Spe 211106 Ms

SPE-211106-MS
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Generation of Complex Emulsions During the Application of Improved
Recovery Methods in Venezuelan Heavy and Extra-Heavy Oil Reservoirs: A
Critical Review
Fernancelys Rodriguez, Independent Consultant; Hadi Belhaj, Khalifa University of Science and Technology; David
Rousseau, IFP Energies nouvelles; Mohammed AlDhuhoori, Khalifa University of Science and Technology
Copyright 2022, Society of Petroleum Engineers DOI 10.2118/211106-MS
This paper was prepared for presentation at the ADIPEC held in Abu Dhabi, UAE, 31 October – 3 November 2022.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
The formation of emulsions during the production of highly viscous crude oils is one of the biggest issues
observed both in cold production and after the application of IOR methods in Venezuelan heavy and
extraheavy oil reservoirs, with impact on the lifting of crude oils, separation of phases, fouling, production
costs, etc. For the cold production case, the presence of water with strong compositional and salinity
variation, coupled with the presence of gas in the case of foamy oil, could generate very stable oil-water
and gas-oil emulsions; hence complicating the phenomena after the application of thermal or chemical IOR
methods.
This article presents a review of: 1) different types of emulsions found in cold production as well as
thermal and chemical IOR methods, 2) factors that affect the stability of the emulsions (compositions
of crude oil and formation and injection waters, type of injection fluid, temperature, etc.), 3) fluid
characterization methods (gravimetric method, droplet size distribution, centrifugation, rheology, etc.), 4)
recommended demulsifiers based on laboratory, and field experiences in Venezuela and internationally.
These criteria will be reviewed in detail, establishing the main insights associated with the emulsion
formation, providing related conclusions and perspectives for treatment and prevention measures.
Based on the results of this review, it can be highlighted that the presence of resins and asphaltenes in the
crude oil has a fundamental role in the stability of the emulsions found during cold production in the Orinoco
Oil Belt and that the composition of the formation water might increase the stability of the emulsions
(Mg2+ and Ca2+). The application of thermal as well as diluent injection methods generates emulsions that
involve precipitation of asphaltenes, which together with sand production in the process, leads to making
phase separation processes more complex. Furthermore, the application of chemical methods could cause
phase trapping (for the surfactant case) with impact on chemical losses, and water- in-oil emulsion with
high viscosity after the addition of alkali in lab experiments. A worldwide review of field and laboratory
remediation methods indicates that possible emulsion treatments include the use of silica nanoparticles,
polyglycerol fumarate ester, heavy aromatic naphtha, electrical heaters, among others. This article presents
the main insights related to the generation of emulsions in Venezuela and for developing strategies for
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emulsions breakers adapted to each IOR process. It also covers the effect of water chemistry, oil composition
and type of IOR/EOR process on the characteristics of emulsion and emulsion stability, and consequently
the impact on the technical and economic criteria of the process.
Introduction
Venezuela traditionally has been a producer of highly viscous crude oils, thanks to its immense resources
located in its main deposits in the Eastern Venezuela and Maracaibo basins as illustrated in Figures 1A and
1B (Baha Al-Deen, 1977; Herrera, 1977; Trebolle et al., 1993; Layrisse, 1999; Rodriguez F., 2016). Due to
the physicochemical characteristics (Hopkinson and Penuela, 1997; Lopez and Lo Monaco, 2010; Borges
et al., 2014; Rodriguez, F., 2016) of the Venezuelan highly viscous crude oils (high viscosities, high acid
numbers, and high content of resins and asphaltenes), they can form very stable water-in-oil (W/O) and oil-
in-water (O/W) emulsions. Table 1 shows the characteristics of several heavy and extraheavy Venezuelan
crude oils.
Figure 1A—Highly viscous Venezuelan heavy and extra-heavy oil fields (Layrisse, 1999)
Figure 1B—Guanoco Lake (Lago-Laguna de Guanoco) in Venezuela - Sucre State (Rodriguez F., 2016).
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Table 1—Typical properties of Venezuelan heavy and extra-heavy crude oils (Rodriguez, 2016).
Some of these highly viscous oil reservoirs are characterized by high water production coming from
aquifers or meteoric waters, with variation in composition and salinity (Parnaud et al., 1995; Marcos et al.,
2007; Florez-Nino and Vega, 2009; Foulon et al., 2009; Martinius et al., 2013; Pulido, 2018) that promote
the formation of stable emulsions that affect artificial lift systems (Gonzalez, 2005), transport of fluids due
to increase in viscosity (Rojas et al., 1977; Belhaj et al., 2003; Walker et al., 2012; Belhaj et al., 2013;
Oliva, 2019; Ghosh, 2020; Liu et al., 2022), separation of fluids and increased production costs (Farouq
Ali, 1976; Boardman and Zerpa, 2001; Alves et al., 2009; Rodriguez, 2021; Faisal and Almomani, 2022).
On the other hand, the foaming nature of Orinoco Belt crude oil (De Mirabal et al., 1996; Huerta et al.,
1996; Li et al., 2012; Fei et al., 2014; Yang et al., 2019) promotes the formation of gas-in-oil emulsions,
which, together with the presence of other phases such as diluents (Rojas, 2001; Argillier et al., 2001;
Michinel, 2017; Meza et al., 2022) and solids/sands (Padron and Percy, 2005; Belhaj and Nouri, 2007;
Marquez and Brito, 2014), complicate fluid separation operations (Pina-Acuna and Ferreira, 2004). The
application of IOR methods in highly viscous oil reservoirs, such as waterflooding (Vidal and Alvarado,
2014; Mendez et al., 2014; Kumar et al., 2020), thermal and CEOR methods, could promote the formation
of more complex emulsions with other fluids and solids in the reservoir, affecting in the same way the
lifting crude oils due to the high viscosity of the emulsified crude oil, separation of phases, corrosion (due
to the presence of alkaline clay products), poisoning of catalysts, fouling and escalated productions costs
(Mittal et al., 2018; Zagitov et al., 2020; Lee and Babadagli, 2020; Almorihil et al., 2021; Mouret et al.,
2022; Yonguep et al., 2022). The emulsions generally generated after the application of IOR processes are
a mixture of crude oil, water, dissolved solid, sand, silt, chemicals and/or other organic compounds injected
during production (Argillier et al., 2018; Graham at Frigo, 2019). Emulsions could also affect the quality
of crude oil (Araujo, 1977; Leon, 2018; Wang et al., 2021; Chang et al., 2022), which must be treated to
meet production and transportation standards to reduce corrosion and catalyst poisoning that could occur
