of nanosensors.

As it is obvious, various imaging techniques have been developed for characterizing the oil
and gas reservoirs, but obtaining a high-resolution image is still incapable. Thus, Khalil et al.
(2017) utilized a novel technique of using nanosensors for investigating the characteristics of
the deep formations by providing the complex fluid and rock contact and designing suitable
future plans. In this work of them, high quality of characterization was achieved by

7
identifying the accurate temperature and pressure profile. From injecting and distributing the
nanosensors into the porous-permeable formation, the high-quality characteristics of the
optical, magnetic, and electrical behavior of nanomaterials make them reliable tools for the
enhancement of the imaging contrast (Krishnamoorti 2006; Ponmani et al., 2013). Zaman et
al. (2013) used the hyperpolarized silicon NPs as nanosensors for measuring images of the
formations in the exploration field. Additionally, nanosensors can have been applied
successfully for monitoring the oil refining processes. Furthermore, nanosensors can also be
used to obtain more detailed and accurate information about reservoirs and smart fluids
during the drilling and enhanced oil recovery (EOR) processes (Kong and Ohadi, 2010;
Odedele, 2014). By adding nanosensors to the reservoir, the flow of hydrocarbons in
subsurface individual pores and channels can be observed in details, and the trapped oil can
be identified (Kong and Ohadi, 2010; Ayatollahi and Zerafat, 2012; Odedele, 2014; Negin et
al., 2016).

2.3. Nanocomposites
Generally, composites are mixtures of two or more substances that are mixed to obtain a
blend bearing the characteristics of the parental substances with enhanced performance. It is
composed of two parts, a discontinuous phase called “reinforcement” and a continuous phase
called “matrix”. However, according to Cammarata (2006), nanocomposites can be defined
as a blend of several mixtures with different phases and one of those elementary particles
must have the scale of less than 100 nm. Okpala, (2014) stated that experiments have proved
adding different types of nanocomposites to their macroscopic counterparts can efficiently
yield new byproducts with enhanced qualities and with higher surface area to volume ratios
compared to conventional composites. The novelty of the new products can be promising in
usage in many fields, such as the preparation of drilling fluids, EOR, shale swelling, fluid
loss control, etc. The properties of nanocomposites are dependent on the morphology,
dimension, agglomeration, diffusion and composition of materials (Kango et al., 2013; Sajadi
et al., 2019; Ali et al., 2019c).
Nanocomposites are basically classified depending on their matrix material into three
different groups; metal matrix nanocomposite MMNC (Tjong and Wang, 2004), polymer
matrix nanocomposite, PMNC (Jimenez et al., 1997; Camargo et al., 2009), and ceramic
matrix nanocomposite, CMNC (Lawn and Fuller, 1975; Pokropivnyi et al., 2002).
Nanocomposites in various ways can be applied as displacing agents to increase the oil
production in enhanced oil recovery (EOR), such as polymer-coated nanocomposites, water-
8
soluble polymers polyacrylamide (PAA) and sodium carboxymethylcellulose (CMC)
(Carlesso et al., 2016). In addition, lost circulation can be treated using nanocomposites
organic/inorganic gel as a cross-linked pill to plug the fractured formations and control the
major losses of the mud. Lecolier (2005) presented the advantages of using nanocomposites
as plugging agents during the drilling process. Moreover, a recent study by Ahmad et al.
(2018) shows that using the CNT-polymer nanocomposite with the concentration of 2 w/v%
reduced the shale swelling by about 90% at HTHP condition. Thus, a stable borehole can be
achieved during drilling the troublesome formation. Sadeghalvaad and Sabbaghi (2015) have
presented the effects of using nanocomposites on the rheological properties. A
nanocomposite that is composed of TiO2 and polyacrylamide (PA) is added as an additive to
the water-based drilling mud. The results have shown that it has increased the viscosity of the
mud and treated fluid loss efficiently and thinned mud cake thickness.
In a recent experiment done by Ali et al. (2018a), ZnO/SiO2/Xanthan NC is made up to
significantly decrease the interfacial tension and improve the oil recovery. First ZnCl2 is
added to Na2SiO3, and then it is mixed with pomegranate extract (Fig. 3). The blend is mixed
until the heavier reddish components are precipitated. The precipitates are segregated using
filtration method. Then the mixture is flushed with hot distillated water to remove excess
impurities. After the mixture has been dried and introduced to Xanthan Gum using mortar
and pestle, finally the blend is ready for EOR applications, which they enabled to reduce the
IFT by 93% and increased the oil recovery by 19.3% OOIP The wide applicability, property
combinations and design uniqueness of nanocomposites make them be called the materials of
the 21st century that are not found in conventional composites.

Fig. 2 Schematic diagram of the process of synthesizing ZnO@SiO2@Xanthan nanocomposite (Ali et al.,
2018a).

9
2.4. Coatinged-Nanoparticles
In the gas and oil industry, new advancement and progress is always essential to provide best
solutions for emerging problems during operations in the harshest environments at surface
and subsurface. Thus, nano-coating can meet the needs and achieve the enhancement of the
tools used in this industry (Glaus et al., 2010). According to Ates et al. (2018) a new
generation of nanocomposite materials is coating the composited nanoparticles, which is
basically divided into two main phases; nanocrystalline phase and amorphous phase.
During drilling oil and gas wells, the drill bit faces the grinding through hard formations to
reach the target. Consequently, the surface of the bit wears out during operation. Thus,
coating the surface of the drill bit with nano-ceramics can greatly enhance the durability and
lifetime of the bit. Additionally, the roughness of the coated-bit by nanomaterials is always
increased two to four times compared to non-nanocoated bits. Therefore, increasing coated
material’s stiffness is the main property of the nanocomposite coating. For this purpose, in
accordance with Sengupta and Kumar (2013) the drill bits are usually exposed to stream-
spraying plasma of Aluminum oxide (Al2O3) and Titanium dioxide (TiO2) of diameter range
20-100 nm. The plasma is sprayed with a velocity range of 1200-1500 m/second out of the
nozzle on the substrate as shown in Fig. 4. The sprayed nanometers are directed to the surface
of the bits and cooled down after being heated. The outcome is a new and strong layer of
nano-coating that can be repaired every time after application instead of changing the bit.
Hence, this technique can highly reduce the cost of tripping in and out of the drill string and
can increase the life span of the drilling bit (Sengupta and Kumar, 2013). Moreover, another
application of the nanocoating is preventing corrosion in transmission pipes. This technique
composed of utilizing the acrylic resin water-based of 30% and 70% nanocomposites, with a
nanometer tunnel that covers the internal surfaces of pipes in order to prevent air to be passed
and moisture to be depleted at the surface. Accordingly, the corrosion can be inhabited inside
the gas and oil pipes (Noveiri et al., 2012).

10
Fig. 3 Nanocoating by Aluminum oxide (Al2O3) and Titanium dioxide (TiO2) (modified after Sengupta and
Kumar, 2013).
2.5. Nanofluid
Nanofluid, as a significant part of nanotechnology, is a new type of fluid (Esmaeili, 2011)
which is generally considered as a special class of colloids (Hendraningrat and Zhang, 2015)
and non-Newtonian fluid (Saenkhumwong and Suksri, 2017). Nanofluids are basically
composed of blending the nanomaterials within the different the liquid solutions including
water, ethylene glycol, ethanol and surfactant as base fluids (Sharma et al., 2016), and
polymetric fluid, engine oil and mixture of two fluids or more as surface-based fluids (Table
1) (Mcelfresh et al., 2012; Yu and Xie, 2012; Hendraningrat and Zhang, 2015; Fakoya and
Salah, 2017; Nwidee et al., 2017). Nanofluids are usually prepared using the two-step
technique. Nanoparticles or alternative nanomaterials employed in this technique are initially
made as dry powders in a chemical or physical way. Then the nanosized powder is mixed
with the dispersion fluid with the assistance of intensive attractive force agitation, inaudible
agitation, high-shear compounding, homogenizing, and ball edge as shown in Fig. 5 (Yu and
Xie, 2012).

Table 1. Summary of nanofluid applications in drilling and EOR.

