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Nanotechnology Applied To The Enhancement of Oil and Gas Productivity and Recovery of Colombian Fields
Nanotechnology Applied To The Enhancement of Oil and Gas Productivity and Recovery of Colombian Fields
Nanotechnology applied to the enhancement of oil and gas productivity and recovery
of Colombian fields
PII: S0920-4105(17)30565-X
DOI: 10.1016/j.petrol.2017.07.004
Reference: PETROL 4090
Please cite this article as: Franco, C.A., Zabala, R., Cortés, F.B., Nanotechnology applied to the
enhancement of oil and gas productivity and recovery of Colombian fields, Journal of Petroleum Science
and Engineering (2017), doi: 10.1016/j.petrol.2017.07.004.
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Nanotechnology Applied to the Enhancement of Oil and Gas Productivity and
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1. Grupo de Investigación en Fenómenos de Superficie – Michael Polanyi,
Facultad de Minas, Universidad Nacional de Colombia-Sede Medellín,
Colombia.
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2. Grupo de Yacimientos, Vicepresidencia de Productividad, Ecopetrol S.A,
Bogotá, Colombia.
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*Corresponding authors: caafrancoar@unal.edu.co; fbcortes@unal.edu.co
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Abstract
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In Colombia, the estimated reserves of crude oil are approximately 2.0 thousand million
barrels, decreasing by approximately 13% in the last year according to the National
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demand for fossil fuels to supply energy requirements. Colombia is aware of this issue
progress in Colombia has been supported by academy – state – industry synergy, which
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has aimed to mitigate formation damage and enhance oil recovery to facilitate increases
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oil rate production. This document presents a review of the recent applications of
wettability from liquid-wet to gas-wet, and inorganic scales, among other applications),
mobility of heavy and extra-heavy oils), enhanced oil recovery (EOR) and heavy oil
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transport. Finally, three cases of field trials employing nanofluids are discussed for
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inhibiting the formation damage of asphaltene in tight-condensate reservoirs and light
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heavy and extra-heavy oils. It is expected that this document will aid in the alignment of
the academic and industrial sectors to pursue and incentivize the opening of a wider
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range of applications under field conditions through the extrapolation of laboratory
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studies.
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Nomenclature
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BSW Base sediments and water
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CHS Chemical Stimulation
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CMC Carboxymethyl cellulose
HO Heavy oil
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K Permeability
Kr Relative permeability
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Kro Relative permeability of water
MD Measured depth
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NP Nanoparticle
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OBN Oil-based nanofluid
PV Pore volume
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PVI Pore volumes injected
Q Injection rate
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Qo Oil rate production
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SP Softening point
W/O Water-in-oil
W/O/W Water-in-oil-in-water
XG Xanthan gum
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Contents
1. Introduction
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2.3.Inorganic scale formation damage
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2.5.Condensate banking
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3. Improving oil mobility under reservoir and surface conditions
3.2.On-site applications
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4. Nanotechnology for enhanced oil recovery (NEOR) applications
The world has faced a crisis in oil prices since 2014 due to oversupply. Therefore,
multiple nations, including Colombia, have elected to reduce their production and even
to close fields for which production costs exceed profits. This decision has generated a
reframing of the Colombian oil and gas industry based on investment in new strategies
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and/or technologies to improve the effectiveness of the production and transportation
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processes. In this sense, nanotechnology has recently emerged as an attractive topic of
research in the oil and gas industry due to its exceptional characteristics that allow
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nanoparticles to travel smoothly through porous media without additional risks of pore
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blockage due to their small size (1 – 100 nm), which can be used to avoid formation
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damage. At the nano-scale, exceptional properties can be obtained, such as a high
significantly enhanced because the functional groups on the material’s surface are less
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hindered as the size of the particle decreases. In other words, atoms on the surface of the
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nanomaterials are not surrounded by other atoms of the material and can therefore
Feynman (1960) entitled “There's plenty of room at the bottom”, in which he expressed
his desire to open a wider landscape in which the problems associated with
is a billion times smaller than a meter (1 × 10-9 m), approximately equivalent to the
diameter of a DNA chain (2.5 nm), one thousand times smaller than the mean size of a
bacterium, and a billion times smaller than a tiny droplet of water (National
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Nanotechnology Initiative). By definition, a nanomaterial is one with dimensions
between 1 and 100 nm; such as material can be classified as a nanoparticle, nanofiber,
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carrier fluid (Sheikholeslami and Ganji, 2016c). Nanotechnology has been applied in
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areas of knowledge such as energy storage, production, and conversion (Elmouwahidi et
al., 2017; Leschkies et al., 2007; Liu et al., 1999; Randviir and Banks, 2017; Rowell et
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al., 2006), agricultural productivity enhancement and food processing (Avella et al.,
2005; Cerqueira et al., 2017; Duncan and Singh, 2017; Grillo et al., 2012; Pérez de
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Luque and Rubiales, 2009; Ramesh et al., 2010; Sorrentino et al., 2007), water
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treatment and remediation (Anbia and Amirmahmoodi, 2011; Dasgupta et al., 2017;
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Franco et al., 2014a; Nassar, 2012), medicine (Bayford et al., 2017; du Toit et al., 2010;
Gupta and Jain, 2010; Jahangirian et al., 2017; Moghimi et al., 2005; Nie et al., 2007;
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Sumer and Gao, 2008; Wagner et al., 2006), air pollution and remediation (Cheng et al.,
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2006; Nakajima et al., 2000; Nel et al., 2006; Yu et al., 2017), heat transfer
and Ganji, 2017a; Sheikholeslami and Ganji, 2017c), construction (De Matteis et al.,
2017; Makar and Beaudoin, 2004; Sierra-Fernandez et al., 2017; Zhu et al., 2004), and
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pest detection and control (Bhattacharyya et al., 2010; Yang et al., 2009; Zhang et al.,
2017), among others. Nanotechnology is currently the focus of attention in the scientific
community, including the most recent Nobel Prize in Chemistry 2016, which was
awarded jointly to Jean-Pierre Sauvage, Sir J. Fraser Stoddart and Bernard L. Feringa
"for the design and synthesis of molecular machines" (Class for Chemistry of the Royal
heavy oils under both surface and reservoir conditions, among others. In Colombia,
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where the drilling and exploration operations have been reduced considerably due to the
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sector’s crisis, a need exists to develop new and cost-effective technologies that allow
the optimization of the available resources for preventing a national energy crisis in a
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short-term period. Thus, the academic sector, as aligned with the industry and the
respective state entities, has focused its efforts in the development of nanotechnology-
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based solutions. One of the primary applications of nanoparticles/nanofluids is the
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inhibition of various mechanisms associated with formation damage for improving the
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productivity of oil and gas wells. On this basis, the first field trial of nanotechnology
application was performed in the Cupiagua Field in Colombia and aimed at inhibiting
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compounds. Other research areas associated with formation damage that have been
studied are fines migration, condensate banking, damage in hydraulic fracturing and
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liquid-wet to gas-wet, and improvement of heavy and extra-heavy oil mobility, among
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damage inhibition has led to expansion in other applications. Indeed, due to the
nanoparticles/nanofluids have been proposed and include the reduction of oil viscosity
and the improvement of oil mobility under both reservoir and surface conditions. In
addition, nanotechnology has shown potential for enhancing the heat transfer efficiency,
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improved oil recovery (IOR) and enhanced oil recovery (EOR) processes and up to the
diluent reduction used for heavy oil (HO) and extra-heavy oil (EHO) transport.