in the process. Emulsions can cause technical and environmental issues in oil production (Wang et al.,
2021). The separation of emulsions is a key process before the transportation and treatment of crude oil,
the most common demulsification processes being those based on thermal, biological, electrical, chemical,
and mechanical techniques (Faisal and Almomani, 2022). A stable emulsion is one that needs some form of
treatment to be separated. Within the necessary conditions for the formation of a stable emulsion of crude oil
and water are the following: presence of two immiscible liquids, supply of energy for agitation, presence of
emulsifying agents (Donis and Ricaurte, 2005). The purpose of emulsion treatment methods is to counteract
the stabilizing effect of natural emulsifying agents or to sufficiently modify their properties, thus promoting
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the approach of droplets to facilitate their coalescence. Among the various emulsion treatment methods
applied to water-oil emulsions are: settling, injection of a demulsifying agent, heating, coalescence packing,
filtration, electrostatic separation, centrifugation, washing with water, combination of systems for treatment
of emulsions, among others (Donis and Ricaurte, 2005).
This article presents a review of the main challenges related to emulsion generation in Venezuela,
including different types of emulsions found in cold production as well as after the application of thermal and
chemical IOR methods. Additionally, a review of aspects such as emulsions stability and characterization
methods, recommended demulsifiers in Venezuela and internationally. These criteria will be reviewed in
detail, establishing the main insights and perspectives for treatment and prevention measures.
Background
Emulsion generalities
An emulsion is a heterogeneous system consisting of a mixture of at least two immiscible liquids, one of
which is dispersed in the other in the form of small droplets; said dispersion is stabilized by the presence of
surfactant agents and/or solid particles that act as emulsifying agents (Donis and Ricaurte, 2005). Emulsions
are formed when at least two immiscible liquid phases are present in a system, this consists of a dispersed
phase and a continuous phase (Faisal and Almomani, 2022). The composition of the continuous phase
is related to the water/oil ratio, the natural emulsifier systems contained in the oil and the origin of the
emulsion. The emulsions commonly found in oilfields are water-in-oil emulsions (W/0) which consist of
water droplets dispersed in the oil, and oil-in-water emulsions (O/W) which consist of oil droplets dispersed
in water, as shown in Figure 2. Relatively hydrophilic emulsifying agents tend to form oil-in-water (O/W)
emulsions while hydrophobic emulsifiers favor the formation of water-in-oil (W/O) emulsions (Donis and
Marvin, 2005).
Figure 2—Different types of emulsions found in heavy oil production and transport (Ma et al., 2022).
Other types of emulsions such as water-in-oil-in-water and oil-in-water-in-oil are also reported in the
literature (Ma et al., 2022). This type of emulsions, called multiple emulsions, are systems in which within
the drops that form the dispersed phase, there are, in turn, drops of the same fluid that form the continuous
phase. Emulsions of the oil/water/oil (O/W/O) type are made up of a continuous oil phase in which water
globules are dispersed, which in turn form a continuous phase in which globules are dispersed; namely, small
amounts of oil forming a dispersed phase. In contrast, water/oil/water (W/O/W) emulsions are made up of a
continuous phase of water, in which there is a first dispersed phase of oil, which serves as a continuous phase
for a second dispersed phase of water (Donis and Marvin, 2005) as indicated in Figure 2. Figure 2 shows
different types of emulsions found in oil production operations. Figure 3 shows some of the emulsions found
in upstream, mid-stream, and downstream of heavy oil production cycles reported by Lee and Babadagli
(2020).
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Figure 3—Emulsions found during the production systems (Lee and Babadagli, 2020): Upstream, midstream, and downstream.
It is reported that among the factors that contribute to maintaining the stability of emulsions are (Donis
and Marvin, 2005):
• Oil viscosity: highly viscous oils tend to form stable emulsions, requiring longer time for the
dispersed phase droplets to unite and coalesce.
• Temperature: emulsions are generally more stable at low temperatures, due to their relationship
with the viscosity of the crude oil and the resistance to droplet movement.
• Water content: In general, low percentages of water in crude tend to form more stable emulsions.
As the amount of water becomes greater, the number of drops in the external phase will also get
higher, thus increasing the number of collisions between the drops and facilitating the approach
between them and their subsequent coalescence.
• Aging of an emulsified crude oil: if the crude oil is stored and not treated, a certain amount of
water will precipitate by gravity and another part will remain emulsified.
• Type of oil: paraffin-based crude oils do not form stable emulsions, while naphthenic and mixed-
base crudes form stable emulsions due to the large amount of asphaltenes they contain. Waxes,
resins, asphaltenes, and other solids tend to influence emulsion stability.
• Emulsifying agent: for the stabilization of the dispersed phase by forming a strong and elastic
membrane or film that surrounds the surface of the globules. Therefore, as the presence of
emulsifying agents in the crude oil and in the water increases, the stabilization of the emulsion
increases.
• Electrical charges: the stability of an emulsion will increase when the electrical charges of the
particles increase. Some emulsions are completely stabilized by electrical attraction.
• Exposure to air: emulsions become more stable when exposed to air, due to processes such as
oxidation, photolysis, evaporation of light and bacterial action that tend to further stabilize the
emulsion.
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• Droplet size: the emulsion tends to be more stable as the droplets are smaller because the interfacial
area is greater and the interfacial tension decreases, making the film more rigid and stable.
Typically, when the droplet diameter decreases to values of 10 microns, the emulsion becomes
more stable.
Emulsion formation and stability (general considerations): emulsions in porous media
Studies have confirmed that the formation of crude oil emulsions and their stability are dependent on the
composition of the crude oil. The natural emulsifying agents such as asphaltenes, resins, naphthenic acids
and fine solids form the rigid layer at the water-oil interface and generate an increase in the viscosity of
the crude oil (Faizullayev et al., 2022).
Emulsion Challenges in Venezuela

