Accepted Manuscript

Nanotechnology applied to the enhancement of oil and gas productivity and recovery
of Colombian fields

Camilo A. Franco, Richard Zabala, Farid B. Cortés

PII: S0920-4105(17)30565-X
DOI: 10.1016/j.petrol.2017.07.004
Reference: PETROL 4090

To appear in: Journal of Petroleum Science and Engineering

Received Date: 27 April 2017

Revised Date: 25 June 2017
Accepted Date: 3 July 2017

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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 ACCEPTED MANUSCRIPT
Nanotechnology Applied to the Enhancement of Oil and Gas Productivity and

Recovery of Colombian Fields

Camilo A. Franco1,*, Richard Zabala2 & Farid B. Cortés1,*

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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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Hydrocarbons Agency (ANH). In addition, the exponential growth of the world

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population as well as increasing motorization and industrialization has led to higher

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demand for fossil fuels to supply energy requirements. Colombia is aware of this issue

and has become a key player of incorporating advances in nanotechnology to address

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this challenge by increasing the productivity/reserves of crude oil. Nanotechnology

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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in oil productivity and reserves based on the development of nanoparticles/nanofluids.

In this sense, Colombia has been a worldwide pioneer in the application of

nanotechnology under field-scale conditions, which has led to significant increases in

oil rate production. This document presents a review of the recent applications of

nanotechnology in Colombia, from laboratory approaches to field conditions. This

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review addresses the development of nanoparticles/nanofluids for application to the

inhibition/remediation of formation damage (asphaltenes, alteration of reservoir

wettability from liquid-wet to gas-wet, and inorganic scales, among other applications),

productivity improvement (hydraulic fracturing, drilling fluids, and improvement

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

oil crude, fines migration in tight-condensate reservoirs and mobility improvement of

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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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Keywords: Colombia, field trial, nanofluid, nanoparticles, nanotechnology.

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Nomenclature

ANH Nation hydrocarbons agency (Colombia)

API American Petroleum Institute

A:R ratio Asphaltene-to-resin ratio

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BSW Base sediments and water

Ci Asphaltene initial concentration

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CHS Chemical Stimulation

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CMC Carboxymethyl cellulose

CNS Synthesized carbon nanospheres

DAO De-asphalted oil

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DAX Diesel-alcohol-xylene (organic removal treatment)

DLS Dynamic light scattering

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DTPMP Diethylenetriamine -pentamethylene

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EDTA Ethylenediaminetetraacetic acid

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EHO Extra heavy oil

EOR Enhanced oil recovery

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e-SDA Enhanced solvent de-asphalting

G’’ Viscoelastic modulus

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HO Heavy oil
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HPAM Partially hydrolyzed polyacrylamide

IEA International energy agency

IOR Improved oil recovery

IPR Inflow performance relationship

K Permeability

Kr Relative permeability
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Kro Relative permeability of water

Krw Relative permeability of oil

M Solution volume to the dry mass of the nanoparticles ratio

MD Measured depth

NEOR Nanoparticles/nanofluids for enhanced oil recovery

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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

Pwf Bottomhole flowing pressure

Q Injection rate
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Qo Oil rate production
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SCMD Simplex-centroid mixture design

SDA Solvent de-asphalting

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SHS Supported hygroscopic salt

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SimDis Simulated distillation

Sor Residual saturation of oil

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SP Softening point

Swr Residual saturation of water

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SY Sylnil (Anionic surfactant)

TGA Thermogravimetric analysis

VLP Vertical-lift performance

W/O Water-in-oil

W/O/W Water-in-oil-in-water

XG Xanthan gum
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Contents
1. Introduction

2. Inhibition and remediation of formation damage

2.1.Asphaltene formation damage

2.2.Formation damage by fines migration

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2.3.Inorganic scale formation damage

2.4.Drilling fluids and hydraulic fracturing fluids

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2.5.Condensate banking

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3. Improving oil mobility under reservoir and surface conditions

3.1.In situ applications

3.2.On-site applications
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4. Nanotechnology for enhanced oil recovery (NEOR) applications

4.1.NEOR in non-thermal processes

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4.2.NEOR in thermal processes

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5. Field trials in Colombia using nanoparticles and nanofluids

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1. Introduction

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

surface-area-to-volume ratio and dispersibility, in addition to high thermal, chemical

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stability and dispersibility. The reactivity of particles with nanometric dimensions is

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

interact with other compounds.