Colombia, the industrial sector still lacks initiative for the implementation of most of
the proposed solutions in field trials, and (for some cases) implementation under field
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conditions. In the specialized literature, different authors have focused their efforts on
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the review of recent advances in nanotechnology to overcome different problems in the
oil and gas industry with emphasis on nanomaterial design (Khalil et al., 2017),
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application of silica nanoparticles (Fakoya and Shah, 2017), drilling (El-Diasty and
Ragab, 2013), heat transfer enhancement (Sheikholeslami and Ganji, 2016c), EOR
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(Cheraghian and Hendraningrat, 2016a; Cheraghian and Hendraningrat, 2016b), and in
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situ upgrading (Hashemi et al., 2014). Nevertheless, to the best of our knowledge, there
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are no reports of the development of field trials that include the use of nanotechnology
for oil productivity/recovery. Therefore, the primary objective of this work is to show
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the potential of nanotechnology applications and the current developments in the oil and
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nanoparticles/nanofluids. This review is divided into four main sections; the first section
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accounts for the description of studies focused on the inhibition and remediation of
damage, ii) formation damage by fines migration, iii) inorganic scale formation damage,
iv) drilling fluids and hydraulic fracturing fluids and, v) condensate banking. The
second section discusses the improvement of oil mobility under reservoir and surface
conditions. The third section surveys various nanotechnology solutions developed for
the improvement of enhanced oil recovery applications. Finally, the fourth section
nanofluids for enhancing oil mobility under reservoir conditions. It is expected that this
review will open a wider landscape for existent solutions based on nanotechnology for
the various problems faced by the oil and gas industry and the challenges and
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2. Inhibition and remediation of formation damage
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2.1.Asphaltene formation damage
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One of the most accepted technical definitions of formation damage is “any process that
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formation, or a reduction in the injectivity of a water or gas injection well” (Bennion,
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2002). In Colombia, different fields feature problems associated with different
fracturing operations, among other mechanisms (Zabala et al., 2016). Among these,
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problems to overcome. Asphaltenes are commonly defined as part of the heavy fraction
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of oil that is soluble in toluene, benzene, and pyridine but insoluble in n-alkanes such as
n-pentane, n-hexane, and n-heptane. Asphaltenes have in their structure metals and
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(Franco et al., 2015b; Mullins, 2010; Mullins, 2011; Mullins et al., 2012; Mullins and
Sheu, 2013). Formation damage by asphaltenes occurs when subsaturated oil reservoirs
lie at pressures above the bubble point (Franco et al., 2013c) and when self-associative
phenomena are promoted. At this stage, asphaltenes undergo exclusion from the oil
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matrix and subsequent deposition over the reservoir rock, which in turn results in a
blockage of the porous media and alteration of the wettability of the system.
In response, different approaches using nanotechnology have been studied; for example,
Cortés et al. (2012) and Franco et al. (2013a) studied the effect of supported
hygroscopic salts (SHSs) over silica and alumina nanoparticles, respectively, on the
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adsorption of n-C7 asphaltene. Silica and alumina nanoparticles were functionalized
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using the incipient wetness technique with different concentrations of 5.0 and 15.0 wt%
of aqueous solutions of nickel nitrate (Ni(NO3)2) and were then calcined at 460°C to
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obtain NiO nanoparticles on the surface. The mean crystallite size of the synthesized
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NiO nanoparticles varied from 15 (Cortés et al., 2012) to 29 nm (Franco et al., 2013a)
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depending on the nature of the support chemical. The authors employed model solutions
prepared with n-C7 asphaltene and toluene for the batch adsorption experiments. It was
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found that the SHSs tended to adsorb the n-C7 asphaltene from the model solutions with
higher efficiency for the nanoparticles functionalized with a higher amount of NiO with
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nanoparticles were able to reach the adsorption equilibrium in short times of less than
10 minutes (Franco et al., 2013a) and that the adsorption process of n-C7 asphaltene was
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Gibbs energy, enthalpy change and entropy change. Subsequently, Franco et al. (2013c)
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performed displacement tests under reservoir conditions for verifying the inhibitor
chemical nature. The results showed that high affinity in the adsorption leads to the
neutralization of the polar forces that remain active during weak adsorption and
damaged system and a treated system, in which the asphaltene damage was induced by
media. The treated system was simulated by injecting a defined dosage of nanoparticles
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simultaneously with the n-heptane injection. The authors observed that the oil relative
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permeability increased sharply after nanoparticle inclusion relative to the damaged and
blank systems, which was attributed primarily to the effect of nanoparticles in the
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prevention of asphaltene self-association and changes in the wettability of the porous
media (Franco et al., 2013c). This change in the wettability of the system was correlated
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with the saturation state, where the residual saturations of oil (Sor) and water (Swr)
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followed the order of damaged system > blank system > treated system and treated
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system > blank system and damaged system, respectively. The curves of cumulative oil
recovery indicated that a higher amount oil can be recovered after nanoparticle
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inclusion, indicating that in addition to their inhibitor effect, nanoparticles may act as
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stimulating agents.
Nassar et al. (2015a) and Betancur et al. (2016b) then demonstrated the effect of the
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evaluate the asphaltene mean aggregate size in the presence and absence of
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nanoparticles with different chemical nature using dynamic light scattering (DLS)
silica and magnetite in the reduction of the n-C7 asphaltene mean aggregate size in
different heptol solutions. The authors showed that the adsorption of n-C7 asphaltene
was dependent on the chemical nature of the adsorbate and that nanoparticles of
different chemical nature lead to different selectivities and thus different efficiencies on
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the prevention of n-C7 asphaltene self-association, with better performance exhibited by
the silica nanoparticles. Furthermore, Betancur et al. (2016b) evaluated the role of
particle size and surface properties of silica nanoparticles in the inhibition of formation
damage by asphaltene. The authors synthesized nanoparticles with sizes ranging from
11 to 240 nm; the total surface acidity values ranged from 1.07 and 1.32 mmol/g. Figure
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1a-c shows field-emission scanning electron microscopy images of the synthesized
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nanoparticles with mean sizes of a) 11, b) 58 and c) 240 nm.
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Figure 1. Field-emission scanning electron microscopy images of synthesized silica
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nanoparticles with mean particle sizes of a) 11, b) 58 and c) 240 nm. The silica
nanoparticles were synthesized through the sol-gel method, and different sizes were
obtained by varying the tetraethyl orthosilicate/water ratio. Adapted with permission
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The best results in the inhibition of asphaltene aggregate growth were found for the
materials with the highest adsorptive capacity with higher total surface acidity and
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lower mean particle size. It is expected that the nanoparticles will interact with the
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asphaltene moieties through acid centers, such as hydroxyl silanol (Si−OH), that would
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be more exposed as the size of the particles decreases at the same time that the smallest
nanoparticles diffuse easily in the model solutions and promote the scavenging of the
dissolved adsorbate (Betancur et al., 2016b). Figure 2 shows the effect of silica
Betancur et al. (2016b) confirmed that nanoparticles can inhibit asphaltene formation
relative to the results obtained by Franco et al. (2013c). In another study, Betancur et al.
with a silica shell can inhibit asphaltene formation damage and that the nanoparticles
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400 2000
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Mean
Amount adsorbed of n-C7
360 1800
n-C7
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asphaltene (mg/g)
11 nm
asphaltene aggregate
320 1600
size (nm)
particle
280
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154 nm
particle
240 1200
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58 nm particle
200 1000
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Figure 2. The influence of the particle size and surface acidity of silica
nanoparticles on the mean n-C7 asphaltene aggregate size. Adapted with permission
from Betancur et al. (2016b).