Cold Production
As it was mentioned above, Venezuelan highly viscous crudes are characterized by their high viscosity and
density due to high content of resins and asphaltenes, natural emulsifiers, which combined with water and
shear in the production and transport may form complex emulsions, generally water-in-oil emulsions (W/
O). Figure 4 shows a water-in-oil emulsion typically formed during cold production in the Orinoco Oil Belt.
This system can be defined as a continuous oil phase with water droplets and asphaltene particles in it as
a discontinuous phase.
Figure 4—Water-in-oil emulsion observed by extra-heavy oil cold production (Rodriguez, 2016).
Water composition could affect the stability of the emulsions found during cold production in Venezuelan
highly viscous oil reservoirs. Water composition and salinity can vary vertically and laterally in some
Venezuelan reservoirs, this is the case of the Orinoco Oil Belt. Differences between connate water and
production water during primary cold production have been reported in the literature (Marcos et al., 2007;
Volcan, 2015; Boschetti et al., 2018; Pulido, 2018; Lopez, 2018). Three families of static waters have been
identified in La FPO: Connate waters, meteoric waters, and mixed waters.
According to Pulido (2018), meteoric waters include ocean waters, water evaporated into the atmosphere,
rainwater, surface water, and moving groundwater. Figure 5 shows an illustration of the hydrological
SPE-211106-MS 7
regimes in a sedimentary basin (Marcos et al., 2007). The term meteoric is applied to waters whose age is
less than the rock that contains them, they are waters that have recently been in atmospheric circulation, and
as such they are hydrodynamic waters in constant movement in the subsoil, for which the solution contains
a greater number of equivalents of the ion Na+ than the Cl− ion, resulting in a Na:Cl ratio greater than 1
(Na/Cl>1). They have low concentrations of dissolved solids, generally less than 10,000 mg/L, and have
considerable amounts of bicarbonate ion.
Figure 5—Hydrological regimes in a sedimentary basin (Galloway, 1983), Marcos et al., 2007.
Connate waters are those trapped during the accumulation of sediments in the sedimentary basin, so their
age is equal to that of the surrounding rock. According to Pulido (2018) as such, they undergo processes
of concentration and ion exchange in closed systems out of contact with the atmosphere for an appreciable
geological time, which results in the Na/Cl ratio remaining equal to or less than 1. These waters are often
displaced towards higher strata and accumulate in aquifers where they can be mixed to a greater or lesser
degree with meteoric waters, in this case it is not connate waters but emigrated waters. They are highly
salty, containing 20,000-250,000 mg/L of total dissolved solids, presenting high concentrations of chloride
and very low concentrations of bicarbonate and sulfate ions.
Mixed waters are those waters that result from the combination of meteoric and connate waters. In most
sedimentary deposits, there is a transition zone that contains water of mixed origin (Shi et al., 2018; Pulido,
2018), which is established between the meteoric waters close to the surface and those of greater depth that
are connate (Pulido, 2018).
Marcos et al. 2007 reported that for some reservoirs in the Orinoco Oil Belt, connate waters show high
content of sodium and chlorites, and relatively high total dissolved solids TDS (TDS>10,000 ppm). TDS
up to 25,000 ppm is reported by Marcos et al, 2007. Meteoric waters show predominance of HCO3- and
moderate TDS (3,000 ppm<TDS<5,000 ppm). Mixed waters show high content of sodium and TDS values
between connate and meteoric waters (Marcos et al., 2007).
It is reported that the composition of the reservoir brine (Henthorne et al., 2014; Meng et al., 2015;
Rayhani et al., 2022) could have an impact on the stability of the emulsions from Venezuelan highly viscous
oils during cold production. Precipitation of solids or scales have been reported after the preparation of a
synthetic brine from the Orinoco Oil Belt due to the presence of Bicarbonate (basic waters with pH close to
8), and in this case precipitation of scale at both room temperature (25°C) and reservoir temperature (50°C)
8 SPE-211106-MS
were reported and are presented in Figure 6. For this case water treatments were required, by eliminating
the calcium, to avoid the formation of scale/solids. Typical compositions by ions of brine from the Orinoco
Belt and Maracaibo basins are reported in the literature (Guerrero, 2010; Rodriguez, F. 2016; Rodriguez,
D., 2016), with an example listed in Table 2.
Table 2—Ion composition and overall properties of a brine from the Orinoco Oil Belt (Rodriguez F., 2016).
Figure 6—Precipitation of calcium carbonate at 50 °C for a brine sample