Area NPs Purposed Outcomes Ref.
Drilling Fe2O3 Mud rheological Increase in concentration of Fe2O3 NPs in Jung et al., 2011
nanofluid properties of the mud the bentonite suspension resulted in
increasing yield stress
Fe3O4 Mud rheological and reduction of 40% of fluid loss compared Vryzas and Kelessidis,
filtration properties to the base fluid at HP/HT conditions 2017
(250 ◦F and 300 psi differential pressure).
Carbon Mud rheological and addition of MWCNT and nanosilica Ismail et al., 2016
nanotube, and filtration properties improved the rheological properties such

11
 nanosilca as plastic viscosity and yield point
compared to that of the base fluid.
CuO and ZnO Na enhanced drilling NWBM had better thermal and filtration Ponmani et al., 2013
mud properties than MWBM.
EOR ZrO2 Oil recovery Only in the water the oil recovery is less Ogolo et al., 2012
nanofluid than the injecting
NWP Wettability and The NWP has greater effect on the Onyekonwu et al.,
interfacial tension wettability than on the interfacial tension. 2010
SiO2 Wettability and The SiO2 is very effective in modifying Maghzi et al., 2014
interfacial tension the interfacial tension and wettability.
Carbon NPs Oil recovery The oil recovery was improved to 95%. Kanj et al., 2009

Fig. 4 Preparation of nanofluid by two-step method (modified after Yu and Xie, 2012).

The unique properties and characteristics of these novel fluids provide huge potential for
developments and advances in a large number of sectors, for example, chemical and
processing, medical (Fakoya and Salah, 2017), environment and energy (Hendraningrat and
Zhang, 2015). Particularly, in recent years, nanofluids have been widely considered for many
various applications in oil and gas industry, for instance, exploration and exploitation of oil
and gas, drilling operation, completion (Hareland et al., 2012), production (Hwang et al.,
2008), enhanced oil recovery (EOR) (Nwidee et al., 2017; Al-Anssari et al., 2018) and
stimulation (Fakoya and Salah, 2017). The suspension stability of nanoparticles is a key
consideration in the nanofluid preparation because it will change the zeta potential and reduce
the role of nanos (Al-Anssari et al., 2018). It has been observed that the very small number of
nanoparticles added to the nanofluid has yielded relatively astonishing increases in its
properties (Hendraningrat and Zhang, 2015). As a rule of thumb, the smaller the number of
nanoparticles in the nanofluid is, the higher the zeta potential is and the more stable the
nanofluid will be (Du et al., 2015).

12
3. Applications of Nanotechnology in Oil Industry

3.1. Exploration and reservoir characterization

Exploration is essentially the first step in developing the oil and gas fields (Agista et al.,
2018). Therefore, hydrocarbon exploration is considered as one of the most essential and
expensive activities, which is also very dangerous and risky (Khalil et al., 2017; Agista et al.,
2018). By definition, petroleum exploration is the process of searching and seeking for
hydrocarbon deposits underlying the earth’s surface, and it is carried out by petroleum
geologists and geophysicists (Ponmani et al., 2013; Khalil et al., 2017; Rezaeyan et al.,
2018). Several sources and techniques, including geologic studies, seismic surveys, well-
logging, well tests, and formation evaluation, are usually used to give information in order to
generate an accurate and precise picture of the reservoir containing hydrocarbons (Ponmani et
al., 2013). According to Ponmani et al., (2013) and Agista et al., (2018) the shrinkage of
existing oil and gas fields as well as increased demand on petroleum have given rise to
exploration and development of more fields, and therefore petroleum explorations have to be
carried out in more challenging regions, which involve high risk and costly activities. On the
other hand, it is reported that many old and conventional electrical sensors and other
measuring means are often unable to give high-resolution reservoir imaging and necessary
information, or can only give knowledge with high uncertainties, about the reservoirs,
especially in conditions of high temperature and high pressure (Esmaeili, 2009; Esmaeili,
2011;Khalil et al., 2017).
Therefore, novel, state-of-the-art and more advanced nanomaterial-based sensing devices
were needed to be developed which both technically and economically are practicable and
feasible (Ponmani et al., 2013; Khalil et al., 2017; Agista et al., 2018). Lately, as technology
advanced, the use of nanosensors in seismic characterization and formation evaluation has
been suggested as a magnificent solution for the problems (Agista, 2018). According to
Ponmani et al. (2013) and Fakoya and Shah (2017), the use of engineered nanoparticles is
one of the available and effective ways for exploring and detecting hydrocarbons in
petroleum reservoirs in different ways and mechanisms as shown in Table 2. Nanoparticles
with considerable and significant alterations in their optical, electrical and magnetic
properties by comparison with their “bulk counterparts” can be used as superb tools for
improving and developing sensors and image contrasts (El-Diasty and Ragab, 2013; and
Rezaeyan et al., 2018). To be more specific, the use of nanosensors in the pore spaces in the

13
form of nanodust is capable of providing information and insight on characterizing the
reservoir, monitoring fluid flow and recognizing fluid type. For example, tight shales, tight
gas sands and tight carbonates are able to be imaged by nano-CT (Kong and Ohadi, 2010). As
another example, hyperpolarized silicon NPs, as the most novel and crucial tool, can be used
for measuring and imaging formations in petroleum exploration (El-Diasty and Ragab, 2013;
Agista et al., 2018; Rezaeyan et al., 2018). Additionally, nanosensors have been used as 3-
and 4-dimensional seismic distribution and sensing mechanism in imaging the subsurface
structure (Ponmani et al., 2013; Peng et al., 2017). Khalil et al. (2017) reported several
multitasking nanomaterials, such as sulfated and non-sulfated polyvinyl alcohol with the
functional group oxidized carbon black (PVA-OCB) nanoparticles, that can be used to detect
subsurface hydrocarbon; and these nanoparticles are called nanoreporters (Fakoya and Shah,
2017). The use of superparamagnetic iron oxide nanoparticles as a contrasting agent in
nuclear magnetic resonance imaging is important for characterizing reservoirs (Khalil et al.,
2017). In Khalil and his coworkers’ view (2017), the build-up and formation of interfacial
fluctuation and pressure wave caused by the moving magnetic nanoparticles, which are able
to probe the distribution of immiscible fluids and can be absorbed at the oil-water interface or
air-water interface owing to an external magnetic field causes the hydrocarbon detection. A
schematic representation of hydrocarbon detection by nanoreporters is shown in Fig 6.

Table 2. Summary of nanotechnology applications in exploration & reservoir characterization.

Nanomaterial Purpose Reference
Superparamagnetic iron It has the ability to provide self-confirmed, targeted MR Yang et al., 2009
oxide (SPIO) NPs imaging of tumors.
Nano-optical fiber It is a sensor tool used to detect oil-microbe and determine the El-Diasty and Ragab,
reservoir pressure and temperature. 2013
Nano-robots It is used to examine individual pores and channels, trace the Fakoya and Salah,
trapped, monitor the flow of hydrocarbons in subsurface 2017
reservoirs, exchange information to the surface.
WO3 NPs-based sensor It has the ability to selectively measure the concentration of Khalil et al., 2017
H2S in the range of 0-200 ppm with a detection limit as low as
1 ppm.
Hyperpolarized silicon It is a nanosensor that provides a novel tool for measuring and Rezaeyan et al., 2018
NPs imaging hydrocarbon reservoirs.
Magnetic (Fe2O3) NPs It detects flood front, fluid contact, hydrocarbon bypass and Agista et al., 2018
fracture.

14
Fig. 5 Representation of oil detection using nanoreporters: (a) Nanoparticles holding hydrophobic cargo are
introduced into the subsurface (b) As they are scattering in the subsurface, nanoreporters run into oil and free the
hydrophobic cargo into the hydrocarbon (c) The nanoreporters are retrieved and analyzed and examined for the
presence of the cargo; the extent of hydrocarbon is determined by the extent of the cargo absence (modified
after El-Diasty and Ragab, 2013).