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was studied by Franco et al. (2015b) through the simultaneous construction of the
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results showed that although the amount of adsorbed n-C7 asphaltenes decreases as
the number of resin I in the system increase, the adsorption is always higher for n-C7
asphaltenes than for resin I for the different asphaltene-to-resin ratios that were
evaluated. The amount of n-C7 asphaltenes adsorbed in the presence of resin I was
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predicted successfully from the known amount of n-C7 asphaltenes adsorbed at a
defined A:R ratio; this model discarded any specific interactions between
asphaltenes and resins either in the bulk or at the surface. The results also suggest
problems.
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Recently, Guzmán et al. (2016) reported a methodology for the design of
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asphaltene-related treatments based on batch adsorption experiments. The authors
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physicochemical properties in adsorption tests in two different ways: (i) by exposing
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a certain mass of nanoparticles in a fixed volume of liquid with a varying initial
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concentration of asphaltenes and (ii) by exposing a given amount of asphaltenes in a
fixed volume of liquid while varying the dosage of nanoparticles. Guzmán et al.
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(2016) demonstrated that both methods used lead to different results in various
(2016) for n-C7 asphaltene adsorption onto silica nanoparticles at 25°C obtained
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through Method i for different ratios of the solution volume to the dry mass of the
nanoparticles for Methods i and ii. The importance of the type of adsorption
isotherms constructed using method (ii) relies on the fact that when treatments are
applied, the amount of asphaltenes present in a reservoir may remain constant. The
for tight condensate-reservoir and light oil crude, until its massification in other
fields. Field trials described in Section 5 below for the application of nanofluids for
asphaltene formation damage inhibition were developed based on the flow assurance
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and the nanoparticle design as described in the aforementioned studies.
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3
M = 5 g/L
M = 10 g/L
Amount adsorbed (mg/m2)
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2.5 M = 20 g/L
Ci = 500 mg/L
2 Ci = 1000 mg/L
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Ci = 1500 mg/L
1.5
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1
M
0.5
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0
0 100 200 300 400 500 600
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fixed mass of nanoparticles) and Method 2 (different mass of nanoparticles but fixed
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(2016).
Another common source of formation damage is the migration of fine particles; this
mechanism depends on several parameters, such as the wettability of the particle, the
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flow rate, the chemical nature of the migrating fine particles (Civan, 2015) and the
relationship between the particle size and the pore throat size (Bratli and Risnes, 1981).
to the bridging/blockage as follows: i) particles larger than 1/3 of the pore size are prone
to generate pore blocking, ii) particles in the range of 1/7 – 1/3 of the pore size produce
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a bridge in the pore throat that generates further pore blockage and iii) particles with a
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size lower than 1/7 of the pore size pass through the pore throat. Nanoparticles, in this
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media surface that contributes to the stabilization of the attractive forces between the
fine particle and the rock matrix. The use of nanoparticles for the inhibition of fines
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migration was first introduced by Huang et al. (2008) and later developed by Habibi et
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al. (2012) and Ogolo et al. (Ogolo et al., 2013a; Ogolo et al., 2013b; Ogolo, 2013;
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Ogolo et al., 2012). According to Ogolo et al. (2013b), fines fixation in the porous
media occurs due to two main mechanisms related to the pH of the carrier fluid and the
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electrostatic forces involved in particle retention. Mora et al. (2013) evaluated the effect
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bed and for different wetting states. The nanofluid was incorporated into the porous
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media in a 2 wt% dosage. The authors showed that the silica nanoparticles were able to
retain the fine particles independently of the wetting state of the sand. A higher
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retention was observed for the oil-wet system and was attributed primarily to the
presence of polar compounds on the rock surface. Recently, Giraldo et al. (2016a)
magnetite, silica, and alumina. The suspension of fines was prepared with quartz,
kaolinite, illite and its combination in different proportions to show the effect of the
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fines’ chemical nature. For this purpose, three components of simplex-centroid mixture
design (SCMD) was employed by evaluating seven points at different concentrations for
each element to adjust the response variable for the design. Alumina nanoparticles
showed high efficiency in the retention of kaolin and illite fine particles due to charge
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treatment would feature high efficiency due to the interaction of the fines with the
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silanol groups on the nanoparticle surfaces for systems with high concentrations of
quartz particles. Furthermore, Céspedes (2015) evaluated the effect of the chemical
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nature of nanoparticles in the inhibition of the migration of a mixture of fine particles of
kaolin, quartz, and illite in proportions of 50, 42 and 7 wt%, respectively. Experiments
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conducted under low-temperature and low-pressure conditions revealed that by
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increasing the nanoparticle dosage, the efficiency in the fines retention was enhanced,
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with better results for a dosage of 0.5 wt% of silica nanoparticles. This behavior was
observed for both water-wet and oil-wet systems. For concentrations higher than 0.5
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wt%, the efficiency was lower. The balance of the attractive and repulsive forces was
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the primary mechanism for the fines retention and was governed by the surface charge
of the nanoparticles employed. Céspedes (2015) also performed displacement tests for
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conditions of a field of interest in Colombia, and the results obtained by Céspedes are
shown in Figure 4. In brief, the critical rate was determined by injecting a defined
amount of pore volumes (PVs) of water at different rates (Q) between 0.2 and 6 mL/min
in the absence and presence of the nanofluid. The author found that the critical rate for
promoting fines migration was increased by 200%, which would allow higher
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production rates under field conditions and served as a base for the scaling and the
1.2 Q=0.2
Q=0.4
1 Q=0.7
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Q=1
0.8 Q=0.7 (Reverse)
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Q=0.2
K (mD)
0.6 Q=0.4
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Q=0.7
0.4 Q=1
Q=1.2
Critical rate
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0.2 before nanofluid Critical rate after Q=1.5
nanofluid
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Q=1.8
0
0 50 100 150 200 250
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Figure 4. Critical rate of oil before (green box) and after (blue box) nanofluid treatment.
The precipitation of inorganic scales in the production system may occur at any stage of
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the productive life of a well. Formation damage occurs when incompatible waters are
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mixed and from changes in pH, pressure and temperature that lead to the formation of
inorganic solids such as CaCO3, CaSO4, and BaSO4, among others, that block the
porous media and reduce the permeability of the system. The inhibitors commonly used
in the oil industry are phosphates and polyphosphates, phosphate esters, organic
carboxylates and sulfonates (RAMZI et al.). However, these types of inhibitors can have
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low efficiencies due to their mechanism of action, which in many cases involves sub-
stoichiometric ratios (Khormali et al., 2014). Relatively few studies have focused on the
inhibition of inorganic scales using nanoparticles (Antonietti et al., 1998; Jordan et al.,
2006; Logan, 2012; Schrick et al., 2004). It has been found that synthesized
nanoparticles for inorganic scale inhibition have excellent transport, diffusion, retention,
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and releasing properties in porous media, indicating that inhibition can be achieved over
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long distances from the injection point (Shen et al., 2008; Zhang et al., 2010).