(synthetic brine reproduced at lab): Orinoco Oil Belt brine composition
An international emulsion study, a rheological study of the behavior of water-in-oil emulsions considering
the effect of salt concentration for samples of Brazilian heavy oils was presented in the literature. It
was reported that emulsification is influenced by the type and salinity of the aqueous phase (Neto et al.,
2019). This study evaluated the rheological behavior of W/O emulsions of five heavy crude oils (10.8
- 19.0 °API) from the sedimentary basin of the Brazilian coast. Factors related to stability (temperature,
salt concentration, amount of emulsified water) and rheological behavior of the W/O emulsions (dynamic
SPE-211106-MS 9
viscosity, stress, and shear rate) were analyzed and related to the oil chemical composition in terms of
saturates, aromatics, resins and asphaltenes. The results of the rheological evaluation indicated that for the
case of stable emulsions there was a 1212% increase in the dynamic viscosity because of the amount of
aqueous phase. In general, the increase in salt concentration and temperature aided in the stabilization of
unstable emulsions.
Foamy oil effect on stable gas-in-oil emulsions. Foamy oil is a form of non-Darcy two-phase flow in
which the viscous forces have become comparable to or stronger than the capillary forces (Maini, 1999).
Foamy oil flow involves dispersed flow of gas in the form of pore size or larger gas bubbles that become
mobilized as a result of high-pressure gradient established during the depletion process. Whether or not
foamy oil occurs, primary depletion depends not only on the oil properties (IFT between oil and the released
gas) but also on the sand properties and operating conditions (pressure gradient); Maini (2001). Claridge
and Prats (1995), suggested that asphaltenes and resins would coat the bubble surfaces and prevent further
bubble growth and coalescence. Bubbles move with the oil through pore throats with the oil phase velocity.
The gradual removal of the asphaltenes from the oil phase causes a significant reduction in the oil phase
viscosity, which is the main reason for the higher well productivity. Eventually the asphaltic film ruptures
and escapes to form a separate phase.
Laboratory experiments on Venezuelan extra-heavy oils have been performed by Li et al., 2012, in which
it is possible to observe the appearance of an extra-heavy foamy oil at the outlet of sand packs (it looks
like a swollen oil) as illustrated in Figure 7. Foaminess improves the primary production of extra-heavy oil
reservoirs which allows an economic oil flow and ultimate recovery, thanks the mechanism of enhanced
solutions gas drive. According to Pina-Acuna (2003), the foamy oil behavior of the crudes of the Orinoco
Oil Belt promotes the formation of very stable gas-oil and oil-water emulsions.
Figure 7—Foamy oil produced from the outlet of a sand pack (after Li et al., 2012).
Emulsion Generation after the Application of IOR methods in Venezuelan Viscous Oil Reservoirs
Different types of emulsions have been observed after the application of IOR methods in Venezuelan highly
viscous oil reservoirs. Figure 8 shows the methods that have been evaluated in Venezuela either at the
laboratory or field scale, being the following: waterflooding, thermal IOR, chemical IOR, miscible gas
flooding, water-alternating-gas (WAG), solvent flooding, microorganism IOR, among others.
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Figure 8—IOR Methods that have been evaluated in Venezuela either at lab or at field scales (Rodriguez, F., 2021).
Thermal IOR Methods. Thermal IOR methods have been traditionally applied in highly viscous crude
oil reservoirs in Venezuela to increase oil mobility. Table 3 and 4 show the main Thermal IOR methods
evaluated in both Maracaibo and Eastern Venezuela basins, respectively. These methods are the following:
Cyclic Steam Stimulation (CSS; Lanfranchi, 1977; Reina, 1994; Ovalles et al., 2001; Ovalles et al.,
2008; Urdaneta et al., 2012; Quintero and Armas, 2012; Mencia, 2018; Pena and Patino, 2019), steam
flooding (Araujo, 1977; Herrera, 1977; Ovalles et al., 2002; Vega et al., 2011; Koottungal, 2014), Horizonal
Alternating Steam Drive (HASD; Fernandez et al., 2008; Deveaux et al., 2009; Hoye et al., 2009); Steam
Assisted Gravity Drainage (SAGD; Deveaux et al., 2009; Hoye et al., 2009; Acasio, 2012; Franco et al.,
2012; Guinand et al., 2012; Koottungal, 2014; Yang et al., 2018), injection of solvents or chemicals with
steam/hybrid methods (Pirela, 1977; Mendez et al., 1992; Valera et al., 1999; Kumar et al., 2001; Castro et
al., 2010; Quevedo, 2013), air injection or in-situ combustion (Herrera, 1977; Terwilliger et al., 1975; Anaya
et al., 2010; Perozo et al., 2011; Hincapie et al., 2011; Arturo et al., 2011; Amaro, 2013; Goncalves, 2015;
Torres and Flores, 2017), downhole electrical cable/electromagnetic heating (Ovalles et al., 2002; Somogyi,
2004; Quintero et al., 2014; Alvarez, 2015; Velasquez et al., 2020; Yadali Jamaloei, 2022), among others.
SPE-211106-MS 11
Table 3—Thermal projects Western Venezuela (Maracaibo Basin), adapted from Koottungal (2014).
Table 4—Thermal EOR Eastern Venezuela Basin, adapted from Koottungal (2014).
Laboratory and field studies have shown the formation of complex emulsions after the application of
thermal IOR methods (Araujo, 1977; Ovalles et al., 1998; Garcia et al., 2016; Lee and Babadagli, 2020).
Araujo (1977) reported complex emulsions of high viscosity during a steam injection project in the Orinoco
Oil Belt (Lot 7 of the Morichal Field; in MPG 7-166 and 7-73 wells). According to Araujo (1977), a dense
water-in-oil emulsion was observed during the period of maximum heating. The analytical results of the
emulsion indicated that the oil phase contained finely divided solids, contributing to its stability. The crude
separated was so dense and of such as high viscosity that it did not represent a commercial product (Araujo,
1977). Emulsion is one of the most common operational issues for in situ combustion projects (Garcia et
al., 2016; Manrique et al., 2022). For the case of the in-situ combustion process, formed emulsions are
very stable water-in-oil ones (Garcia et al., 2016). Figure 9 presents the formation of emulsions (effluents)
12 SPE-211106-MS
in an extra-heavy crude from the Orinoco Oil Belt (9 °API and 4500 cP at 50°C) due to temperature and
composition changes by diluent after core displacement tests, which have been reported in the literature by
Rodriguez, F. (2016). In this image it is possible to observe the existence of different phases in the emulsion
such as: crude oil, water, asphaltenes and solids (sand particles).
Figure 9—Complex emulsion due to changes of composition (addition of diluent) and temperature (after Rodriguez, 2016).
Chemical EOR (CEOR) Methods. These type of emulsion issues become more complicated and involved
when there are also alkali, surfactant, and/or polymer in their composition in a combined or separate manner
(Sheng, 2010; Walker et al., 2012; Cendejas et al., 2013; Kronberg et al., 2014; Fortenberry et al., 2015;
Curren et al., 2018; Argillier et al., 2018; Mittal et al., 2018; Leon, 2018; Graham and Frigo, 2019; Zagitov
et al., 2020; Su et al., 2021; Zhu et al., 2021; Chang et al., 2022; Rousseau et al., 2022; Mouret et al., 2022).
This represents a big challenge for the application of any CEOR processes because of emulsion stability
versus coalescence, separation of phases, oil and water quality specifications, recycling of chemicals, etc.
Several IOR/EOR methods through the injection of chemical additives such as alkali, surfactants, and
polymers, have been evaluated in Venezuela (Lichaa, 1977; De Ferrer, 1977; Farouq Ali et al., 1979;
Mendoza et al., 1991; Guerrero, 2010; Mendoza, K., 2010; Manrique et al., 2012; Fabbri et al., 2013;
Oliveros et al., 2013; Fabbri et al., 2014; Rodriguez et al., 2014; Oliveira, 2015; Rodriguez, F. 2016;
Rodriguez, D., 2016; Rodriguez F., et al., 2016; Guevara, 2017; Hernandez et al., 2020; Ramirez et al.,
2020; Rodriguez, 2021) as shown in the following Table 5.
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Table 5—Characteristics of several chemical injection projects in Venezuela: Oil recovery factors before and after chemical flooding.
Among the chemical methods evaluated that have led to evaluating the impact of emulsions in the process
are the following tests:
Alkali-polymer flooding. An experimental study to evaluate the feasibility of alkali and polymer injection
for the Urdaneta Field (Maracaibo Basin) has been reported in the literature by Guerrero (2010). In this
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study, different tests were carried out to determine the concentration of alkali required to reduce the viscosity
of the original crude oil (12 °API and 318 cP at 82°C) through the formation of oil-in-water emulsions. The
characterization of the formation water was also done and is shown in Table 6.
Table 6—Characterization of reservoir water (Guerrero, 2010).
For these tests, alkali dilutions at concentrations between 0 and 1% alkali were performed at a temperature
of 82°C to measure the viscosity of each solution by means of a rheometer, before being subjected to
a centrifuge to evaluate their stability. For the final crude displacement, the concentration of 0.2% was
considered as the optimal alkali concentration (Guerrero, 2010). Table 7 shows the viscosity results of the
emulsion crude oil-alkali formulation at different alkali concentrations and at shear rate of 10 s−1.
Table 7—Viscosity values of the crude oil/alkali emulsions (μ) at different