3.2. Production technology

Taking a quick look at the past few years, it can be seen that the conventional oil and gas
resources and reserves are difficult to explore and produce from them. Due to the limited
conventional oil reserves, a large number of companies have started to exploit and produce
the unconventional oil resources such as heavy and extra heavy oil, tight gas and oil, coal bed
methane, and shale gas and oil as well as bitumen hydrocarbons (Khalil et al., 2017).
Recovery of unconventional oil is considered as one of the most serious challenges because
of the presence of sulfur, oxygen, nitrogen, and metals as well as the nature of their physical
and chemical properties such as viscosity and density (Li et al., 2013; Khalil et al., 2017).
Apparently, heavy oil and bitumen exist in large quantities. Li et al. (2013) claimed heavy oil
and bitumen constitute about 70% of the remaining 10 trillion barrels of oil worldwide, and
this makes the recovery more challenging. Along with the high viscosity of the heavy oil,
there happen numerous problems during the production process that give rise to a reduction
in production efficiency (Agista et al., 2018). A promising technology, nanotechnology, can
make the hydrocarbon harvesting easier and more abundant (Bera and Belhaj, 2016).
Shokrlu and Babadagli (2010) stated that in order to recover the unconventional reserves, i.e.,
heavy oil and bitumen, extensive reservoir heating is required. Such heating techniques
include steam and air injection and/or unconventional methods like electrical and
electromagnetic methods. For instance, aquathermolysis, which is a series of reactions

15
occurring to alter the physical properties of the hydrocarbons, can present and give great
impacts including reduction of asphaltenes and resins, increase of aromatics and saturates,
decrease in sulfur content and the produced oil viscosity reduction (Shokrlu and Babadagli,
2010; Maity et al., 2010). To provide a better insight into this, Muraza and Galadima (2015)
conducted a research study to find one of the ways to produce from unconventional reserves
through aquathermolysis process in which catalysts, such as nano oxides of copper and iron,
Ni-chelates supported by nano-iron particles and Cu2+ and Fe3+ complexes, were used to
break the C-C, C-O, and C-S bonds, and they figured out that the viscosity of the heavy oil
was highly reduced. Afterward, the heavy oil was converted to lighter and less viscous oil
components that were producible. Additionally, Kong and Ohadi (2010) reported that nano-
catalysts might also propose a solution for improving the properties of heavy oil and bitumen.
Li et al. (2016), on the other hand, also conducted an experiment investigating the role of
nano-nickel catalysts in reducing the viscosity of heavy oil, and they eventually found that
these nano-sized catalysts had the ability to fulfill their duty.
One of those problems that can arise in the production process is the asphaltenes
precipitation. The formed solids can be either removed mechanically or by adding additives
that contain TiO2, SiO2, and ZrO2 nanoparticles forming nanofluids to inhibit the
precipitation of asphaltene. Mixing TiO2 nanoparticles to the asphaltene at acidic conditions
may improve the stability of the asphaltene nanoaggregates by forming a hydrogen bond
(Mohammadi et al., 2011). Another challenge that occurs is the formation and precipitation of
wax crystals which increases the viscosity of the oil entrapping the oil in the reservoir or
accumulating them in the pipe during production (Sun et al., 2017; Agista et al., 2018).
Interestingly, pour-point depressants have the ability to solve this problem, and recently a
researcher created a new type of hybrid PPDs based on POA functionality and
POA/nanosilica hybrid particles. They discovered that the POA/nanosilica hybrid particle
system gives spherical shapes for wax precipitation resulting in a compact precipitate
structure, and this enhances the flowability of the waxy oil (Sun et al., 2017). An amazing
application of nanotechnology is the optimization in the production of oil and gas from shale
and tight reservoirs through hydraulic fracturing and fracking technique (Li et al., 2016;
Khalil et al., 2017). Li and co-workers (2016) defined hydraulic fracturing as the process of
stimulation hydrocarbon-producing wells in order to enhance the production in reservoirs of
low permeability or damaged wells. This is executed by injecting a fracturing fluid under
pressure so as to produce and generate a fracture or fractures into the rock formation (Barati
et al., 2012). The viscosity and stability of the fracturing fluid are important, for instance,
16
foam fracturing fluids have a high viscosity which provides them astonishing proppant
transportability, and using nanoparticles in them gives further stabilization (Lv et al., 2015).
In matrix acidizing, one of the major challenges is the delivery of the acid into the targeted
zone with no, or little, damage to the wellbore and surface facilities. One excellent way to
solve this problem is to use nanoparticle-stabilized double emulsions. Such double emulsions
could be an excellent well stimulating agent (Ko and Huh, 2018).

3.3. Enhanced oil recovery

The rapid increase in energy (oil) demand and extracting crude oil, the resources of global oil
have to be used as efficiently and competently as possible, and more oil is to be recovered
(Rychlicki, et al., 2006; Landa-Marbán et al., 2017; Ketzasmin, et al., 2017; Underwood et
al., 2015; Ali and Stephen, 2018). It has been proved that after exploring and detecting a
petroleum reservoir about 15-50% vol. of the oil in the reservoir can be retrieved and
recovered by maintaining initial reservoir pressure using first and second oil recovery
methods (Rychlicki et al., 2006; Mohd et al., 2016; Landa-Marbán et al., 2017). However,
50-85% vol. of the original oil in place remains in the reservoir after primary and secondary
recovery methods (Underwood et al., 2015; Mohd et al., 2016; Landa-Marbán et al., 2017;
Gbadamosi et al., 2018b). There are various methods to optimize rates of oil recovery and to
increase the production efficiency; one of the most effective ways is the employment of more
developed and advanced methods, such as enhanced oil recovery (Rychlicki et al., 2006;
Mohd et al., 2016; Landa-Marbán et al., 2017; Kamaei et al., 2019). EOR, which stands for
enhanced oil recovery, is a method for recovering hydrocarbons by injecting materials that do
not normally belong to or are not typically present in the reservoir (Sengl et al., 2006; Agi et
al., 2018).

17
Fig. 6 Categories of enhanced oil recovery technologies.

Mohd et al. (2016) and Gbadamosi et al. (2018b) reported that according to the injectant type
injected, enhanced oil recovery is usually categorized as chemical (surfactant flooding),
(Sengl et al., 2006; Bera et al., 2017), thermal, gas and microbial (Landa-Marbán et al.,
2017). Thermal methods mainly introduce heat into heavy oil reservoirs by various methods,
such as cyclic steam simulation (CSS), steam flooding and steam-assisted gravity drainage
(SAGD), to better the flow ability of the heavy oil or bitumen in reservoirs by changing its
physical properties (viscosity and density) (Thomas, 2008). Gas methods utilize hydrocarbon
gases (CH4, C3H8 or natural gas) or non-hydrocarbon gases (N2 or CO2) that dissolve in oil. In
this way, the injected gas can improve oil recovery by decreasing oil viscosity and expanding
oil volume (Sun et al., 2018). Chemical methods mainly involve the use of long-chained
molecules called polymers to increase the effectiveness of waterflood, or the use of detergent-
like surfactants to help lower IFT that often prevents oil droplets from moving through a
reservoir as shown in Fig. 7 (Mandal, 2015). In this figure, different categories of EOR are
shown with their sub-divided methods and related EOR mechanisms. For example, there are
different types of chemical EOR, such as alkaline, surfactant, polymer, ASP and micellar gas.
Which they can provide several EOR mechanisms in increasing the ultimate oil recovery
including IFT reduction, wettability alteration, mobility control and emulsification. Adil et al.
(2018) stated that the injected fluids in enhanced oil recovery processes tend to interact with
and have influences on rock/oil system of the reservoir. Lower interfacial tensions
(Ketzasmin et al., 2017; Bera et al., 2017; Bahraminejad et al., 2019), wettability alteration
(Bera, et al., 2017; Asl et al, 2019; 2020), oil swelling, oil viscosity reduction and/or

18
favorable phase behavior might be resulted from the interactions. The following Fig. 7 shows
the EOR technologies.

Fig. 7 Application of nanotechnology in EOR.

A new technology that has recently attracted attentions is smart fluids (nanofluids), which are
used in enhanced oil recovery (Evdokimov et al., 2006; Mahmood et al., 2017; Abhishek et
al., 2018). Smart fluids can help drilling by giving better wettability alteration, binders for
sand consolidation and advanced drag reduction (Chaaudhury, 2003; Hendraningrat et al.,
2013). Moreover, the introduction of nanoparticles has led to and generated thin film
nanocomposite membranes concept, which offers novel potentials, like reduced fouling (Liu,
2016). By nanotechnology new metering techniques with tiny sensors have been developed to
provide improved information about the reservoir and nano-catalysts may also offer a
solution for an on-site upgrading of bitumen and heavy crude oil (Ying et al., 1997). It is
worth saying the most parts of nanoparticles are in the early stage of research and laboratory
development of the petroleum industry (Saleh, 2017). Fig. 8 summarizes the applications of
nanotechnology in EOR. As is clear, nanopartciles have several usages in EOR dependent on
their types, for instance, nanofluids can be used to to reduce IFT, alter the wettability, provide
better emulsion and improve the viscosity. While, nano-emulsion can have benefits in
improving a better stability and control the mobility. In addition, nano-catalyst can reduce the
viscosity of oil.
Vryzas and Kelessidis (2017) found that the nanoparticles in the nanofluids have the ability to
construct ordered structures, called wedge-shaped film, on contact line with oil phase as
shown in Figs. 9 A and 10. This film spurs the nanofluid spreading throughout the surface