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Further, it is of primary importance to clarify the nanotechnology concept and selected

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pioneer applications. Nanotechnology refers to the work of the professor Richard P.

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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

“manipulating and controlling things on a small scale” could be solved. A nanometer

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,

nanosphere or nanofilm depending on its morphology and its physicochemical

characteristics. Specifically, a nanoparticle is a solid particle with defined geometry in

the nanosize range and a nanofluid is a stable suspension of nanoparticles in determined

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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

enhancement (Dogonchi et al., 2017; Sheikholeslami and Ganji, 2016c; Sheikholeslami

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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

Swedish Academy of Sciences, 2016).

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For the oil and gas industry in particular, different applications of nanoparticles and

nanofluids applications have been proposed, including drilling operations, production

improvement, inhibition of formation damage, enhanced oil recovery, heat transfer

improvement, wastewater treatment, and improvement of mobility of heavy and extra-

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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the formation damage caused by the precipitation and deposition of asphaltenic

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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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drilling operations, inorganic scale deposition, alteration of reservoir wettability from

liquid-wet to gas-wet, and improvement of heavy and extra-heavy oil mobility, among
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other areas. Furthermore, the success of the nanotechnology applied to formation

damage inhibition has led to expansion in other applications. Indeed, due to the

significance of heavy and extra-heavy oils in Colombia, different solutions based on

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.

Nevertheless, despite significant advances in nanoparticle and nanofluid technology in

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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gas industry in Colombia, including field trials for several applications of

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

formation damage and consists of five subsections, namely: i) asphaltene formation

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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

describes the implementation of nanofluids/nanoparticles on field trials, including the

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inhibition of formation damage by asphaltenes and fines migration and the injection of

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

perspectives of this technology.

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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

causes a reduction in the inherent natural productivity of an oil or gas producing

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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

formation damage mechanisms, such as asphaltene precipitation/deposition, fines

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migration, condensate banking, inorganic scales, and damage during hydraulic

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fracturing operations, among other mechanisms (Zabala et al., 2016). Among these,
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formation damage due to asphaltene precipitation/deposition is one of the most difficult

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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heteroatoms of O, S, and N that—according to their location in the asphaltene

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structure—provide high polarity to the compound and thus self-associated properties

(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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amount-adsorbed values of up to 160 mg/g. In addition, the authors observed that

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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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spontaneous and exothermic according to the thermodynamic properties of the free

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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

effect of nanoparticles against asphaltene-induced formation damage. For this, the

interaction adsorbent – adsorbate was evaluated for 12 nanoparticles of different

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

ultimately prevents precipitation and deposition (Franco et al., 2013c). The

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displacement tests showed that damage from asphaltenes can be inhibited through the

inclusion of nanoparticles. Three systems were evaluated, namely, a blank system, a

damaged system and a treated system, in which the asphaltene damage was induced by

the injection of certain pore volumes (PVs) of n-heptane to an oil-containing porous

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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nanoparticles in the prevention of asphaltene self-assembly, where the authors aimed to

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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)

measurements. Nassar et al. (2015a) focused on the effect of nanoparticles of alumina,

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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from Betancur et al. (2016b).

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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

nanoparticle properties on asphaltene self-association. Displacement tests performed by

Betancur et al. (2016b) confirmed that nanoparticles can inhibit asphaltene formation

damage under high-temperature and high-pressure conditions and that silica

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nanoparticles with high total surface acidity may increase the oil recovery by up to 3%

relative to the results obtained by Franco et al. (2013c). In another study, Betancur et al.

(2016c) demonstrated that core-shell type nanoparticles composed of a magnetite core

with a silica shell can inhibit asphaltene formation damage and that the nanoparticles

can be recovered and regenerated by taking advantage of their magnetic properties.

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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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1.05 1.1 1.15

Increasing nanoparticles 1.2
surface acidity
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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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The competitive adsorption of n-C7 asphaltenes and resin I on silica nanoparticles

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was studied by Franco et al. (2015b) through the simultaneous construction of the
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respective adsorption isotherms by employing a novel method based on

thermogravimetric analysis (TGA) and softening point (SP) measurements. The

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

that silica nanoparticles hold promise for the treatment of asphaltene-related

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

evaluated nanoparticles with different chemical nature and different

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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

applications. Figure 3 shows the adsorption isotherms obtained by Guzmán et al.