alkali concentrations and at shear rate of 10 s−1 (after Guerrero, 2010).
Results reported by Guerrero (2010) show an increase in the viscosity of the crude-oil/alkali mixture at
0.1%, 0.3 and 0.6 alkali, with respect to the original crude. Additionally, the stability of crude oil viscosity
for each oil-alkali solution at different alkali concentrations was analyzed after centrifugation. According
to Guerrero (2010), this increase in the viscosity of crude oil was attributed to the generation of an inverse
emulsion (water-in-oil emulsion). It is reported that the formation of this type of emulsion could generate
operational issues along with the implementation of a CEOR process, such as injectivity and plugging issues.
Figure 10 shows two samples with 0.1% and 0.2% alkali emulsion percentages.
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Figure 10—Emulsions with 0.1% (on the left) and 0.2% (on the right) alkali (Guerrero, 2010).
Alkali-surfactant-polymer flooding. Phase behavior studies for the evaluation of alkali-surfactant and
polymer injection in the Lagunillas Field have been reported by Mendoza K., 2010 presented in Figure
11. The experiments were carried out at 55°C, which made it possible to observe the interval in which the
spontaneous emulsion was formed. The results indicated that the optimal ASP composition for the evaluated
system was 10,000 ppm alkali, 696 ppm surfactant and 2,100 ppm polymer. The interfacial tension values
measured between the ASP solution and the crude were in the order of 0.002 mN/m (Mendoza K., 2010).
Figure 11—Phase behavior tests in a crude oil/ASP system at 55°C (Mendoza, 2010).
The adsorption test results indicated that 33.45% w/w of alkali, 34.98% w/w of polymer and 20.86% w/w
of surfactant were adsorbed in the Berea rock. According to Mendoza (2010), phase trapping was observed
in these experiments, indicating that 61.16% of the surfactant migrated to the crude phase.
Polymer flooding (Plot test at Petrocedeno Field, Orinoco Oil Belt). A polymer injection pilot project was
implemented in the Petrocedeno Field (Ramirez et al., 2020), where the water cut, the presence of polymer
and the production of fines make the dehydration process of the emulsions in the production streams critical,
producing crude oil out of specifications (Leon, 2018).
Leon (2018) studied the formation and stability of emulsions generated by varying the fluomechanical
properties of the emulsion. Subsequently, the effect of the concentration of the aqueous solution to be
injected and the presence of divalent and monovalent salts on the stability of the emulsions was evaluated by
means of bottle tests, implementing the dehydrating chemistry used in the field. Then, the presence of fines
was added to the system, by passing the polymer solution through a cell with synthetic sand to subsequently
16 SPE-211106-MS
generate a water/polymer/fines/crude system and study the cause of the stability of the emulsions. The main
objective of this study was to study the effect of the HPAM 3630S polymer on the formation and stability of
emulsions found in the field, in-depth study of all the agents involved (crude oil, sand, water, polymer, and
salts) and a search for a solution to this problem to avoid the production of crude oil out of specifications.
Figure 12 shows various bottles with different fines content during withing 24 hours. Among the results
obtained by Leon (2018), it is highlighted that the presence of fine particles is the cause of the stability of
the emulsions, greatly reducing the efficiency of dehydrating chemicals.
Figure 12—View of the bottle tests with fines content at 24 hours (Leon, 2018).
Characterization of Emulsions, Liquid-Liquid and Liquid-Solid Interfaces