19
(Hendraningrat and Torsæter, 2014). Ehtesabi et al. (2013) investigated and found that this
process was produced due to the induced structural disjoining pressure by the nanoparticles.
The structural disjoining pressure is related to the ability of a fluid to scatter and disperse
throughout the surface of a substrate owing to the difference in interfacial forces between the
oil and the solid phases (Hendraningrat and Torsæter, 2014; Afolabi and Yusuf, 2018). Pore
channel plugging is one of the favorable outcomes of using nanoparticles in EOR (Ali et al.,
2018). Vryzas and Kelessidis (2017) shed light on the two major mechanisms that cause pore
channel plugging: mechanical entrapment and log-jamming (see Fig. 9B). Afolabi and Yusuf
(2018) stated that nanoparticles have the ability to give rise to a phenomenon called
mechanical entrapment: a phenomenon that can be perceived when the size of the pore or
pore throat of the formation is smaller than the size of the nanoparticles. On the other hand,
pore channels plugging occurs due to log-jamming when the accumulation of nanoparticles of
the nanofluids moving through pores to pore throats takes place (Vryzas and Kelessidis,
2017). The accumulation occurs due to the increased velocity of the nanofluids, which caused
by the differential pressure and flow area narrowing, giving a faster flow to small H2O
molecules and leaving the nanoparticles behind. This accumulation produces additional
pressure in the neighboring pore throat and hence pushing the oil droplets trapped in the
pores (Afolabi and Yusuf, 2018). Rock wettability, which is a crucial parameter to manage
recovery of oil, is defined as a fluid’s tendency to adhere to the surface of rock contending
with another immiscible fluid (Vryzas and Kelessidis, 2017; Ali et al., 2020). Oil recovery
can be enhanced by changing wettability from oil-wet to water-wet (Nazari et al., 2015; Al-
anssari et al., 2018; Zargar et al., 2019). The addition of nanoparticles to the used fluid has a
tremendous effect. Cheraghian and Hendraningrat (2016) reported that the rock surface can
absorb nanoparticles causing changes in the level of the rock wettability, as illustrated in Fig.
9C. Asphaltene precipitation along with mechanical or chemical processes can head to some
problems like reduction of effective permeability and blockage of transportation pipelines,
and therefore a solution should be sought (Guo et al., 2011; Vryzas and Kelessidis, 2017). As
it can be seen in Fig. 9D, in the presence of nanoparticles, nanoparticles adsorption onto the
surface of asphaltene molecules can occur, and this reduces the flocculation of asphaltene in
the porous medium (Vryzas and Kelessidis, 2017).

20
Fig. 8 Mechanisms of nanofluid within the porous media.

Fig. 9 The disjoining pressure at the oil droplet nanofluid interface.

Nowadays, several types of nanoparticles were used to achieve the above mentioned EOR
mechanisms (Table 3). The impact of some NPs on IFT reduction, contact angle decrease and
oil recovery improvement used by numerous researchers from 2009 to 2019 are illustrated in
Figs. 11-13. Naziri et al. (2015) examined the extent of the effect that MgO nanoparticles
would have on the wettability of Carbonate core. In their experiment, they measured the
contact angle between a mixture of 0.5gr of MgO and 10 mL of SPAN83. Prior to applying
the nanoparticle, the contact angle was 140.2°, but after using the MgO nanoparticle it was
reduced to 98.2°. In part of their experiment, Moslan et al. (2017) added zirconium oxide
21
with weight concentration 0.05 wt% to CTAB (cationic surfactant), SDS (anionic surfactant)
and TX-100 (non-ionic surfactant) for measuring and presenting the effects of ZrO2
nanoparticle on IFT and contact angle in carbonate dolomite. The results revealed that IFT
reduced to 1.85, 2.78 and 2.64 in CTAB, SDS and TX-100, respectively. Likewise, with the
addition of ZrO2, the contact angle reduced to 60° in CTAB, 84° in SDS and to 71° in TX-
100. Alnarabiji et al. (2016) conducted a test on Glass micromodels using hydrophobic multi-
wall Carbon Nanotubes. They used three different concentrations of nanoparticles which
were (0.01, 0.05, and 0.1) wt% and mixed each of them with 0.3wt% of brine. The purpose of
their experiment was to observe the effect of nanoparticles on the recovery of Residual Oil
in-Place (ROIP). The maximum recovery efficiency obtained was 31.8% ROIP with the 0.05
wt%, with the other recovery efficiencies being 29.2% with the 0.01wt% and 23% with the
0.1wt%. According to Azarshin et al. (2017), SiO2 was pecked and added to this solution and
the mixture of ethanol while being sonicated and stirred vigorously and have been selected to
be used on Glass micromodels were used as porous media. In this experiment 1ml of APTS
was dissolved in EtOH (200 ml) in a beaker. Then, 10 g SiO2 was added to this solution. The
state of wettability between silica NPs injected water and the rock surface. Results
demonstrate that the contact angle decreases from 134.4 to 54.52 in the presence of 0.25 wt%
silica NPs. The IFT between injected water and crude oil is one of the other parameters which
affect the sweep efficiency. Experimental results show that in the presence of only 0.25 wt%
FSNPs, the IFT decreases up to 68% from 37.5 to 22.1 mN/m.

100

90

80
IFT reduction (%)

SiO2
70
AL2O3
60 TiO2
ZrO2
50
HLP
40 ZnO
30

20
2008 2010 2012 2014 2016 2018 2020
Time (year)

22
Fig. 10 Rduction percentage of the interfacial tension using different nanoparticles from 2009 to 2019 (Ju et al.
2009; Yoon et al. 2012; Roustaei et al. 2012; Joonaki and Ghanaatian, 2014; Zargartable et al., 2014; Bayat et
al., 2014; Hendraningrat et al., 2013; Esmaeilzadeh et al., 2014; Azarshin et al., 2017; Emadi et al. 2017;
Moslan et al., 2017; Ali et al., 2019b).

In addition, Hendraningrat and Torsæter (2014) conducted a series of experiments involving

the use of metal oxide nanoparticles in brine dispersion in sandstone cores for calculating
their effect on enhancing recovery factor. As the NPs and Povidone, a polyvinylpyrrolidone
stabilizer, were mixed, it was found that the total recovery increased significantly. With
initial water saturations 19, 20 and 32%, the total recoveries were found to be 66, 77 and 74%
using Al2O3, TiO2 and SiO2 nanoparticles, respectively. Joonaki and Ghanaatian (2014) used
sandstone core plugs in their laboratory experiment for determining the effects of different
nanoparticles of various concentrations dispersed in propanol on measurements of contact
angle, interfacial tension and oil recovery. The results showed that the IFT reduced from 38.5
dynes/com to 2.25, 2.75, and 1.45 dynes/cm after employing Al2O3, Fe2O3, and SiO2
nanofluids, respectively. Moreover, the addition of SiO2 NPs amongst the other NPs affected
the contact angle measurement the most. Furthermore, after employing Al2O3, Fe2O3, and
SiO2, the results showed that the extra oil recoveries were 92.5%, 88.6%, and 95.3%,
respectively.
In terms of oil recovery, the results of the set of experiments of Ogolo et al. (2012) showed
that only hydrophobic silicon oxide and silane treated silicon oxide had given positive results
with ethanol as the dispersing medium. In the case of brine as the dispersing medium,
aluminum oxide had given the best result. Roustaei et al., (2012) treated the surface of a
sample of sandstone core plug with NWP and HLP nanoparticles, and they found that the
contact angle reduced to 81.88° (HWP) and 95.44° (HLP). Meanwhile, they observed that in
the presence of nano-HWP and nano-HLP fluids, the interfacial tension reduced to 2.55
mN/m and 1.75 mN/m, respectively. Ali et al., (2018a) examined and identified that
ZnO/SiO2 nanocomposite coated by Xanthan reduced IFT tremendously to 2.547 mN/m as it
was added to distilled water, and 2.016 mN/m to LoSal water.

23
 100

90 SiO2
AL2O3
80
CA reduction (%)

TiO2
70
ZrO2
60 HLP
50 MgO

40

30

20

10
2008 2010 2012 2014 2016 2018 2020
Time (year)
Fig. 12 This chart shows the impact of different nanoparticles on the contact angle reduction (Ju et al. 2009;
Wasan et al. 2011; Giraldo et al., 2013; Joonaki and Ghanaatian, 2014; Hendraningrat and Torsæter, 2014;
Bayat et al., 2014; Nazari et al. 2015; Azarshin et al. 2017; Maurya et al. 2017; Moslan et al., 2017; Ali et al.,
2019b).