Rodríguez (2016) focused his study on the development of a nanofluid for the inhibition
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of the precipitation of CaCO3 scales under high-pH conditions. Nanoparticles of metal +
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metal compounds and were tested as inhibitors of CaCO3 precipitation through batch
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titration experiments with ethylenediaminetetraacetic acid (EDTA). In most of the
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inhibition and reduced the efficiency of the nanoparticles by increasing the system
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temperature, which was attributed primarily to the reduction of CaCO3 solubility. For a
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temperature of 70°C, the best performance was observed for the Ca-DTPMP
nanoparticles at a concentration of 200 mg/L and is mainly due to the inhibition of the
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nucleation process. In addition, the author found that the preparation of a nanofluid
composed of ca-DTPMP nanoparticles and the fluid remaining after the synthesis
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process enhanced the inhibitory effect with efficiency values higher than 80%.
for the inhibition and remediation of formation damage due to inorganic scale
precipitation. In the oil and gas industry, fluids that permit simultaneous inhibition and
remediation of the formation damage by inorganic scales are uncommon. The results
precipitation in both batch and dynamic experiments. In The results obtained by Franco
damage are presented in Figure 5. In displacement tests under reservoir conditions for a
tight-condensate reservoir, it was observed that the inclusion of the nanofluid inhibited
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the reduction of porous media permeability to a lower degree than in the absence of
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nanofluid; the effect remained after two attempts of damage induction. Furthermore, in
the remediation step (Figure 5b), it was observed that the nanofluid (in addition to
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removing previously generated damage) tended to stimulate the system with an increase
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a 1 Kro base
Kro perdurability 1
Kro perdurability 2
0.8 Kro perdurability 3
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Krw base
Krw perdurability 1
0.6 Krw perdurability 2
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Krw perdurability 3
Kr
0.4
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0.2
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0
0 0.2 0.4 0.6 0.8 1
C
Sw
AC
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b 2
Kro nanofluid treatment
Kro base
1.5 Kro damage
Krw nanofluid treatment
Krw damage
1
Kr
Krw base
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0.5
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0
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0 0.2 0.4 0.6 0.8 1
Sw
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Figure 5. Relative permeability curves before and after injection of nanofluid treatment
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for a) inhibition and b) remediation of formation damage due to inorganic scales under
During the injection of different fluids into the reservoir, several problems may arise,
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such as the intrusion of external solids and changes in wettability. In the case of drilling
fluids, an optimal mudcake with low permeability and reduced thickness is desirable for
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inhibiting the loss of the fluid from the annular region to the formation. Several authors
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(Abdo and Danish, 2010; Hoelscher et al., 2012; Saboori et al., 2012; Zakaria et al.,
2012) have evaluated the use of nanoparticles in drilling fluids, showing that
induction of damage, leading to savings in the amount of additives required (Abdo and
Danish, 2010). Betancur et al. (2014) evaluated the effect of silica- and alumina-based
nanoparticles on the reduction of the mudcake thickness and the loss filtration in water-
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based muds through the American Petroleum Institute (API) filter test following the
API RP 13B-1 standard. Silica and alumina nanoparticles were functionalized with
surfaces. Although a reduction in the loss filtrate and the mudcake thickness was
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observed for both polar and non-polar materials, better results were obtained for the
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former. A dosage of 0.05 wt% of silica nanoparticles functionalized with 10 wt% of
CMC was identified as producing the best result with reductions of both loss filtrate and
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mudcake thickness of 23 and 70%, respectively, relative to the drilling fluid in the
absence of the material. The authors also recommended for future studies the
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application of hydrophobic nanoparticles for optimizing oil-based muds.
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In the case of fracturing fluids, water blockage due to low flowback of the injected fluid
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and mudcake formation around the fracture due to the remaining polymer are key
parameters associated with formation damage. The fluid remaining in the fracture and
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the formation after the hydraulic fracturing ends may lead to low-efficiency stimulation.
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Thus, different approaches have been studied to reduce the traditional guar gum loading
(Ely., 1989; Holtsclaw, 2011; Loveless, 2011; Qun, 2008; Williams, 2012) or the
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polymer dosage (Economides, 2000; G., 2014; Harris, 1998; Nimerick, 1997; Peles,
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microemulsions (Paktinat et al., 2005; Paktinat et al., 2007; Penny et al., 2006; Zelenev
and Ellena, 2009) and improve the flowback process with the addition of breakers
(Crews, 2013; Economides, 2000; G., 2014; Gulbis, 1992; Hanes, 2006; Nolte, 1985;
Reddy, 2013; Sarwar, 2011). Regarding nanoparticles for the inhibition of formation
incorporation of nanoparticles with mean particle sizes of 8 and 19 nm with basic and
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acidic surface modifications into a fracturing fluid for reduction of methanol loading
a fracturing fluid was assessed through rheology, wettability, and core-flooding tests,
allowing the modification of the fracturing fluid by decreasing the methanol loading up
to 33% and altering the porous media wettability to a water-wetted state. In addition,
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core-flooding tests were performed using a bauxite-based porous media and using a
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formation core of low permeability for simulating the flow through the proppant
material and the formation, respectively. Figure 6 shows the relative permeability
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curves before and after injection of an optimized fracturing fluid with nanoparticles in
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(Guzmán et al., 2017b). In the bauxite-based core-flooding tests, the formation damage
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was reduced by 71% after including the nanoparticles. Similarly, tests using the
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a 1
0.8
0.6
Kro Base
Kr
Kro Optimized
0.4 Kro Original
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Krw Base
Krw Optimized
0.2 Krw Original
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0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
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Sw
b 1
U
0.8 Kro Base
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Krw Base
0.6 Krw after damage
Kro after damage
Kr
0.4
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0.2
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0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Sw
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Figure 6. Relative permeability curves before and after injection of optimized fracturing
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2.5.Condensate banking
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In reservoirs of gas-condensate, one of the most common sources of formation damage
is condensate banking, which occurs when the reservoir reaches values of pressure that
are lower than the dew point (Hammami et al., 2000). The gas production is inhibited
by a reduction of the effective permeability to gas due to the condensate level in the
porous media (Amani and Nguyen, 2015; Fan et al., 2005; Li et al., 2015). The
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remediation or inhibition of condensate banking can be achieved by the alteration of the
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porous media wettability from a liquid-wet to a gas-wet state. This treatment approach
can facilitate the mobility of the condensate by increasing the formation roughness and
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thus decrease the energy of the rock surface (Wang et al., 2015). The use of
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is a promising alternative for enhancing the wettability alteration of gas-wet systems.
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Further, few researchers have focused on the development of nanoparticles/nanofluids
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for altering the wettability of reservoirs from liquid-wet to gas-wet (Aminnaji et al.,
2015; Esmaeilzadeh et al., 2015; Jin et al., 2016; Mousavi et al., 2013; Sharifzadeh et
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al., 2015). Cortés et al. (2016) synthesized a nanofluid based on the interaction between
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an anionic surfactant and silica nanoparticles for altering reservoir wettability from a
(SY) at different concentrations, and the nanofluids were prepared with the modified
wettability alteration from contact angle and imbibition tests on oil-wet and water-wet
sandstone samples were obtained for a nanofluid containing 500 mg/L of SY-modified
water-rock systems for a) water-wet (virgin) and b) oil-wet (restored) restored sandstone
samples before and after treatment with an SY solution at 0.46 wt% and with a
nanofluid consisting of 500 mg/L of SY-modified nanoparticles and 0.46 wt% of SY are
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shown in Figure 7. The treatment was suitable for altering the wettability preference of
the samples. Due to the synergistic effect of the treatment with nanofluids (SY + SY-
modified nanoparticles) on wettability alteration from liquid to gas, the imbibed liquid
level was considerably reduced for both sandstone samples using water and oil as the
imbibition fluids.