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(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 ( M ) of 5, 10 and 20 g/L and Method ii for various values of n-C7

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asphaltene initial concentration ( Ci ). Differences between adsorption isotherms

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were attributed to the interaction between asphaltene-asphaltene and asphaltene-

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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

nanoparticle dosage for asphaltene-related problems could be selected based on

sharp changes in the slope of the Method ii adsorption isotherms.

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All these reported works favor the scaling and application of nanotechnology in

field trials to inhibit formation damage for the precipitation/deposition of asphaltene

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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Equilibrium concentration (mg/L)

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Figure 3. Adsorption isotherms for n-C7 asphaltene adsorption onto silica

nanoparticles using Method i (different initial concentration of n-C7 asphaltene but

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fixed mass of nanoparticles) and Method 2 (different mass of nanoparticles but fixed
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initial asphaltene concentration). Adapted with permission from Guzmán et al.

(2016).

2.2.Formation damage by fines migration

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).

According to the one-third- to one-seventh-arch principles, the particle size contributes

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

case, are specifically designed to generate a monolayer of nanoparticles on the porous

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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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of a silica-nanoparticle-based nanofluid on fines retention in an Ottawa-sand-packed

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)

evaluated the selectivity of nanoparticles on the inhibition of fines migration of different

chemical nature. Ottawa-sand-packed beds were treated with nanoparticles of

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

neutralization of these clays. Moreover, it was observed that a silica nanoparticle-based

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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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corroborating the effect of the nanoparticles in the inhibition of fines migration.

Dynamic experiments of rate alteration were conducted under typical reservoir

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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

implementation of nanotechnology in a field trial (see Section 5 below).

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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Pore volumes injected

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Figure 4. Critical rate of oil before (green box) and after (blue box) nanofluid treatment.

Adapted with permission from Céspedes (2015).

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2.3.Inorganic scale formation damage

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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

phosphonates, polyacrylates and various polymers and copolymers of phosphonate,

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 +

diethylenetriamine -pentamethylene (DTPMP) were synthesized using Zn and Ca as the

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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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experiments, it was observed that an increase in nanoparticle dosage promoted

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%.

Similarly, Franco (2016) optimized the formulation of a Ca-DTPMP-based nanofluid

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

obtained by Franco (2016) showed that a nanofluid composed of 50 mg/L of

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nanoparticles and 10 vol% of the synthesis fluid was efficient in the inhibition of scale

precipitation in both batch and dynamic experiments. In The results obtained by Franco

(2016) regarding the a) inhibition and b) remediation of inorganic scale formation

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

of 57% in oil permeability relative to the blank system.

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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
EP

0
0 0.2 0.4 0.6 0.8 1
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Sw
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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

RI
0

SC
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

tight-condensate reservoir conditions. Adapted with permission from Franco (2016).

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2.4.Drilling fluids and hydraulic fracturing fluids

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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

nanoparticles can be adapted to a variety of settings to simultaneously inhibit the

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

different amounts of vacuum residue, NiO nanoparticles, n-C7 asphaltenes and

carboxymethyl cellulose (CMC) for inducing different polarities on the nanoparticle

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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2002; Weaver, 2002a; Weaver, 2002b), enhance post-fracturing cleansing using

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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

damage in hydraulic fracturing operations, Guzmán et al. (2017b) evaluated the

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

and enhancement of fluid flowback. The inclusion of nanoparticles in the formulation of

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

a) bauxite-based porous media and b) a formation core from a tight-condensate reservoir

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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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formation core led to a reduction of the permeability relative to water of up to 82%,

indicating that nanoparticles may act as a relative permeability modifier.

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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

SC
Sw
b 1

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0.8 Kro Base
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Krw Base
0.6 Krw after damage
Kro after damage
Kr

0.4
D

0.2
TE

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Sw
EP

Figure 6. Relative permeability curves before and after injection of optimized fracturing
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fluid with nanoparticles in a) bauxite-based porous media and b) a formation core.

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Adapted with permission from Guzmán et al. (2017b).

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

nanoparticles/nanofluids based on the interaction of fluorosurfactants and nanoparticles

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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

liquid-wet to a gas-wet state. Nanoparticles were modified with an anionic surfactant

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(SY) at different concentrations, and the nanofluids were prepared with the modified

silica nanoparticles dispersed in an SY solution in deionized water. Improved results of

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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

silica nanoparticles in a 0.46 wt% SY solution. Spontaneous imbibition curves in air-

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
EP

0.2
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0.1
AC

0
0 0.5 1 1.5 2
Time (hours)

Figure 7. Spontaneous imbibition curves in air-water-rock systems for a) virgin and b)

restored sandstone samples before and after treatment, respectively, with an SY solution
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at 0.46 wt% and 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.