60
Oil recovery improvment (%OOIP)

SiO2 AL2O3 MgO

50

40

30

20

10

0
2008 2010 2012 2014 2016 2018 2020
Time (year)
Fig. 13 Improvement in oil recovery using different nanoparticles from 2009 to 2019 (Ju et al. 2009; Maghzi et
al. 2011; Wasan et al. 2011; Latiff et al.2011; Ogolo et al. 2012; Zaid et al. 2013; Sharma et al. 2016; Tajmiri et
al. 2016; Liu et al. 2016; Jafarnezhad et al., 2017)

24
Table 3. Summary of the studies about nanomaterials in EOR processes.

Type of NPs NPs Concentration Dispersion IFT (mN/m) Contact angle o Pours media EOR (%) Reference
media Ref. With NPs Ref. With NPs
Metal oxides Aluminum oxide NPs (Al2O3) 0.5-3 g/L Propanol 38.5 2.25 131 92 Sandstone rocks 92.5 Joonaki and Ghanaatian
nanoparticles (2014)
Iron oxide NPs (Fe2O3) 0.5–3 g/L Propanol 38.5 2.75 132.5 101 Sandstone cores - Joonaki and Ghanaatian
(2014)
Nickel oxide NPs (NiO) 15.295 vol% Brine - - - - Carbonate cores 7.592 Haroun et al., (2012).
Magnesium oxide NPs (MgO) 0.05 g/10 ml Span83 - - 140.2 98.2 Carbonate cores - Nazari et al., (2015).
Copper II oxide CuO 17.464 vol% Brine - - - - Carbonate cores 14.07 Haroun et al., (2012).
TiO2 NPs 1wt% Brine - - 125 90 Core-flooding 80 Ehtesabi et al., (2013).
Zinc oxide NPs (ZnO) 0.05-0.5w% SDS 27.43 18.65 - - Core-flooding 11.82 Soleimani et al., (2018).
Zirconium oxide NPs (ZrO2) 0.05 wt% TX-100 9.13 2.64 85 71 Carbonate dolomite - Moslan et al., (2017).
Zirconium oxide NPs (ZrO2) 0.05 wt% SDS 9.88 2.78 92 84 Carbonate dolomite - Moslan et al., (2017).
Organic Hydrophobic Multiwall Carbon 0.01, 0.05, 0.1 Brine - - - - Glass micromodels 29.2, 31.8, Alnarabiji et al., (2016).
nanoparticles Nanotubes (HMECTs) wt.% 23.0
Nanoparticle-Stabilized CO2 50 vol.% - - - - - Glass micromodels 15 IOIP Nguyen et al., (2014).
Foam
Inorganic SiO2 NPs 0.5–3 g/L Propanol 38.5 1.45 134 82 Sandstone cores - Joonaki and Ghanaatian
nanoparticles (2014).
HLP 0.05 wt% Surfactant 18.4 5.4 - - Quartz plate 29.5 RF El Shafey, (2017).
hydrophobic silica 0.2-0.3wt% Ethanol - - - - Sandstone cores 50 Ogolo et al., (2012)
hydrophilic silica 0.01, 0.05, and Brine (NaCl - - - - Berea Sandstone 53 Ogolo et al., (2012)
0.1wt% 3wt%) cores
HLP 4 gr/L Ethanol 26.3 1.75 135.5 95.44 Sandstone cores - Hendraningrat and
Torsæter, (2014)
NWP 4 gr/L Ethanol 26.3 2.55 135.5 81.88 Sandstone cores - Roustaei et al., (2012)
SiO2 NPs 1–4 g/L Brine 26.5 1.95 135.5 66 Sandstone cores - Joonaki and Ghanaatian
(2014).
SiO2 NPs 10gr/200ml Ethanol 37.5 22.1 134.4 54.52 Glass micromodels - Azarshin et al., (2017).
SiO2 NPs 0.5-3g/L Brine 38.5 1.45 134 82 Carbonate cores - Ali et al., (2019b).
SiO2 + ZnO NPs 2000 ppm Distillate 31.8 2.547 - - - - Ali et al., (2019b).
water
SiO2 + ZnO NPs 2000 ppm seawater 28.312 2.016 - - - - Ali et al., (2019b).

25
3.4. Drilling Technology
Drilling operation is one of the most essential and critical processes in accessing the
hydrocarbons down in the reservoir rocks (Ponmani et al., 2013; Khalil et al., 2017).
Extracting oil and gas involves the digging and boring a hole of a few inches, with the aid of
a drilling bit attached to drillstring, into the reservoir rock in the subsurface (Vryzas and
Kelessidis, 2017). To be more specific, every rotary drilling operation consists of three core
systems that function simultaneously at the time of drilling, and these systems are rotary
system, hoisting system and circulating system (Al-Yasiri and Al-Sallami, 2015). Vryzas and
Kelessidis (2017) explained the process as follows: the bit crushes and grinds the rock into
small pieces called the cuttings; next, the cuttings are brought to the surface through the drill
pipe with the help of drilling fluid; then the cuttings and drilling fluid are separated from each
other by the means of separation equipment; finally, the drilling fluid is circulated back to the
well using powerful pumps. Therefore, effective development in drilling operation plays a
vital role in the optimization of hydrocarbon productivity (Khalil et al., 2017). Al-Yasiri and
Al-Sallami (2015) reported that there are various definitions for drilling fluid, and they also
reported that several experts had defined a drilling fluid as a mixture of fluid and additives
that removes the cuttings from a wellbore. Selecting the suitable and right drilling fluid and
maintaining the desirable properties in them is important for a successful drilling operation
because they enhance the oil recovery and decrease the amount of time it takes to extract the
first drop of oil (Kasiralvalad, 2014, Al-Yasiri and Al-Sallami, 2015). On the other hand, in
efficacious drilling process is dependent highly on the used drilling fluid’s effectiveness
(Vryzas and Kelessidis, 2017).
One of the other crucial processes is cementing. Jafariesfad et al. (2017a) defined primary
cementing as the process of mixing cement slurry and water and pumping it down into the
annulus between the casing and formation. Providing a complete zonal isolation is the main
objective of primary cementing in order to prevent the occurrence of fluid migration
(Rahimirad and Baghbadorani, 2012; Lavrov and Torsæter, 2016). The zonal isolation is
helpful in ensuring the safety as well as preventing environmental problems (Jafariesfad et
al., 2017a). The cured cement must also act as a mechanical support for the casing (Agofack
et al., 2018) and protect it from attacks by corrosive fluids (Nygaard, 2010). Additionally,
selecting the materials to be used and the procedure to be followed for the cementation is the
key factor in insuring a successful hydrocarbon production (Khalil et al., 2017).
During the drilling and completion operations a large number of problems may occur and
leave negative economic and environmental impacts. Like every other industry, oil and gas
26
industry can benefit from the use of the novel technology, nanotechnology, in order to solve
these problems (Al-Yasiri and Al-Sallami, 2015). Nanotechnology can be used in many fields
of oil and gas industry such as drilling fluid and tools and cementation (Bera and Belhaj,
2016) to prevent the lost circulation, wellbore instability, pipe sticking and recovery
efficiency (Al-Yasiri and Al-Sallami, 2015; Peng et al., 2017). Likewise, well cementing is
not out of problems. Wellbore failures and well integrity problems because of cementing and
cementing stability problems are regarded as one of the serious difficulties in the petroleum
exploration and production (Khalil et al., 2017). For instance, the poor performance due to
the natural brittleness, low tensile strength as well as bulk shrinkage of the conventional
cement-based materials has called for the use of developed nanotechnology for the well
cementing process, and this advanced technology has the ability to improve the mechanical
properties of the cement sheath, to accelerate the cement hydration and to prevent gas
migration (Jafariesfad et al., 2017a). Table 4 shows the influences of nanoparticles in
different drilling applications.
Nanotechnology has another potential application which is in the designing and developing
tools and equipment in the oil and gas industry (Amanullah and Ramasamy, 2018). There are
several tools, e.g., drill pipe and drilling bit, used in the drilling process. These tools are
sometimes subjected to loads and forces, i.e., friction, and high temperatures, that cause them
to be deteriorated, damaged and worn. Recently, nanoparticles and, in the last couple of
years, nanocomposites attracted a lot of attention and emerged in the industry owing to the
superb physical, chemical, mechanical and electrical properties (Amanullah and Ramasamy,
2018). Application of nanotechnology in the drilling tools can extend the lifetime of the tools
by improved corrosion and wear resistance property of the nanomaterials used (Nabhani and
Emami, 2012).