The stability of emulsions in heavy crude oils is attributed to the presence of interface-active species at
the oil/water interface such as asphaltenes, resins, naphthenic acids, and fine solids. These interface-active
species adsorb at oil/water interface and form a rigid film, which significantly influences the interactions
between the droplets in the continuous fluid phase, interfacial properties of oil/water interface, and bulk
properties of the emulsions.
Stability of the extra-heavy oil by the relationship between resins and asphaltenes
As the solubility of the asphaltene in highly viscous oils is controlled by resins, this could have an important
role in the formation of very stable oil-water emulsions. The stability of the W/O emulsions could be
due to strong interfacial films formed by asphaltenes that are very resistant to coalescence. It is reported
that the droplet size distribution influences the properties of the emulsion in terms of degradation rates,
long terms stability, viscosity, chemical reactions (e.g. the kinetic of polymerization, catalyzed reaction
for refinery process) where the interfacial area between oil/aqueous phase has strong influence (Jurado et
al., 2007). Some methods to characterize the size distribution of the emulsions is the use of parameters
such as median drop size, Sauter diameter, and diameter of the largest stable drop size; additional methods
for characterization of emulsions are reported by Jurado et al., 2007. Carboxylic acids of relatively low
molecular weight (compared to asphaltenes) and high interfacial activity could also be adsorbed at the
interfaces (Acevedo et al., 1998). Carboxylic acid fraction of crude oils, with compounds including linear
fatty acids, isoprenoid acids, monocyclic, polycyclic, and aromatic acids and the cyclic acids have been
identified according to their ring structure (Meredith et al., 2000).
SPE-211106-MS 17
Natural surfactants play an important role in the stability of emulsions (Forte, 1994; Acevedo et al.,
1999; Vezaro et al., 2002; Alvarez et al., 2009; Borges, 2012; Abubakar et al., 2018; Patil et al., 2021). One
method to break water-oil emulsions could be the application of the centrifugation technique. However, this
is a risky technique because centrifugation can modify the original composition of the oil by precipitating
asphaltenes, inorganic sediments and ions presents in the oil and water (Si, Ca, Mg, Fe, V, Ni, etc). Due to
the characteristics of highly viscous Venezuelan crude oils (high viscosities, high acid numbers, and high
content of resins and asphaltenes) (Lichaa and Herrera, 1975; Rojas et al., 1977; Acevedo et al., 1993;
Murillo and Chirinos, 1994; Acevedo et al., 1999; Trebbau et al., 1999; Dusseault, 2001; Fan and Buckley,
2007; Huc, 2011; Sorondo, 2012; Huc 2013; Borges et al., 2014; Wuyke, 2016; Rodriguez, F., 2016), they
can form very stable water-in-oil (WO) emulsions. The stability of emulsions in a heavy crude is strongly
related to the content of asphaltenes and resins present in the crude as illustrated in Figure 13.
Figure 13—Scheme of stabilization of water droplets by natural emulsifiers (Faizullayev et al., 2022).
The resins have a large influence on the stabilization of the crude oils (Argillier, 1999; Matthew Spiecker
et al., 2002; Velasquez et al., 2021). Argillier et al., 1999 reports that the resins, generally described as
peptizing, can be characterized by their absorbing ability at the periphery of asphaltene micelles, and thus
acting as dispersants, stabilizing the interface between the asphaltenes and the rest of the crude oil. As
the solubility of the asphaltene in heavy and extra-heavy oils is controlled by resins, this could have an
important role in the formation of very stable oil-water emulsions in their variety of forms. The influence of
the chemical nature of heavy oil phases on the performance of demulsifiers is reported by Meza et al., 2022.
A stability study focused on observing the coalescence and flocculation phenomena of emulsions of
extraheavy oil in water stabilized with natural surfactants, using crude oil samples from the Cerro Negro
Field, was described by Guanchez (2005). The emulsions were stored over time and their static and dynamic
stability were determined. In addition, stress studies of these systems were carried out. Among the results
obtained, it was observed that some ionic and non-ionic surfactants produce a positive synergy with natural
surfactants, reflecting a decrease in the average droplet diameter and interfacial tension values (Guanchez,
2005).
Wang et al., 2021 presented a review of the stabilization mechanisms of complex emulsions, including the
presence of interface-active species, their effects on the intermolecular, surface forces involved, properties
18 SPE-211106-MS
of oil/water interface and bulk properties of their emulsions. According to the different stabilization
mechanisms of O/W and W/O emulsions, they subdivide demulsifiers into breakers (EBs) applied to
demulsify W/O emulsions and reverse brakers (REBs) for O/W emulsions.
A study of water-in-oil (W/O) emulsions during a thermal EOR project (in-situ combustion EOR method)
for three different Colombian crudes has been reported by Alvarez (2021). This study considered the
characterization of emulsions through their gravimetric behavior, droplet size distribution, rheology, and
viscosity. After the study of critical variables of emulsion generation (shear rate, water content, oxidation
level and addition of silica nanoparticles), it was determined that the inclusion of silica nanoparticles (1,000
mg/L) had a slight positive impact on the emulsion formation process, due to an increase in the rate of
evaporation of the water in the emulsion, a reduction in the viscosity of the emulsion and a reduction in
the size of the droplets. The application of nanotechnology to improve oil and gas operations and emulsion
issues has been also reported by Franco et al. 2017, Bera and Belhaj (2016), Lee and Babadagli (2020),
and Zhu et al., 2021.
Demulsification Techniques and Treatments