Panels a and b in Figure 8 show the relative permeability curves and oil recovery curves

obtained under tight gas-condensate reservoir temperature and pressure conditions

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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,

an enhancement of 68% in oil recovery and an increase of 6% in the gas effective

permeability were observed.

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a 1.5 b 100
M

Kro treatment
Krw treatment 80
Recovery (%)

1 Kro base
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Krw base 60
Kr

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40
0.5
20 Treated system
EP

Base system
0 0
0 0.5 1 0 20 40
C

Sw Pore Volumes Injected

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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.

3. Improving oil mobility under reservoir and surface conditions

3.1. In situ applications

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The production of heavy oil (HO) and extra-heavy oil (EHO) is adverse due to the

rheological properties that the crude oil presents because of its high content of heavy

hydrocarbons, such as asphaltenes and resins. In addition, the upgrading of these

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

is expected to increase to up to 60% (Energía, 2013). In response, different solutions

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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;

Taborda et al., 2017d) assessed the effect of nanoparticles/nanofluids on the rheology

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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

nanofluid at different concentrations in distilled water. Increasing the concentration of

nanoparticles in the system to up to 10,000 mg/L generated a viscosity reduction of 90%

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

under typical reservoir conditions of temperature, pore and overburden pressures

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indicated that the addition of nanoparticles enhances the HO mobility and leads to an

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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be induced to a strongly water-wet condition. Similarly, Betancur et al. (2016a)

evaluated the effectiveness of silica-based nanofluids in altering sandstone core

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wettability with an induced oil-wet wettability and compared its performance with that
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of a commercial surfactant. Nanofluids with different concentrations between 100 mg/L

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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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

from a strongly oil-wet to a strongly water-wet condition. Additionally, a core

displacement test was performed by injecting in the sand pack a nanofluid by dispersing

silica nanoparticles in aqueous solution. A reduction in the residual oil saturation, an

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increment of oil mobility and a displacement to the right of the oil relative permeability

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

rheological techniques that changes in the viscoelastic network of asphaltenes intrinsic

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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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Heavy oil viscoelastic network

Change in heavy oil internal structure
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Addition of
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SiO2 nanoparticles
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Viscosity reduction
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Yield stress reduction

Viscoelastic modulus
alteration
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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

that nanoparticles disrupt/modify the viscoelastic network formed by asphaltene

aggregates in the presence of resins.

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3.2. On-site applications

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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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solutions become important, as an IOR/EOR process can be directly affected by the

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

water-in-oil-in-water (W/O/W), which in turns reduces the system viscosity

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

nanofluid in the viscosity and optimization of transport conditions of an EHO for

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

conditions) the naphtha requirements could be reduced by up to 80% in the presence of

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

on conventional solvent de-asphalting; selected results obtained for a solvent-to-oil ratio

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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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respectively, relative to the conventional SDA process. Furthermore, the results

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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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the process in the absence of nanoparticles. After the de-asphalting process,

nanoparticles can be regenerated by thermal processes and re-used.

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Untreated EHO:
API = 6.4°
Asphaltene content = 20 wt%
Sulfur content = 4.5 wt%
Viscosity = 1'000,000 cP or higher

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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after SDA and e-SDA processes for a solvent-to-oil ratio of 4.

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Aristizábal-Fontal et al. (2017) based their research on the interaction of asphaltenes

with magnetic nanoparticles. The synthesis of magnetite nanoparticle-based ferrofluids

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for reducing the viscosity of an EHO is expected to improve the flow conditions of this
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type of unconventional hydrocarbons in terms of control and optimization at both the

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

functionalized aluminosilicates, with active phases of Ni-Mo and Mo-Co nanoparticles

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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heteroatomic bonds. In addition, coke formation after steam gasification process is

reduced by the application of the bimetallic catalyst, yielding a conversion rate greater
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than 93%.
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4. Nanotechnology for enhanced oil recovery (NEOR) applications

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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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section includes the application of nanotechnology in non-thermal or cold EOR

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techniques as well as those that use heat injection for enhancing the recovery of heavy

oil (HO) and extra heavy oil (EHO).