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a 1
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Normalized liquid uptake
0.8
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0.6
0.4
U Virgin sandstone
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0.2 SY solution
Nanofluid
0
M
0 0.5 1 1.5 2
Time (hours)
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b 0.3
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Restored sandstone
SY solution
Normalized liquid uptake
Nanofluid
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0.2
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0.1
AC
0
0 0.5 1 1.5 2
Time (hours)
Panels a and b in Figure 8 show the relative permeability curves and oil recovery curves
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obtained by Cortés et al. (2016). The values of krw and kro were always higher for the
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treated system than that of the base system. The state of saturation was modified after
nanofluid inclusion, confirming that the nanofluid inclusion led to an increase in the
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mobility of both oil and water in the saturation window that was evaluated. In addition,
Kro treatment
Krw treatment 80
Recovery (%)
1 Kro base
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Krw base 60
Kr
TE
40
0.5
20 Treated system
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Base system
0 0
0 0.5 1 0 20 40
C
Figure 8. a) Relative permeability curves and b) oil recovery curves for the base and
treated systems with a nanofluid consisting of 500 mg/L of SY-modified nanoparticles
and 0.46 wt% of SY. Adapted from Cortés et al. (2016) with permission.
rheological properties that the crude oil presents because of its high content of heavy
unconventional oils requires massive amounts of energy, leading to processes with low
cost effectiveness under either surface or sub-surface conditions. Fossil fuels currently
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supply approximately 82% of the world's energy demand (Ghannam et al., 2012). The
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growing demand for crude oil worldwide has led to the need to exploit deposits of
heavy and extra-heavy crude oils, which are approximately of the same order as those of
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conventional crude oil according to the International Energy Agency (IEA, 2013;
Tedeschi, 1991). In fact, in one scenario, from 2014 to 2035, approximately 9% of the
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cumulative investment upstream is predicted to be necessary for developing HO and
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EHO resources (IEA, 2014). For the case of Colombia, for instance, heavy and extra-
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heavy crude oils represent 55% of the total local oil production; and by 2018, this value
based on nanoparticles and nanofluids have been proposed for application under both
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surface and reservoir conditions. Under reservoir conditions, Taborda et al. (2016;
and mobility of HO on porous media. The effect of magnetite, alumina, silica, and
acidic silica nanoparticles was evaluated through n-C7 asphaltene adsorption, and
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aggregation tests and nanoparticles of acidic silica were used to prepare a water-based
regarding the crude oil in the absence of the nanomaterial. Rheological tests showed a
non-Newtonian behavior for the mixtures tested at 25°C. Core-flooding tests conducted
improvement in oil recovery of 16%. The effect of nanoparticles was attributed not only
to the reduction of HO viscosity but also to the change of the wet preference of the
systems. These results are consistent with those of the investigation performed by
Giraldo et al. (2013), who evaluated the effect of nanoparticles in altering the
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wettability of sandstone samples with an induced oil-wet condition. The nanoparticles
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concentration was varied to up to 10,000 mg/L in an anionic surfactant. Through contact
angle and imbibition tests, it was demonstrated that nanofluids could significantly
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change the wettability of the samples from a strongly oil-wet to a strongly water-wet
condition. The results showed that the effectiveness of nanofluids for wettability
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modification could be enhanced for concentrations equal or lower than 500 mg/L. From
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displacement tests, the authors observed that the wettability of the porous media could
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wettability with an induced oil-wet wettability and compared its performance with that
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and 10,000 mg/L were prepared by dispersing silica nanoparticles in aqueous solution.
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Similarly, fluids with commercial surfactant were prepared with concentrations between
100 mg/L and 10,000 mg/L by dispersion in an aqueous solution. The nanofluids
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AC
showed better performance in the modification of the wettability of the rock than that of
commercial surfactant. The best performance was achieved when a concentration of 100
mg/L was used. It was shown the nanofluids could change the wettability of the cores
displacement test was performed by injecting in the sand pack a nanofluid by dispersing
curve were obtained, which indicates that the nanofluid can restore the wettability of the
system.
Furthermore, Taborda et al. (2017b; Taborda et al., 2017c) demonstrated using dynamic
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to an HO structure after silica nanoparticle addition were the driving mechanism for
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reducing the viscosity, contrary to expectations from Einstein’s viscosity theory in
particulate systems (Taborda et al., 2017c; Taborda et al., 2017d). Figure 9 shows a
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schematic representation of the alteration in the heavy crude oil viscoelastic structure
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upon addition of silica nanoparticles and its effect on viscosity reduction, viscoelastic
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modulus alteration and yield stress reduction.
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Addition of
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SiO2 nanoparticles
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Viscosity reduction
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AC
Figure 9. Alteration in the heavy crude oil viscoelastic structure upon addition of
silica nanoparticles. Adapted with permission from Taborda et al. (2017b).
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The presence of nanoparticles in the HO changes the internal structure of the fluid that
nanoparticles impart directly to the asphaltenes and thus the viscoelastic network. By
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the addition of 1,000 mg/L of nanoparticles, the magnitude of the viscoelastic moduli
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(G´´) is reduced relative to the values for the HO in the absence of the material, proving
The aforementioned studies lead to the development of a field trial in heavy oil (HO)
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and extra heavy oil (EHO) reservoirs, as will be discussed in Section 5. Nevertheless,
when the HO and EHO viscosity cannot be changed under reservoir conditions, on-site
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transportation economics. Riaza et al. (2014) evaluated the effect of silica nanoparticles
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on the inversion of water-in-oil (W/O) emulsions for a Colombian heavy oil at water
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cuts higher than 48%. Through nanoparticle inclusion, emulsions can be transformed in
substantially due to the water is the external phase, allowing the crude oil to slide easily
on the determined surface. Taborda et al. (2017a; 2015) evaluated the effect of a
dosages between 0 and 4 vol% and temperatures between 30 to 70°C. It was observed
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that the nanofluid could reduce the EHO viscosity by up to 99% and that (for transport
the nanofluid. In addition, dynamic tests of EHO flow in a pipeline in the presence of
the nanofluid resulted in a reduction of 70% of the pressure differential relative to the
system in the absence of nanofluid and of 15% for the system in the presence of
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naphtha. Guzmán et al. (2017a) proposed a new process named enhanced de-asphalting
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(e-SDA) that uses nanoparticles for de-asphalting heavy oil and extra-heavy oil based
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of 4 are shown in Figure 10. The authors evaluated the separation efficiency of the e-
SDA process and de-asphalted oil (DAO) fraction quality using fume silica
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nanoparticles under different conditions of nanoparticle dosage, solvent-to-oil ratio,
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operating temperatures, and solvent type. The improvement of the process due to the
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use of nanoparticles was confirmed for all of the effects tested, and there were important
reductions in the contents of asphaltene and sulfur in the DAO of up to 24% and 23%,
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demonstrated that the API gravity could be increased by approximately 14% with the e-
SDA process with reductions in the viscosities of the DAO greater than 50% relative to
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SDA:
API = 11°
Asphaltene content = 8.6 wt%
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Sulfur content = 2.6 wt%
Viscosity = 54,000 cP
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e-SDA:
API = 13°
Asphaltene content = 7.0 wt%
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Sulfur content = 2.0 wt%
Viscosity = 33,000 cP
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Figure 10. Changes in API gravity, asphaltene content, sulfur content and oil viscosity
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for reducing the viscosity of an EHO is expected to improve the flow conditions of this
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surface and subsurface. In the presence of an external field, the magnetic moments of
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each nanoparticle in the ferrofluid will align along a preferential direction according to
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the applied field, modulating the mechanical behavior of the fluids and allowing for
arbitrary flow control through the manipulation of the magnetic effect (Kothari et al.,
2010; Saint-Martin de Abreu Soares, 2015). The results showed that the viscosity and
shear stress of EHO could be reduced by up to 81% and 78% in the presence of
ferrofluid. Other solutions based on the on-site upgrading of HO and EHO have been
studied. For example, Hassan et al. (Hassan et al., 2015) pioneered the use of NiO
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nanoparticles over alkali and alkaline earth metal oxides for the low-temperature
catalytic steam gasification of asphaltenes. Further, López et al. (2016) evaluated the
uptake and the subsequent decomposition of the heavy fraction of an EHO over
for partial upgrading. The catalytic behavior of the synthesized catalysts was evaluated
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with model solutions of asphaltenes and resins (R-A) in toluene, with a weight ratio
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corresponding to the ratio of these fractions in the crude. A composite adsorbent with
various selectivities for heavy-fraction functional groups more efficiently attracted the
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heavy compounds to the catalyst surface. An improvement in the catalytic behavior
could be achieved with the functionalization process, where the presence of a bimetallic
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active phase increases the decomposition of the heavy compounds at low temperature
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due to an enhancement of aliphatic chain decomposition and the dissociation of
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reduced by the application of the bimetallic catalyst, yielding a conversion rate greater
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than 93%.