Demulsification is the process of separating an emulsion into its constituent phases. This usually involves
two distinct steps: a) droplet aggregation, b) aggregate droplet coalescence (Jarjour, 2015). The mechanisms
involved in the breaking of an emulsion are: sedimentation, flocculation, coalescence, Ostwald maturation
(Leon, 2018). Crude dehydration is one of the main operations to break the emulsion (Dalmazzone et
al., 2010), which counteracts the action of the emulsifying agents present in the crude, destabilizing and
breaking the emulsion. Dehydration of heavy crude oil emulsions using novel imidazolium-based poly ionic
liquids is proposed has been proposed in the literature by Ezzat and Al-Lohedan (2021).
Studies have shown that asphaltene concentrations stabilize water-in-crude emulsions; therefore,
electrostatic coalescers have proven to be a very efficient means for separating water-in-oil type
emulsions (Lichaa and Herrera, 1975; Lichaa, 1977; Guardia, 2007). Demulsification is often achieved
in many industrial processes with the application of mechanical (centrifugation, filtration, and associated
membrane), thermal (direct heat exchangers and defrosting), electrical (electrocoalescence) (Rivero, 2007;
Rebolledo, 2007; Ansari et al., 2015), reactive chemicals (demulsifiers) and electromagnetic processes
(ultrasound and microwave radiation) (Jarjour, 2015). An evaluation of the impact of using membranes and
one-dimensional scanning techniques on droplet size distribution and the type of resulting emulsion was
presented by Matos (2009).
Faizullayev et al., 2022 presented a review of the most recent demulsification methods of crude oil
emulsions, indicating the advantages and disadvantages of several methods based on chemical, membrane,
electric, magnetic, microwave separation, biological method, among others, used for the breaking of
water-in-oil emulsions. Faizullayev et al., 2022 reported that membrane separation is one of the most
efficient methods used for the separation of oil and water emulsions, which does not require high energy
and thermal expenditure. However, this technology is susceptible to fouling with the need for periodic
cleaning. According to Faizullayev et al., 2022, electrical demulsification offers an advantage over other
demulsification techniques in terms of energy consumption and ecological validity. Nevertheless, one of
the disadvantages of this technique is the creation of secondary fine droplets during electrocoalescence,
which makes the separation process even more difficult. On the other hand, Faizullayev et al., 2022 indicates
that microwave heating technology can be used as a demulsification method, reducing the requirement for
chemical demulsifiers.
It is reported that steam injection in heavy oil reservoirs can promote the formation of stable water-in-oil
emulsions (W/O emulsions) which increase the original viscosity of the oil and make it difficult to transport
it to the surface (Araujo, 1977; Martinez, 2010). In order to try and solve this problem, different formulations
of aqueous surfactants are used to mix them with W/O emulsions and produce unstable inverse emulsions
SPE-211106-MS 19
of extra-heavy crude oil in water (O/W emulsions). This method allows the reduction of viscosity for the
crude oil and consequently improves its transport to the treatment plants where the emulsion is broken and
dehydrated (Martinez, 2010).
A method for the destabilization of W/O emulsions by applying microwaves in Venezuelan heavy crude
oils was presented by Jarjour (2015). A microwave magnetic field was used, which interacts with the water
droplets present in the sample, producing coalescence of the same and separating a certain amount of water
from the crude oil. Emulsions with 20, 30 and 40% volume of water, respectively, were prepared and passed
through the microwave at different exposure times, where a percentage of water separation of around 60 to
40% was obtained in general for residence times in the microwave for 40 to 30 seconds.
An optimal thermo-chemical treatment was presented by Donis and Ricaurte (2005), to achieve the
separation of water and sediments from a Venezuelan "Slop" crude oil to levels below 1% required for its
commercialization. Due to its properties and characteristics the "Slop" crude oil presented a stable emulsion
(high viscosity, between 60 and 66% of emulsified water, and 14-18% of fines). Static stability tests of the
crude "Slop" were carried out at different treatment temperatures and various demulsifying and wetting
products for solids, while other treatment variables were also carried out, such as dilution of the crude "Slop"
with a crude of lower viscosity and higher °API (Sur Mediano crude oil), and the filtration of the solids
present in the previous crude "Slop" to the thermochemical treatment. Based on the treatment practices
carried out, a crude oil with 0.3% of water and sediments was obtained (Figure 14) by means of the following
treatment procedure: dilution 75% crude oil Slop-25% crude oil Sur-Mediano (%v/v), demulsifier B (2,000
ppm), humectant F (500 ppm), treatment temperature 80°C and 7 days of rest time (Donis and Ricaurte,
2005).
Figure 14—Microphotograph of the best result obtained for the treatment of Slop crude
(a) compared to untreated Slop crude (b) (adapted from Donis and Ricaurte, 2005).
Martinez (2010) presented a study for the evaluation of water demulsifying formulations in Venezuelan
extra-heavy crude. This study considered different formulations of alkaline surfactants with the purpose of
activating the natural surfactants present in crude oil and to form O/W emulsions. Additionally, mixtures of
fatty acids, mainly oleic and linoleic acid, with sodium salts and monoethanolamine were evaluated. The
results of this study show the formation of emulsions type W/O/W when the O/W emulsion is mixed with
the formulation of surfactants. However, the viscosity of multiple emulsions is similar to that of water and
can be easily transported. In order to break and dehydrate the multiple emulsions, the method of heating in
synergy with brine for several hours was used. The best results were obtained when the multiple emulsions
were in contact with a natural chemical compound of alkyl polyglucoside extracted from the Aloe Vera
plant. This alkylpolyglucoside worked as an excellent demulsifier in synergy with the heating and brine
solution, since the emulsions dehydration percentage was up to 98%.
The detailed characterization of an emulsion produced during SAGD operations was reported by Balsamo
et al. 2014. For this study, techniques such as Differential Scanning Calorimetry (DSC) and Multiple Light
Scattering with near infrared radiation were used, with the purpose of determining the type of emulsion, the
20 SPE-211106-MS
amount of free and emulsified water, as well as to monitor the stability of the evaluated emulsions. Balsamo
et al. 2014 states that a comparison of the results with droplet size and zeta potential values indicated that
stability in this type of emulsion results from a balance of the steric and electrostatic mechanisms, the
former being the dominating force. It was demonstrated that asphaltene aggregates can be present at low
concentration (i.e. 0.005 wt%) and they play a key roles on SAGD emulsion stabilization. A recent study
for the separation of emulsions produced from a SAGD operation has been reported in the literature by Shu
et al., 2021. In this case, five demulsifiers (synthesized by polymerization of the polycyclic phenol-amine
resin, polyoxyethylene and polyoxypropylene) and six polyamine block polyether reverse demulsifiers were
evaluated through laboratory bottle tests and field tests. The effects of chemical properties (resins and
asphaltene contents and molecular weight), injection dosage, injection scheme (demulsifier only versus
the combined demulsifier and reverse demulsifier), and treatment density on separation efficiency were
also evaluated. Within the results of Shu et al. 2021 the following stand out: Polyamine block polyether
demulsifiers were able to migrate to the oil-water interface immediately in the pre-treatment stage, replace
the pre-existing natural surfactants, weak the strength of interface film, partially neutralize surface charges,
and promote coalescence and separation of water droplets. In this case, the emulsion type changed from
oil-in-water (O/W) to water-in-oil (W/O) after treatment. Additionally, within the results of Shu et al., 2021
indicates that in the subsequent demulsification process, the injected high-temperature resistant demulsifier
separated the W/O emulsion with multiple effects. The asphaltene dispersant and sand/clay removing
additive blended into the demulsifier strengthened the separation performance by affecting the stability of
the emulsion and reducing the surface activity of clay particles. According to Shu et al., 2021, the field test
results exhibited that the selected chemicals treated the SAGD produced emulsions efficiently, as it was
observed a more stable density profile, lower oil content of the separated water, and lower water content of
the separated oil. A schematic of the field test system is shown in Figure 15.
Figure 15—Schematic of field test for the evaluation of separation performance of the produced emulsion (Shu et al., 2021).
SPE-211106-MS 21
Regarding other international experiences with demulsifiers at field scale, for the case of an in-situ field
project in Louisiana-USA (Bellevue Field), chemical treatments to break emulsions based on a mixture of
polyglycerol fumarate ester, heavy aromatic naphtha, and electrical heaters have been successfully applied
(Sharma et al., 2021).
Almorihil et al., 2021 reports that a second stage of gravity settling with the addition of demulsifiers is a
common practice in processing plants to further treat the separated water. In the same way Almorihil et al.,
2021, based on laboratory results, reported that single-stage gravity settling is not good to achieve acceptable
water quality levels for disposal and re-injection into oilfield, and that secondary centrifugation allowed
clear and significant improvement in water quality even in the presence of EOR chemicals. Almorihil
et al., 2021 indicated that the separation efficiency with centrifugation was a function of the rotational
speed; higher operational speed resulted in higher creaming velocities and faster separation. In terms of the
effects of investigated EOR formulations, SP (surfactant-polymer) addition produced minor but manageable
reduction in separated water quality at a level that would not harm conventional disposal practices.
A study on the impact of back-produced EOR polymer at the laboratory scale on various topside
equipment before implementing a polymer injection project at a wider scale in a Colombian heavy oil
reservoir (18°API, Casabe Field) was reported by Mouret et al., 2022. This study considered primary
separation, static gravity clarifying, deep-bed filtration and heater fouling. Additionally, a large residual
polymer concentration and water cut ranges were evaluated to consider some produced fluid composition
change over time. Within the results of the study by Mouret et al., 2022, it is indicated that: 1) the selected
polymer does not stabilize tight water-in-oil emulsions, but it has a negative impact on the water quality;
2) compatibility issues were observed with the evaluated demulsifiers which are related to both polymer
concentration and water cut, 3) the fouling risk of heat exchanger was very low in the testing conditions,
4) filtration and gravity settling performance were reduced on the oil removal side of the water, but the
right chemical and equipment combination enabled to obtain a better water quality and to meet injection
specification targets.
A review performed by Faisal and Almomani (2022) introduced different chemicals applied for the
demulsification and recovery of oil from oil-in-water emulsions. They reported that main types of surfactants
(anionic, cationic, nonionic and amphoteric) involved the formation of emulsions and enhanced their
stability. Also, it is reported promising demulsifiers such as nanoparticles, hyperbranched polymers,
and ionic liquids. According to Faisal and Almomani (2022) functionalized magnetic nanoparticles and
hyperbranched polymers were effective in recovering O/W emulsions with an efficiency >95%.
Conclusions and perspectives