4.1. NEOR in non-thermal processes

In non-thermal EOR processes, nanoparticles and nanofluids can be useful in terms of

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

viscosity of the injection water by adding polymers (partially hydrolyzed

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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processes flooding have been scrutinized: i) the inclusion of nanoparticles in the

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

nanoparticle surface (Liu et al., 2017; Rezaei et al., 2016).

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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,

as the design of a nanofluid can serve as a cost-effective solution that guarantees an

increase in oil recovery. A multilayer interaction was observed and was attributed to the

intermolecular forces between the most-polar components of the polymer (mainly

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functional groups) and the silanol groups present in the fumed silica. Desorption

percentages lower than 1% indicated an irreversible adsorption process, indicating

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

and absence of silica nanoparticles. The systems containing nanoparticles in the

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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

resistance to degradation is enhanced.

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500 mg/L
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500 mg/L Polymer + 500 mg/L Np

500 mg/L Polymer + 3000 mg/L Np
a 80
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60
Viscosity (cP)

40
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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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4.2. NEOR in thermal processes

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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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processes such as in situ combustion, changes in the asphaltene chemical

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

drops in the dispersed phase, which impedes hydrocarbon production. Currently, a

variety of methods is applied for the treatment of emulsions; however, some of these

treatments involve significant economic and energy expenses that increase

operational and technical costs. Thus, Llanos et al. (2016) focused their study on the

use of nanoparticles for the inhibition of emulsion formation as a viable alternative

 ACCEPTED MANUSCRIPT
for in situ applications. The behavior of W/O emulsions was evaluated with

different concentrations and chemical natures of SiO2 nanoparticles and synthesized

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

nanoparticles and the emulsifying agent (asphaltenes) was evaluated. The

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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

aromatic/hydrogen aliphatic cores to the carbonyl group tends to increase,

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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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in the concentration of SiO2 nanoparticles in the samples, better performance is

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achieved by increasing the coalescence of the water droplets to promote a lower

volume of the emulsified phase and a greater amount of free water.

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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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altered. The catalytic thermal decomposition of asphaltenes onto different surfaces of

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

nanoparticles significantly decrease the activation energy, confirming their catalytic

activity toward asphaltene decomposition. The authors confirmed that the asphaltene
 ACCEPTED MANUSCRIPT
adsorption/decomposition is specific to the metal oxide (Nassar et al., 2011a). In

particular, the catalytic activity of nanoparticles of different chemical nature followed

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

activity towards the reduction of the decomposition temperature of refractory

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compounds of crude oil such as asphaltenes and resins. Different physicochemical

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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

processes in the absence or presence of nanoparticles. In the adsorption process,

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functionalized nanoparticles tend to reduce the degree of asphaltene self-association and

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

gasification processes by reducing the degree of asphaltene self-association over the

catalyst surface, decreasing the temperature of asphaltene decomposition and by the

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

of asphaltene decomposition in the presence of nanoparticles is significantly reduced up

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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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investigated the effect of resin I on the decomposition of n-C7 asphaltenes in the

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presence of SHS nanoparticles of NiO and PdO supported over fumed silica

nanoparticles. The authors observed that the temperature of n-C7 asphaltene

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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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AC

catalytic asphaltene decomposition under low-temperature oxidation conditions. The

synthesized CNSs were effective in reducing the temperature of asphaltene

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

Rate of mass loss (%/°C)

Rate of mass loss (%/°C) 0.02 Virgin Asphaltenes
0.05
0.02 0.04

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)

Rate of mass loss (%/°C)

0.012 0.05
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0.04
0.008
0.03
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0.02
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0.004
0.01
EP

0 0
0 200 400 600 800
Temperature (°C)
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AC

Figure 12. Rate of mass loss of n-C7 asphaltene in the absence and presence of a) Pd-

and Ni functionalized monometallic SHS and b) bimetallic SHS under an inert

atmosphere. The main peak of asphaltene decomposition occurs at lower temperatures

for the bimetallic SHS that for the monometallic ones. Adapted with permission from

Montoya et al. (2016a).

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Catalytic nanoparticles may be used for in situ heavy oil upgrading, leading to an

economic expense by reducing the negative environmental impact and increasing oil

recovery (Galarraga and Pereira-Almao, 2010; Hamedi Shokrlu and Babadagli;

Hashemi et al., 2012). Galarraga and Pereira-Almao (Galarraga and Pereira-Almao,

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

nanoparticles in the enhancement of the efficiency in recovery of a continuous steam

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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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simulated distillation (SimDis) measurements. Displacement tests were conducted in

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,

reaching a recovery of 36%. Oil recovery is enhanced by steam injection due to

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viscosity reduction, thermal expansion, and variation of the relative permeability and

capillary pressure. Similar percentages of recovery to that in the absence of

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

nanoparticles relative to the system without nanoparticles. As nanoparticles enter the

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porous media, they may alter the system wettability to a strong water-wet condition,

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.