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The concept of nanotechnology enhanced oil recovery (NEOR) is based on the inclusion
of nanoparticles and nanofluids for the improvement of traditional EOR processes. This
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techniques as well as those that use heat injection for enhancing the recovery of heavy
sweep efficiency when polymers or/and surfactants are injected. Among the different
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types of non-thermal processes, polymer flooding is one of the most commonly used
methods for increasing sweep efficiency in reservoirs and is based on increasing the
polyacrylamide (HPAM) or xanthan gum (XG)) and thus improving sweep efficiencies
at the same time that viscous fingering is inhibited (Kulicke et al., 1988; Needham and
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Doe, 1987; Sheng et al., 2015). However, the efficiency of the polymer flooding can be
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affected by factors such as excessive blockage of the pore throats, adsorption of the
polymer over the porous media surface and the degradation of the polymeric
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compounds due to thermal, chemical, biological and/or mechanical processes, leading to
the reduction of the injectant viscosity (Caulfield et al., 2003; Moan and Omari, 1992;
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Muller, 1981; Pu et al., 2016; Ramsden and McKay, 1986; Seright, 1983; Seright et al.,
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2010; Shupe, 1981). Currently, two methods to incorporate nanoparticles in polymer
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polymeric system for the preparation of nanofluids (Kennedy et al., 2015; Maghzi et al.,
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2013; Zhu et al., 2014), which has been assessed primarily by mixing the nanoparticles
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and the polymer, or ii) synthesis or chemical attachment of the polymer to the
However, scaling-up and production of large volumes of material can result in high
costs due to the manufacturing charges (synthesis route) required in this type of
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applications. In this sense, Giraldo et al. (2016b) evaluated the interaction of silica
nanoparticles and the polymer for inhibiting the degradation of the polymeric solution.
The authors focused on the adsorption phenomena of HPAM over SiO2 nanoparticles,
increase in oil recovery. A multilayer interaction was observed and was attributed to the
difficulty in removing the polymer from the surface of the nanoparticles, thus
corroborating that the modifications made to the polymers in the surface of the
nanoparticles can inhibit the degradation of the system. Rheological studies indicated
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that polymeric solutions subjected to temperature increases under an inert atmosphere
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were more prone to degradation than samples in the presence of the silica nanoparticles,
which impacted the sweep efficiency of the system directly. Figure 11 shows the
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evolution of a) viscosity and b) oil recovery with polymeric solutions in the presence
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polymer solutions led to a higher recovery of oil for a fixed value of pore volumes
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injected relative to the system lacking SiO2 nanoparticles. In addition, from the
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inclusion of nanoparticles, the polymer dosage can be reduced at the same time that the
500 mg/L
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60
Viscosity (cP)
40
AC
20
0
0 Days 7 Days 15 Days 30 Days
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b 100
80
Recovery (%)
60
40
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500 mg/L polymer + 3000 mg/L Np
20 500 mg/L polymer + 500 mg/L Np
600 mg/L polymer
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500 mg/L polymer
Water Injection
0
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0.0 1.0 2.0 3.0 4.0 5.0
Pore volumes injected
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Figure 11. a) Viscosity evolution and b) oil recovery curves with polymeric solutions in
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the presence and absence of silica nanoparticles.
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Oil production is accompanied by the use of large amounts of water. Water obtained
from the reservoir can be in the form of free water or an emulsion. In thermal (EOR)
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composition and structure could improve the process of emulsification. The main
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problems associated with emulsion formation are the high increase in oil viscosity
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and the possibility of pore blockage due to the physicochemical properties of the
variety of methods is applied for the treatment of emulsions; however, some of these
operational and technical costs. Thus, Llanos et al. (2016) focused their study on the
NiO nanoparticles (using the sol-gel method) to inhibit and/or break the emulsions
and obtain the maximum amount of free water. The specific interaction of
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asphaltenes were extracted from a Colombian heavy crude oil and were then
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thermally treated in an oxidizing atmosphere at different temperatures. The authors
observed that as the treatment temperature of asphaltenes increases, the H/C ratio,
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the length of the aliphatic chains and the branching decrease, while the ratio of
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contributing to the stabilization of W/O emulsions. SiO2 nanoparticles offered better
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performance than NiO nanoparticles in the inhibition of emulsion formation,
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possibly due to higher adsorptive capacity towards the asphaltenes, which could
hinder the active sites responsible for the emulsification process. With the increase
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Nanomaterials with high catalytic activity can contribute to the upgrading of the heavy
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oil at the same time that petrophysical properties such as system wettability can be
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nanoparticles was first introduced by Nassar and coworkers (Hassan et al., 2013;
Nassar, 2010; Nassar et al., 2012; Nassar et al., 2011a; Nassar et al., 2011b; Nassar et
al., 2011c; Nassar et al., 2011d; Nassar et al., 2011e; Nassar et al., 2013). The
activity toward asphaltene decomposition. The authors confirmed that the asphaltene
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adsorption/decomposition is specific to the metal oxide (Nassar et al., 2011a). In
the trend NiO > Co3O4 > Fe3O4. Similarly, Hosseinpour et al. (Hosseinpour et al., 2013;
Hosseinpour et al., 2014) employed metal oxide nanoparticles for adsorption and
subsequent oxidation and pyrolysis of Iranian asphaltenes, indicating that the outcome
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gasses in the process are particle-type dependent and confirming the catalytic role of the
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selected metal oxide nanoparticles. Thus, different supported hygroscopic salts (SHS)
nanoparticles of PdO and/or NiO supported on silica (Franco et al., 2016a; Franco et al.,
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2016b; Franco et al., 2013b; Franco et al., 2014b; Franco et al., 2015c; Lozano et al.,
2016; Montoya et al., 2016b), alumina and titania (Nassar et al., 2015b) have been
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synthesized for the adsorption and subsequent catalytic decomposition of heavy
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compounds. Functionalized nanoparticles, including monometallic (SNi2 and SPd2) and
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bimetallic SHS (SNi1Pd1), have enhanced adsorption capacity and high catalytic
properties of nanoparticles of the same chemical nature play a more important role in
the n-C7 asphaltenes adsorption than in the catalytic cracking (Franco et al., 2016b).