27
Area Author NPs Concentration Outcome
Drilling Pan et al., 2016 Micro-arc0.5-2 g/L The coating prevents the oxidation of aluminum
tool oxide and the corrosion rate was reduced from
0.032g.m2.h-1 to 0.024g.m-2.h-1
Drilling Ragab and Noah, 2014 Nanosilica 20-30 wt% Reduces up to 56% of the fluid loss compared to
fluid ordinary drilling fluids.
Sadeghalvaad and TiO2 NCs 14 gr Less mud thickness and enhanced fluid loss
Sabbaghi, 2015 treatment up to 64% compared to conventional
drilling fluids.
Vryzas et al., 2015 Fe2O3 0.5 w/w %. Reduction in filtration loss.
Vryzas et al., 2015 SiO2 0.5-1.5% (w/w) Increased the filtration volume.
Ismail et al., 2016 SiO2 0.01 gr Reduce filtration.
Ismail et al., 2016 MWCNT - Decreasing filtration and reduce mud cake.
Mahmoud et al., 2016 Ferric 0.5%wt. Increased the filtration loss and mud cake
Oxide+SiO2 thickness.
Mahmoud et al., 2017 Ferric NPs 0.3-1.0 wt% Reduce mud cake thickness.

Vryzas and Kelessidis, Calcium 0.5 wt% Reduce fluid loss considerably and produce a
2017 NPs thinner filter cake, and hence reducing the
permeability.
Table 4 Summary of nanotechnology applications in drilling operations.

3.4.1. Cementing
The cement is able to perform its job efficiently when a proper cement job has been executed,
otherwise various problems may arise since the cement will experience harsh conditions;
such as, being exposed to extreme temperatures and pressure (Fridriksson, 2017; Nelson et
al., 1990; Choolaei et al., 2012). Alkhamis (2018) reported that variations in temperature and
pressure causes cement to shrink, leading to an incomplete zonal isolation. Several NPs were
used to improve the properties of cement slurry as shown in Table 5. In a study, Jafariesfad et
al. (2017b) added different amounts of nanorubber with various sizes ranging from 50 nm to
100 nm to a Class G cement with a (W/C) of 0.44. The experimental results revealed that the
addition of 8% nanorubber caused reductions in the cement shrinkage after different periods
of time. Polat et al. (2017) also observed less cement shrinkage in their case study when they
investigated the impact of MgO nanoparticles on a Portland cement. Other problems such as
insufficient cement-formation bond and insufficient cement-casing bond arise if the cement
does not have enough strength (Parker et al., 1966). In several cases, adding nanoparticles to
the cement formulation, boosted its compressive strength and accelerated the time needed for
developing the strength. In a comparative study by Alias et al. (2014) on the effect of raw rice
husk ash, synthesized nanosilica from RHA and commercial nanosilica on the compressive

28
strength and porosity of a Class G cement with a (W/C) of 0.5 showed that the cement with
commercial nanosilica showed superior properties to its counterparts, in which a 1.5%bwoc
of the commercial nanosilica reduced compressive strength development time, increased
maximum compressive strength and reduced porosity which lead to prevent fluid migration.
In a recent investigation by Mohammed (2018) on silica nanoparticles, different amounts of
30 nm-sized nanosilica were added to a class H cement with a (W/C) of 0.38. The test results
showed that the cement with 1%bwoc nanosilica had a higher maximum compressive
strength, a faster compressive strength development and improved electrical resistivity
properties. In another work, Souza et al. (2015) examined the outcome of adding carbon
nanotubes to a Brazilian type CPV cement with a (W/C) of 0.4. The resulting cement attained
more compressive and tensile strength, less porosity and permeability and an improved
stability. Filtration of cement slurry and cement contamination by mud (Frigaard and
Pelipenko, 2003) are also very well-known issues which can eventually cause gas migration
(Pour and Moghadasi, 2007). For the case of filtration, Rabbani and Soltanian (2011)
conducted an experiment in which they mixed different amounts of 20 nm silica
nanoparticles with a Class G cement with a (W/C) of 0.6 and observed that a small amount of
it made great changes in the cement properties, such as reducing fluid loss and permeability,
as a consequence preventing gas migration. The modified cement also had a higher maximum
compressive strength and a faster compressive strength development than the standard
cement.
Furthermore, to overcome mud contamination problems, Maserati et al. (2010) designed a
new cement spacer using nano-emulsion and investigated its cleaning performance (Fig.14).
The test results showed that the nano-spacer resulted in a better removal of drilling mud in
comparison to conventional cement spacers and wettability alteration causing a stronger bond
to form between cement and the casing. Addition of different types of nanomaterials into the
cement slurry leads to elevated performances of the cement, such as gas migration prevention
(Alkhamis, 2018), improved hydration process (Baig et al., 2017), enhanced sensing
properties (Vipulanandan et al., 2015), decreased filtration (Rabbani and Soltanian, 2011),
and providing more strength and earlier strength development; preventing collapsing of the
casing (Sun et al., 2016).

29
 Table 5. Summary of the nanoparticles used in oil and gas well cementing.
Types of cement NPs Size Conc. Outcome Reference
(nm) (BWOC)
Kerman Class G with Nanosilica 20 1% Less porosity and permeability, less density, improved rheological behavior, early Rabbani and Soltanian, 2011
W/C of 0.6 compressive strength development, more compressive strength, less thickening time, less
free-water development, and less fluid loss
Class H with W/C Nanosilica 30 1% Early compressive strength development, more compressive strength, early compressive Mohammed, 2018
0.38 strength development, and more compressive strength
Class G with W/C Nanosilica 10-20 1.50% Less porosity & permeability, more hydration, more density, improved electrical Alias et al., 2014
0.5 1.50% resistivity index, improved rheological properties, and early compressive strength
1.50% development
Class H with W/C Nano-Fe - 1% More compressive strength, less porosity and permeability, more density, early Vipulanandan et al., 2015
0.38 compressive strength development, and more compressive strength
Class G with W/C <100 2% Less porosity & permeability, more hydration, less free-water development, improved Baig et al., 2017
0.44 electrical resistivity index, and improved rheological properties
Class H with W/C Nano-Na - 1% Early compressive strength development, more compressive strength, more hydration, Vipulanandan and Amani, 2015
0.38 with 3% OBM carbonate less density, less shrinkage, and less free-water development
Class G with W/C Nano-rubber 50-100 2 - 4% Less stiff, more compressive strength, more tensile strength, early compressive strength Jafariesfad et al., 2017b
0.44 development, and more compressive strength
- Nano-MgO - 7.50% Less porosity & permeability, less shrinkage, more hydration, more density, and early Polat et al., 2017
compressive strength development
Class G with W/C NMK 75 6% More compressive strength, less porosity and permeability, more hydration, more Dawood 2018
0.44 density, and improved rheological properties
Class H with W/C Nano-clay 25 1% More stiff, early compressive strength development, more compressive strength, more Mohammed, 2018
0.38 hydration, same rheological properties, and more compressive strength
Brazillian type CP V CNT 21 0.30% More tensile strength, less porosity & permeability, more hydration, and improved Souza et al., 2015
with W/C 0.4 rheological behavior
Class H with W/C CNF 4-20 0.04% More hydration, less porosity & permeability, and more flexural strength Sun et al., 2016a
0.38
Class H with W/C CNF+GNP 20-30 0.04% CNF Improved rheological behavior, more compressive strength, more flexural strength, early Sun et al., 2016b
0.38 0.05 strength development, less porosity & permeability, and more hydration
Type V with W/C CNC 0.05-0.5 0.20% More flexural strength, improved hydration process, and improved rheological behavior Cao et al., 2014
0.35
Class H with W/C Nano-alumina - 0.10% More stiff, early compressive strength development, and more compressive strength Vipulanandan & Mohammed,
0.38 2018
---- Halloysite 30-70 1.50% More compressive strength, and more tensile strength Deshpande and Patil, 2017
nanotube