Trough the study of different geometries (Sheikholeslami et al., 2014a; Sheikholeslami

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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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al., 2012b; Sheikholeslami et al., 2014b; Sheikholeslami et al., 2016a; Sheikholeslami

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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nanoparticles (Sheikholeslami and Ganji, 2017b; Sheikholeslami and Ganji, 2017d;

Sheikholeslami and Ganji, 2014; Sheikholeslami and Ganji, 2017e), the flow regime
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(Sheikholeslami and Ganji, 2016d), the viscosity parameters (Sheikholeslami et al.,

2016b), and magnetic parameters (Sheikholeslami and Ganji, 2015a; Sheikholeslami et

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al., 2015).
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100

80

recovery (%) 60 Steam + nanofluid

Steam
40

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

nanoparticles. Adapted with permission from Franco et al. (2016a).

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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

under determined conditions of temperature, asphaltene loading, degree of self-

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association around nanoparticle active sites, chemical nature of the nanoparticulate

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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,

and the residue content (620°C+) decreased by 47%.

5. Field trials in Colombia using nanoparticles and nanofluids

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Colombia has taken advantage of the synergy among the state, academy, and industry

for the development of specialized human resources around nanotechnology

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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asphaltenes inhibition trial involved the injection of nanofluids containing nanoparticles

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

components in the formulation of asphaltene inhibitors and dispersants. The nanofluid

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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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showed the improvement (skin reduction) obtained in the inflow performance

relationship (IPR) and indicated that the vertical-lift performance (VLP) was altered
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because of the increase in oil production. The concentration of nanoparticles in the

water produced showed that the inhibition process still works, which is indicated by the

production performance remaining above the baseline.

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CUP SUR XL-4 Oil production after CHS
Oil production without CHS
4000
Selective chemical stimulation
3500 Organic Scale inhibition
3000
Produced oil (bopd)

2500 Base line

1708 bopd
2000 Post pickling

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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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The application of nanofluids in the Cupiagua Field for the inhibition/deposition of

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

on perforated intervals, followed by a soaking time of 6 hours; iii) organic removal

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

a baseline in terms of selected physicochemical parameters of the water, mainly pH and

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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

well returns to production.

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AN
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Residual
Soaking
•Well • Inorganic nanoparticles
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preparation • Organic treatment •Run nanoparticles

•Nanofluid residual
treatment characterization
•Baseline comparison
N2 flow
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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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stimulation with nanofluids.

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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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A typical response of the residual amount of nanoparticles in a selected well is shown in

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Figure 18. A sampling protocol was followed up to measure the residual amount of

nanoparticles in the effluents. Initially, a higher concentration of nanoparticles is

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observed, which is normal at the flowback initial stage. Then, the concentration drops

over time. The current inhibitor residual concentration of nanoparticles is as low as 1 or

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2 mg/l, showing favorable performance in the inhibition process.

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600

Nanoparticles residual (mg/L)

500
400
300
200

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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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Based on these results regarding the inhibition of formation damage from

precipitation/deposition of asphaltene, nanotechnology has also been considered for the

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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

to the post-pickling operation.

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For HO and EHO, a field evaluation of nanofluids for improving oil mobility and

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)

containing nanoparticles was evaluated as a viscosity reducer under static conditions.

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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are still under evaluation.

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a Skin 6.2, BSW 12.95% b 600 Water Oil

3500 13% 20%
Pressure at casing (psia), MD Skin Initial 23, BSW 5.65%
3000 Measured Data 500 20%
2500
400
2000 BSW

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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Nanotechnology-based developments in Colombia have shown great potential for

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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

of different nanoparticles and nanofluids specially designed according to the problem of

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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

innovative technology such as nanotechnology.

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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Highlights

• Colombia has pioneered the worldwide use of nanoparticles/nanofluids through

field trials in different applications.

• Recent advances in nanotechnology applications for formation damage

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inhibition/remediation are described.

• An overview is provided of the effect of nanoparticles/nanofluids for improving

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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

processes under thermal and non-thermal scenarios using nanotechnology.

•
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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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