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Furthermore, water from the same reservoir may behave similarly in oxidation
increase the adsorption affinity. A trend between the effective activation energy
required for asphaltene decomposition and the degree of asphaltene self-association and
the adsorption affinity was found, where the catalytic activity of the materials is
inhibited by higher self-association at the same time that it is enhanced for higher
affinity between the catalyst-asphaltene couple (Franco et al., 2015c). Nanoparticles can
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also enhance asphaltene decomposition under oxidation, thermal cracking, and
inhibition of coke formation and catalyst poisoning (Franco et al., 2014b; Montoya et
al., 2016b). This catalytic property of the nanoparticles makes them promising
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candidates for improving the process of air injection (Franco et al., 2013b; Hosseinpour
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et al., 2014), steam injection (Franco et al., 2016a) or reservoir heating. The temperature
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to 220°C with the bimetallic SHS independently of the employed support (silica,
alumina or titania), indicating that the material has a synergistic effect by combining the
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selectivity of both PdO and NiO (see Figure 12). In addition, it was observed that in the
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gasification case, the functionalized nanoparticles can reduce the production of CH4 in
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the process and increase the CO, indicating that steam-reforming reactions are occurring
and that the production of H2 will increase. Lozano et al. (Lozano et al., 2016)
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presence of SHS nanoparticles of NiO and PdO supported over fumed silica
decomposition was not affected significantly by the inclusion of resin I in the system. In
another study, Franco et al. (2015a) synthesized carbon nanospheres (CNSs) for
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decomposition, with conversions of higher than 90% for temperatures lower than 300
°C.
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a 0.03 SNi2
0.07
SPd2 0.06
0.01 0.03
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0.02
0.01
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0.01
0.00 0.00
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0 200 400 600 800
Temperature (°C)
b 0.016
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SNi1Pd1 0.07
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Virgin Asphaltenes 0.06
Rate of mass loss (%/°C)
0.04
0.008
0.03
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0.02
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0.004
0.01
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0 0
0 200 400 600 800
Temperature (°C)
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Figure 12. Rate of mass loss of n-C7 asphaltene in the absence and presence of a) Pd-
for the bimetallic SHS that for the monometallic ones. Adapted with permission from
economic expense by reducing the negative environmental impact and increasing oil
2010), Hashemi et al. (Hashemi et al., 2012) and Hamedi et al. (Hamedi Shokrlu and
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Babadagli) have studied the effect of nanoparticles on the upgrading of heavy oils under
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dynamic conditions. Franco et al. (2016a) investigated the effect of catalytic active
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injection process under laboratory conditions. Oil recovery was evaluated using a slim
tube filled with a non-confined sand pack in steam injection scenarios in the absence
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and presence of a water-based nanofluid. Changes in physicochemical properties of
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crude oil were evaluated through n-C7 asphaltene content, viscosity, API gravity and
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three steps, namely, (1) construction of base curves, (2) oil recovery with steam
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injection and (3) oil recovery with steam injection assisted by catalytic nanoparticles.
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Figure 13 shows the oil recovery curves for steam injection with and without
nanoparticle assistance. The oil recovery with the injection of steam without
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nanoparticles stopped earlier than that of the system in the presence of nanoparticles,
viscosity reduction, thermal expansion, and variation of the relative permeability and
nanoparticles are achieved with less vapor PVI with a final recovery of up to 82%,
representing a value that is 46% more that in the absence of nanoparticles. Four main
reasons are responsible for the enhanced recovery of oil using steam assisted with
thus altering the rock surface to enhance its affinity for water. Also, nanoparticles have
shown a higher potential than larger particles for enhancing heat transfer processes due
to their high surface area to volume ratio (Xuan and Li, 2000). It has been reported that
the capacity of the nanofluids to enhance heat transfer increases as the size of the
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nanoparticle decreases (Sasmal and Nirmalkar, 2016; Sheikholeslami and Ganji, 2016c)
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and as the nanoparticles volume fraction increases (Sheikholeslami et al., 2012a). In this
sense, Sheikholeslami et al. (2012a; 2016; 2016a; 2016b; 2016c; 2016d; 2017b; 2012b)
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have dedicated their efforts in the numerical study of heat transfer with nanofluids.
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and Ganji, 2013; Sheikholeslami et al., 2013b; Sheikholeslami et al., 2014c) and using
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different numerical approaches (Sheikholeslami and Abelman, 2015; Sheikholeslami et
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and Ganji, 2015b; Sheikholeslami et al., 2013a), they concluded that the ratio of
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convective to conductive heat transfer is directly influenced by the type and volume of
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Sheikholeslami and Ganji, 2014; Sheikholeslami and Ganji, 2017e), the flow regime
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al., 2015).
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100
80
20
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0
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0 10 20 30 40 50
PVI
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Figure 13. Oil recovery curves for steam injection in the absence and presence of
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In addition to wettability changes and heat transfer enhancement, asphaltene adsorption
over the injected nanoparticles also leads to increase in oil recovery. Once asphaltenes
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are adsorbed over the nanoparticle surface, they can be converted into lighter products
catalyst, and chemical nature of the asphaltene molecule, among others. The formation
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of lighter products will change the chemical composition of crude oil and enhance the
processes described above that affect the oil recovery with steam (Patiño and Cortés,
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2016). The API gravity of crude oil increased from 7.2 to 12.1°. A reduction of 59% in
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the apparent oil viscosity was also observed. The n-C7 asphaltene content decreased by
40% after vapor injection in the presence of nanoparticles relative to the virgin EHO,
applications to overcome various difficulties present in the oil and gas sector. In this
sense, Colombia has been a pioneer in field applications involving nanofluid and
nanoparticles. The first trial worldwide for formation damage inhibition was performed
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in the Cupiagua Field and was focused on the injection of a specially designed
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nanofluid for inhibiting formation damage due to asphaltene precipitation/deposition
(Zabala et al., 2014). The Cupiagua Sur Field (Franco et al., 2013d) is located 110
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kilometers northeast of Bogotá in the foothills of the eastern mountain chain of the
Colombian Andes, close to other fields discovered in this area, such as Floreña, Pauto,
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Volcanera, Receptor, Cupiagua, and Cusiana. Cupiagua Sur is a compositional volatile
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oil reservoir with an average API gravity of 38°; there is no free gas cap under the initial
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conditions. The main formations are Mirador and Barco, which are quite similar in their
petrophysical and fluid properties (the average permeability is 21 mD, and the average
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porosity is 6.5%). Asphaltene precipitation in the near wellbore have been confirmed as
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one of the major components of formation damage in this field. In the Cupiagua Sur
Field, certain traditional methods have been evaluated for asphaltene inhibition. The
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to adsorb the asphaltenes before being flocculated and transported in the produced fluids
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avoiding precipitation near the wellbore and at the downhole. The CPSXL4 Well was
the well selected to operate the field trial of the new stimulation technology with
nanoparticles. This well was considered a candidate based on past interventions in the
well that showed significant benefits from these studies. It is possible to obtain accurate
information related to the formation damage mechanism, and this is achieved with clear
interpretations, analysis of production data and laboratory testing of the well fluid. The
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main wellbore damages are organic deposits (asphaltenes), the presence of mineral
deposits, blocking fluid problems (e.g., condensate water and completion fluid) and
fines migration. The first part of the work was focused on laboratory experiments for
evaluating the adsorption capacity with different nanomaterials for asphaltene samples.
The sorption kinetics of asphaltenes over locally produced nano-alumina and other
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nanomaterials was determined in a concentration range of asphaltenes between 250 and
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1500 mg/L. From the results of the first phase, it was determined that the locally
produced nano-alumina had excellent properties for asphaltenes sorption and could be
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incorporated into a nanofluid free of aromatic solvents, which traditionally are major
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was evaluated in core flow testing under reservoir conditions, and it was observed that
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the synthesized nanofluid improved the permeability to oil. Subsequently, a field trial in
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CPSXL4 well was recommended for field application involving the injection of 220
bopd of nanofluid containing alumina nanoparticles into the formation. Figure 14 shows
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the increases in oil production after the CPSXL4 chemical stimulation (CHS). After 8
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months of job tracking, asphaltenes were still stable in the produced oil, and the oil
production was above the baseline of approximately 300 bopd. Nodal system analysis
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relationship (IPR) and indicated that the vertical-lift performance (VLP) was altered
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water produced showed that the inhibition process still works, which is indicated by the
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1500
1000 Declination -2.3%
500
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0
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Figure 14. Incremental in oil production after nanofluid injection in the CPSXL4 Well.
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Adapted with permission from Zabala et al. (2014).
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After this first trial, the technology was extended to other fields in Colombia (Botero et
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al., 2015). In another well of the same field, the production incremental was estimated
to be 700 bopd and led to the re-intervention of the CPSXL4 Well with increases in
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cumulated oil production of approximately 23,600 and 276,000 bbl up to August 2015.
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asphaltene has also been extended to other fields due to the success of the application.
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The next field application was performed in determined TN Field, which is located in
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the Magdalena Medium Valley in Colombia between mountain chains of the Colombian
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Andes. TN crude is light oil with an average API gravity of 36°, chemical stimulation
based on nanofluids was conducted from June 2014 to October 2015 in five wells
according to the following procedure (see Figure 15): i) Preparing well: comprising the
steps of well control, withdrawing the artificial lift system, well calibration and running
an in-hole working string for stimulation treatment; ii) organic inhibition treatment:
using a coiled tubing (the entire volume was pumped this way), nanofluid is injected
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into formation in a designed volume to reach a radial penetration of ~4 ft, reciprocating
treatment: the solvent system is designed with diesel, alcohol, and xylene (DAX) to
reach a penetration radius of ~5 ft and is pumped in the same way as the nanofluid with
a soaking time of 6 hours; iv) inorganic removal treatment: designed with EDTA for a
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penetration radius of ~3 ft and a soaking time of 6 hours; v) N2 flow induction in the
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two first wells: the stimulation fluid was recovered by lifting with nitrogen for obtaining
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iron content; vi) post-treatment follow-up: a sampling protocol was defined to
characterize the residual nanoparticles, which determines the sampling time after the
Residual
Soaking
•Well • Inorganic nanoparticles
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Soaking
induction
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Figure 15. Stages for stimulation job with nanofluids in the TN Field.
Figure 16 shows that matrix treatments to remove organic and inorganic scales have
regularly been performed in the TN Field (in 2010, 2011, and 2013). A blend of organic
acids or EDTA was used for inorganic scale dissolution and aromatic/diesel mixtures
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for organic deposition dissolution. Although the initial oil rate increment was
satisfactory, the fast post-treatment declination enabled production to reach the baseline
faster than expected (treatments were still economically viable). The post-nanofluid-
inhibition stimulated production performance exhibits a different behavior (in 2014 and
2015), in which the incremental production is sustained over time and a change is
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observed in the decline of 25 to 21% per year.
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10000
Nanofluid
Oil production
Incremental
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Oil rate (bopd)
Baseline
1000
Stim
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Stim Stim
100 Stim Stim
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10
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10 11 12 13 14 15 16 17 18 19 20 21 22
Year
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Figure 16. Rate-cumulative decline analysis for field production before and after
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Figure 17 shows the typical behavior after stimulation in one of the treated wells (in
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2011 and 2012). The effectiveness of the treatment is clear, specifically the inhibition of
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organic damage by 2014 as the increase of production is stabilized at 60 bopd for more
than 18 months. This behavior was observed in the five treated wells.
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10000
Oil production
Nanofluid Baseline
1000
Incremental
Oil rate (bopd)
100
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10 Stim
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Stim
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1
10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Year
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Figure 17. Typical well production behavior after nanofluids application in the TN
Field.
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Figure 18. A sampling protocol was followed up to measure the residual amount of
observed, which is normal at the flowback initial stage. Then, the concentration drops
600
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100
0
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0 50 100 150 200 250 300
Days after job
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Figure 18. Residual concentration of nanoparticles after stimulation in a specific well of
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the TN Field.
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inhibition of formation damage from the migration of fines particles. The field trial
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consisted of three stages: the first involved the cleaning of pipes and drilling; a chemical
stimulation was then used for removing organic and fine components in the Barco
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Formation. Subsequently, inhibition test and fines stabilization were performed with a
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silica-based nanofluid, where 148 bbl of nanofluids was pumped. The production
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increased in the first two days of nanofluid application. The increase of 48 bopd of oil
was relative to the baseline before the start of operations, and the increase of 134 bopd
regarding the previous treatment stage indicated the optimum behavior of nanoparticles.
The production of gas increased by 1,000 kscfd relative to the baseline. The production
of water was not significantly different from the baseline but decreased by 40% relative
mitigate alteration of wettability in two Colombian heavy oil fields was performed in
the Castilla and Chichimene fields (Zabala et al., 2016). An oil-based nanofluid (OBN)
Displacement tests through a porous media in core plugs from Castilla and Chichimene
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under reservoir conditions were also performed. The use of the nanofluid increased oil
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recovery in the core-flooding tests, caused by the removal of asphaltenes from the
aggregation system, reduction of oil viscosity, and the effective restoration of original
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core wettability. Two field trials were performed in Castilla (CN154 and CN174 wells)
by injecting 200 bbl and 150 bbl of nanofluid, respectively, as the main treatment within
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a radius of penetration of ~3 ft. Instantaneous oil rate increases of 270 bopd in CN154
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and 280 bopd in CN174 and BSW reductions of ~11% were observed. In Chichimene
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(see Figure 19) two trials were performed (CHSW26 and CH39), by injecting 86 bbl of
and 107 bbl of nanofluid, respectively, as the main treatment within a radius of
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penetration of ~3 ft. Instantaneous oil rate increases of 310 bopd in CHSW26 and 87
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bopd in CH39 were achieved, but no BSW reduction has yet been observed (Zabala et
al., 2016). Interventions were performed several months ago, and the long-term effects
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BOPD
8770.5 ft
300 6%
1500 i ii
200
1000
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500 100
0 0
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0 500 1000
Total Production Rate (STB/day)
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Figure 19. a) Skin before and after the job: i-Pre stimulation 263 bfpd, 5.65% BSW,
248 bopd and Pwf = 1303 psi; ii-Post stimulation 641 bfpd, 12.95% BSW, 558
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bopd, Pwf = 1278 psi and ∆Qo = 310. b) The resulting production increases.
Adapted with permission from Zabala et al. (2016).
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6. Conclusions
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increasing the efficiency of different operations in the oil and gas industry.
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Experimental efforts conducted by the academic sector have resulted in the realization
interest. Thus, it can be said that the synthesis of smart fluids and particles is currently a
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reality. Approaches for formation damage inhibition have led to the expansion of these
nano-based solutions in various wells and several fields in the country. NEOR
approximations are aligned with the current needs of the national oil and gas industry,
and the academic sector is prepared for the challenges involved. Many studies have not
yet been implemented under field conditions, and it is necessary that oil-producing
countries and the industrial sector pay more attention and to implement an appropriate
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selection of the available smart solutions by considering the sponsorship of international
research and development efforts. This work opens a promising landscape in the oil and
gas industries for the improvement and/or enhancement of oil recovery based on an
Acknowledgments
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The authors acknowledge COLCIENCIAS, Agencia Nacional de Hidrocarburos
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(Colombia) and Ecopetrol S.A for their support provided. They also acknowledge the
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Universidad Nacional de Colombia for logistical and financial support.
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inhibition/remediation are described.
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the mobility of heavy and extra-heavy crude oils.
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• An overview is provided of mechanisms for assisting enhanced oil recovery
•
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Field trials have shown the potential of using nanotechnology for increasing the
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productivity of oil and wells and increasing reserves.
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