30
Fig. 11 Gas migration with conventional cement and with nanoparticles.

3.4.2. Drilling Tools

Drilling for hydrocarbon extraction calls for a drill string, which consists of drill pipe and
drill collar, in order to transmit the surface-provided torque to rotate the drilling bit and to
transmit the required load for drilling the formation (Nabhani and Emami, 2012). Obviously,
conventional drilling bits and drill pipes are worn due to abrasive formations and this leads to
the dramatic reduction of the drilling performance. An effective solution to this problem is
the wear resistance improvement of these tools (Amanullah and Ramasamy, 2018).
Furthermore, corrosion as one of the most serious problems can lead to the demolition and
deterioration of metallic structures, such as drilling tools, and this problem has to be
hampered; moreover, preventing corrosion in the petroleum industry is of great attention and
emphasis (Fakoya and Shah, 2017; Ali et al., 2019d). Manufacturing and constructing
superior drill bits from nanostructured coatings in order to improve abrasion and corrosion
resistance of the drilling tools is an excellent solution (Ponmani et al., 2014).
Properties of tools and platforms used whilst drilling onshore and offshore can be enhanced
against water and corrosion, endurance, abrasion and thermal conductivity by coating them
with a special type of nanoparticles (Kong et al., 2010). One of the inevitable problems
encountered whilst drilling process offshore is corrosion of aluminum-alloyed drill pipes. The
aluminum alloy interacts with the oxygen forming compacted Al2O3 layer. The coating
prevents the oxidation of aluminum. However, the corrosion occurs because of chlorination
process. The diameter of the chlorination is so small that it capable of penetrating the
oxidized layer and make an extension into the drill pipe. Thus, corroding the drill pipes and
impoverishing its quality. Uprising issue of the drill pipe corrosion can be treated by micro-

31
arc oxidation (also abbreviated as MAO). The metals are exposed to an electrolyte solution
containing layers of ceramic in the form of MoS2 nanoparticles under high temperature
effects. The corrosion rate was reduced from 0.032 g.m2.h-1 to 0.024 g.m-2.h-1 when the
addition of the number of nano-particles increased from 0.5g/L to 2g/L (Pan et al., 2016).
Aluminum alloys are used in horizontal well and ultra-deep wells onshore (Gwilliam,1999).
However, those pipes had drawbacks such as poor hardness and low salt corrosion resistance
that lead to corrosion and low strength. Therefore, in another paper work done by Liang et al.
(2018), an aluminum alloy 2618 was modified by a combination of two methods, micro-arc
oxidation (MAO) and ultrasonic cold forging technology (UCFT) that enhanced the quality of
aluminum alloy up to 94% compared to the conventional ones. Drill bits are worn and
corroded in harsh environments and HPHT whilst quarrying the formations. Thus, coating the
bits with certain types of nanoceramic coating can highly enhance the performance of the
drill bits and their lifespan (Agista, 2018). PDC nano diamonds are earning more popularity
in the gas and oil industry as it has shown great resistance against abrasion especially in
reservoir extreme conditions. Due to the small size of the nano diamonds, the surfaces have
high energy and they are controlled by gathering those energies into clusters of microns or
sub microns. This technique leads to the clusters formation and it would be more difficult to
exploit. Thus, the surfaces are chemically modified by attaching organic moieties at the
active sites and forming covalent bonds. The derivatization or functionalization of the
clusters on the molecular level make an even distribution of the nano diamonds and enhance
the performance with increasing lifespan of the bits (Chakarborty, 2012). In another research
done by Sengbuta et al. (2013) about coating the bits with nano ceramics, it has shown two to
four times increased strength compared to conventional bits against abrasion and wear in the
drill bits. Al2O3-TiO2 nano ceramics powder are sprayed by plasma coating method that
those coatings do not let the materials underneath to get affected. Therefore, re-coating of the
bits is a better and more possible alternative instead of changing the bits entirely. They are
commonly used in highly abrasive formations such as igneous rock.

3.4.3. Drilling Fluids

Various different drilling fluids have been formulated because of the numerous problems
faced during drilling operations. The principal elements in all the types of drilling fluids are
water, oil and gas (Al-Yasiri and Al-Sallami, 2015). A drilling fluid has various functions
including removing the cuttings from the wellbore and transporting them up to the surface
and stabilizing and supporting the wellbore, as well as lubricating and cooling the drilling bit
32
(Al-Yasiri and Al-Sallami, 2015; Annis and Smith, 1996; Khodja et al., 2010). In comparison
to the conventional drilling muds, nanofluids with water as the base have the ability to lessen
the formation damage, control loss circulation and increase penetration rate (Kasiralvalad,
2014). On the other hand, adding nanoparticles to drilling fluids promotes the rheological,
mechanical and thermal properties of the fluids (Al-Yasiri and Al-Sallami, 2015).
Consequently, nanotechnology can play the role in meeting the uprising needs for
accomplishing a successful drilling programs which is both cost and time effective especially
in the HPHT conditions.

3.4.3.1. Fluid Loss

In a study conducted by Sharma et al. (2016), some certain types of drilling fluids containing
Nano silica have been prepared to plug in the microcracks and treat water invasion in Mancos
and gas shale formations. Three samples of mud are prepared; type A is WBM brine which is
the base mud, type B contains pure nanoparticles, and type C contains a third of the amount
of the nanoparticles contained in type B mud sample. Pressure penetration test was used to
measure the effects of the three different types of mud. Results have shown as the amount of
the nanoparticles increase, the ability of the permeability plugging increases. Thus, type B
has shown the optimum results with 98% reduction in permeability and mud permeability of
0.0018 nDarcy. Hence fluid loss, borehole instability and water invasion can be highly
reduced 10 to 100 times. In another research done by Ragab and Noah. (2014), Nano silica in
concentrations between 20-30% wt. reduced up to 56% of the fluid loss compared to ordinary
drilling fluids.
Metal oxides are also used as additives in drilling mud to prepare Nano fluids. Moreover,
Sadeghalvaad and Sabbaghi (2015) prepared a nanocomposite from the polymerization of
acrylamide monomer with the presence of TiO2 nanoparticles. In their study, 14 grams of the
nanocomposite is added to 350 mL distilled water. Then the latter is mixed with 10 grams of
natural bentonite. The lab tests have shown less mud thickness and enhanced fluid loss
treatment up to 64% compared to conventional drilling fluids. In another research by Vryzas
and co-workers (2015), an experiment was done on the effects of using iron oxide (Fe2O3)
nanoparticles in drilling fluids concluded that the maximum amount of the nanoparticle that
has the ability to bring maximum reduction in filtration loss, which was 42.5% in comparison
to the base fluid alone, was 0.5w/w %. On the contrary, the addition of silica nanoparticles
increased the filtration volume considerably, for example, as silica nanoparticles with
concentrations 0.5% and 1.5% (w/w) were added, increases of 54.1% and 46.8% were
33
observed, respectively. In a lab experiment that was conducted by Ismail and his co-workers
(2016), it was found that addition of 0.01g of nanosilica to the drilling mud at the temperature
of 200°F provides 6.5 ml fluid loss which is the lowest. Furthermore, they also found that
using xanthan gum with 1 g of multi walled carbon nanotubes (MWCNT) at 200°F results in
a fluid loss of 4.9 ml and a mud cake thickness of 4 in. Additionally, Mahmoud and the co-
workers (2016) conducted an experiment searching for the influences of ferric oxide and
silica nanoparticles and their optimum concentrations on the fluid loss characteristics. The
results showed that adding 0.5% of ferric oxide nanoparticle to the mud exhibited the best
improvement by reducing the filtrate volume by 42.7% compared to the base fluid, and hence
this is the optimal concentration on the other hand, they investigated that the addition of silica
nanoparticles increased the filtration loss and mud cake thickness. In another experiment
done by Mahmoud et al. (2017) on the impacts of ferric oxide nanoparticles, they
experimented that the addition of ferric oxide nanoparticles with concentrations 0.3, 0.5 and
1.0 wt% could reduce mud cake thickness by 8.4, 21.9 and 38.7%, respectively, compared to
base fluid cake thickness. On the other hand, reduction of cumulative filtrate volume by 16.9
and 3.9% was observed for the mud with 0.3 and 0.5 wt% of ferric oxide nanoparticles, and
an increase by 15.6% was observed when the sample of mud contained 1.0 wt% of the
nanoparticle. Borisov and co-workers in 2015 discovered that drilling fluids combined with
lost circulation materials (LCM) and nanoparticles reduce fluid loss considerably and
produce a thinner filter cake, and hence reducing the permeability, and that is because
nanoparticles are capable of filling the tiny gaps between the micron-sized particles (see Fig.
15). In their experiment, they used calcium nanoparticles of 0.5 wt% concentration and this
resulted in the reduction of 22-34% of the total fluid loss.