The stability of emulsions of the heavy and extra-heavy crude oils of Venezuela is attributed to the presence
of interface-active species at the oil/water interface such as asphaltenes, resins, naphthenic acids, ions, and
fine solid. With all heavy crudes, including the Venezuelan, mobility of oil through the reservoir, production
string, flowlines, pipelines, and other surface facilities is a serious concern and poses many technical and
economical challenges. In this article, we studied different aspects of emulsion stability with a focus on the
water-oil and the gas-oil. In this assessment, different types (in terms of crude composition) of Venezuelan
heavy oils have been used and among other different concerns, emulsion stability and fluid characterizations
and rheology were found to be the most decisive features. We used the Orinoco Oil Belt crude as a case study
and a pilot for other Venezuelan crudes. For this crude oil, the resins and asphaltenes content represented
fundamental and essential elements for the stability of the emulsions in the cold production scenario, and the
composition of the formation water increases the stability of the emulsions, specifically with an increase of
Mg2+ and Ca2+ concentrations. The authors believe that the used case study has the potential for generalized
to other types of Venezuelan crude oils with a strong faith that this investigation will help boost primary
and IOR production from Venezuelan crude oils.
22 SPE-211106-MS
Acknowledgements
The authors thank Petroleos de Venezuela S.A, Khalifa University of Science Technology, and IFP Energies
nouvelles for their support.
Nomenclatures
Bbl: Barrels
CEOR: Chemical enhanced oil recovery
CSS: Cyclic Steam Stimulation
HASD: Horizonal Alternating Steam Drive
ISC: In-situ combustion
IOR: Improved oil recovery
PVI: Injected pore volume
SAGD: Steam Assisted Gravity Drainage
TDS: Total dissolved solids
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28 SPE-211106-MS
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Emulsion formation and stability (general considerations): emulsions in porous media

Emulsion Challenges in Venezuela

Figure 6—Precipitation of calcium carbonate at 50 °C for a brine sample

Table 6—Characterization of reservoir water (Guerrero, 2010).

Table 7—Viscosity values of the crude oil/alkali emulsions (μ) at different

Characterization of Emulsions, Liquid-Liquid and Liquid-Solid Interfaces

Demulsification Techniques and Treatments

Conclusions and perspectives

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