34
Fig. 12. A pictorial illustration of drilling fluid loss during drilling in the case of LCM (left) and nanoparticles
(right) (Vryzas and Kelessidis, 2017).

4.4.3.2. Rheological Properties

In a research done by Sedaghatzadeh and co-workers (2012), MWCNT was used with
different concentrations to test the rheological properties and thermal conductivity of the
mud. An addition of 1% volume of CNT to the mud enhanced the thermal conductivity by
23.2% in comparison to the base mud. Moreover, the rheological properties such as annular
viscosity and yield point have been improved. The annular viscosity is increased as the depth
of the penetration is increased as shown in Fig. 16. This induces the formation rock fragments
lifting and helps cleaning the annular space of the well.
In another report done by Sadeghalvaad and Sabbaghi, (2015), characterization studies and
tests were conducted to investigate the effects of addition of TiO2/PAM of different
concentrations between 1–10 and 14 g in 350 ml distilled water. Results as shown in Fig. 17,
have shown adding 14 grams can highly increase the viscosity of the mud.

35
Fig. 13 A comparison between the yield point of a mud with CNT and the reference mud (Sedaghatzadeh et al.,
2012).

In another research done by William et al. (2014), an addition of 1% (by volume) of CuO and
ZnO nanofluids in synergy with aqueous Xanthan gum as an additive to WBM have shown
promising results. The thermal and electrical conductivity have been improved by 35%
compared to conventional WBM. The rheological properties are further investigated at
different temperatures varying from (25, 70,90, and 110 0C) and concentrations between (0.1
MPa and 10 MPa). Results show that pressure has the highest effect on the rheology at
elevated temperature in comparison with low temperature.

Fig. 14. The plastic viscosity of the NWBF at different concentrations over time (Sadeghalvaad and Sabbaghi,
2015).

4. Nanotoxicity
Despite the technological and commercial uprising of nanotechnology in many aspects with

their importance, their application is limited due to the fact they are so expensive to produce

36
and also to maintain (Jones and Grainger, 2019). The fact that they are in a tiny size with a

very high surface area that if exposed during the utilization and manufacturing inevitably

might make nanoparticles as a toxic material in the Oil and Gas sector (Bera and Belhaj,

2016). These nanoparticles are so small that can accumulate in single cells and easily

penetrate the cell wall (Arnot and Gobas, 2006). Some of the most widely studied

nanomaterials in the oil and gas sector are nanosilica and metallic oxide nanoparticles, that

have various effects on the human and the environment (Sarkar et al, 2019). One of the

implications of aluminum oxide, it can oxidize cells and prevent respiration, thus, causing

death of the organisms exposes (Prakash et al., 2011). According to Valdiglesias et al. (2013),

zinc oxide can produce reactive oxygen that damages the cell membrane, leading to DNA and

cell alteration. Additionally, titanium oxide can cause some interaction on the surface of the

cells that produces ROS, depolarization, plasma membrane leakage, intracellular calcium

influx, and cytokine secretion (Xiong et al., 2013; Ghosh et al., 2013). Being exposed to

nanosilica for the long term, can prompt the death of the cell bodies and lethal dose applied

because of these implications and the disadvantages that they have, nanoparticles have been

limited in their application in the oil and gas sector (McCarthy et al., 2012; Murugadoss et al.,

2017).

5. Detailed Summary
Thought out this study, the application of the nanotechnology in oil and gas industry, more

specifically in drilling engineering, can be summarized as follows:

• Nanotechnology is focused to be applied in oil and gas industry to improve oil

production, enhance the quality and resistance of drilling, production, logging and seismic
tools and increase the performance of drilling fluids and cementing.
• Researchers mostly focused on studying the application of nanotechnology in enhanced
oil recovery compared with other fields of petroleum engineering, such drilling,
production and exploration.

37
• Although commercial nanoparticles (such as SiO2, TiO2, Al2O3 and ZnO) showed a good
performance, researchers tried to design some specific nanoparticles called
nanocomposites, functionalized nanoparticles or coating nanoparticles (i.e.
ZnO/SiO2/Xanthan nanocomposites).
• SiO2 and TiO2 are the most effective and common types of nanoparticles which are used
in oil and gas industry.
• Nanosensors showed a good performance in imaging testing of the wellbore and
reservoir.
• Researcher tried to formulate a novel solution called nanofluid which is composed of
dispersing nanoparticles within the aqueous phase.
• The main mechanisms of the role of nanoparticles in enhanced oil recovery are the IFT
reduction and wettability alteration as reported by researchers.
• According to the studies, calcium and ferric oxide nanoparticles resulted a good
improvement in the performance of drilling fluids due to the fluid loss reduction
mechanism.
• Silica and ferric oxide nanoparticles fill in the micro and nanopores that exist in the
cement and provide the cement sheath with outstanding compressive strength.
• Organic nanoparticles such as a combination of CNF and GNP led to strengthening and
stuffing the cement sheath and also improved rheology of the cement slurry.
• The maximum reduction in the mud fluid loss is achieved with TiO2 by 65%, however,
the maximum reduction in the IFT and contact angle are also obtained with using TiO2
and SiO2 by 95% and 86%, respectively.
• The disadvantages include agglomeration of the particles in HPHT conditions, the high
cost and difficulty of manufacturing them, and environmental issues.

6. Conclusions
Many research studies on the application of nanotechnology in the oil and industry have been
performed and have shown promising results. Generally, the application of nanotechnology
in EOR to improve the ultimate oil recovery has been more widely studied compared with the
other fields, such as in exploration, drilling, production and refinery. Different types of
nanomaterials are used in the industry, such as nanoparticles, nanocomposites, functionalized
nanoparticles, coating-nanoparticles, nanotubes, nanosheets and nanosensors, but NPs are the
(i)
most common used type. NPs have some crucial features: a high surface area-to-volume

38
ratio and easily movable through porous media; (2) the potential to improve fluid
performance with only a small amount; (3) applicable in high-temperature conditions with the
improved heat and mass transfer; and (4) high dispersion stability when mixed with water,
alcohol, surfactants and polymers. According to the experimental studies, nanotechnology
has led to a great deal of improvements in the reducing the uncertainties in hydrocarbon
exploration, solving fluid loss problems of drilling mud, promoting cement compactness and
strength, increasing the efficiency of EOR mechanisms along with carrying out a more stable
stimulation job with less adverse effects all leading to a more fruitful production life.
Although almost all the researches are only being conducted in the laboratory and still not
converted to the field scale; nonetheless, more studies on nanotechnology will be carried out
in order to achieve the greatest output of them since the success rate of oil industry in the
future will be dependent on the advancements made in nanotechnology. It is recommended
that the researchers, from now on, focus more on the pursuance of the determination and
staging an optimum range of nanomaterials for acquiring desirable results.

List of Abbreviation
GPT GUID Partition Table OOIP Original Oil in Place
MWCNT Multi walled carbon SPIO Superparamagnetic iron
nanotubes oxide
EOR Enhanced Oil Recovery ASP Alkaline Surfactant Polymer
NPs Nanoparticles WAG Water Alternating Gas
NCs Nanocomposites LPG Liquefied Petroleum Gas
PMNC Polymer Matrix CSS Cyclic Steam Simulation
Nanocomposite CTAB Cetyl Trimethylammonium
CMNC Ceramic Matrix Bromide
Nanocomposite SDS Sodium Dodecyl Sulfate
CMC Ceramic Matrix Composites ROIP Residual Oil in Place
CNT Carbon nanotubes HMECT Hydrophobic Multiwall
PAM Polyacrylamide Carbon Nanotubes
IFT Interfacial Tension
39
HLP Hyper-crosslinked Poly MAO Micro-Arc Oxidation
styrene UCFT Ultrasonic Cold Forging
HWP Half-Wave Plates Technology
NWP Naturally Wet Polysilicon HPHT High Pressure High
CNF Carbon Nano-Faber Temperature
GNP Gold Nanoparticles SAGD Steam-assisted gravity
CNC Cellulose Nanocrystals drainage
MNK Nanoparticle-Modified
Kaolin

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Research Highlights

A critical review on application of nanotechnology in petroleum was done.

SiO2 and TiO2 can highly improve oil recovery compared with other nanos.

IFT reduction and wettability alteration are the main EOR mechanism of nanos.

Nanometrials can provide better compressive strength to cement slurry.

Nanomaterials can reduce the filtration rate of drilling mud and cement slurry.

Surface modified nanoparticles showed better performance in petroleum applications.

Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests: