Revista Fuentes: El Reventón Energético

Vol. 16 n.º 2 de 2018 - Jul/Dic - pp 55/71

Polymers for application in high temperature and

high salinity reservoirs – critical review of properties
and aspects to consider for laboratory screening
Yani Carolina Araujo1; Mariela Araujo2

1
SGS North America, The Woodlands, TX
2
O&G Consultant, Houston, TX

E mail: Yani.AraujoDeItriago@sgs.com

Abstract
A significant amount of oil resides in deep reservoirs characterized by relatively high temperature and high salinity. In such
reservoirs, most available chemicals fluids for EOR have limited applicability. Even though recent effort has been dedicated
to the development of high temperature polymers, there is no clear understanding of what would work best in those harsh
environments. In addition, the oil and gas community is also evaluating potential applications of chemical EOR to offshore assets
where similar conditions are often found. Field applications in harsh reservoirs have shown limited success in the use of polymers
for improved oil recovery. Detail analysis reveals that screening of the fluids was done under ‘model’ laboratory conditions, using
non-reservoir core samples and non-representative fluids. These facts have motivated research and development work towards
understanding the type of polymers that may be suitable for use in high temperature and high salinity reservoirs and to determine
the type of tests to use to assess their performance in a field application for use as lab screening criteria. In this paper, we provide
a critical review of the available polymers for application in high temperature and high salinity reservoirs and summarize best
practices for their laboratory screening though a recommended workflow.

Keywords: Harsh Reservoirs, Polymer Flooding, Laboratory Screening, Enhanced Oil Recovery (EOR) High Temperature and
High Salinity Reservoirs.

Polímeros para aplicación en yacimientos de alta temperatura y alta salinidad – revisión

crítica de propiedades y aspectos a considerar para selección en laboratorio

Resumen
Una cantidad significativa de petróleo reside en yacimientos profundos caracterizados por estar asociados a temperaturas y
salinidades relativamente altas. Para estos yacimientos la mayoría de los químicos disponibles para EOR tienen una aplicabilidad
limitada. Aun cuando recientemente se han reportado esfuerzos en el desarrollo de polímeros para altas temperaturas, aún no se
tiene un entendimiento claro de lo que funcionaría mejor en ambientes severos, con alta salinidad. Adicionalmente, la comunidad
petrolera está evaluando posibles aplicaciones de tecnologías químicas de EOR en activos costa afuera donde se observan con
frecuencia condiciones similares. Las aplicaciones en campo que involucran el uso de polímeros en yacimientos con ambientes
hostiles han demostrado un éxito limitado en el mejoramiento de la recuperación de petróleo. Un análisis minucioso revela que
la selección de los fluidos se realizó bajo condiciones de laboratorio “modelo”, utilizando muestras de rocas y fluidos diferentes
a los encontrados en el yacimiento. Estos hechos han motivado el trabajo de investigación y desarrollo para comprender el tipo
de polímeros que pudieran ser adecuados para uso en reservorios de alta temperatura, que presentan fluidos de alta salinidad, y
para determinar el tipo de pruebas a utilizar para evaluar su desempeño en una aplicación de campo que podrían utilizarse como
criterios de selección de laboratorio. En este trabajo se ofrece una revisión crítica de los polímeros disponibles para aplicación en
yacimientos de alta temperatura y alta salinidad, y se reporta un resumen de buenas prácticas para su selección en el laboratorio
siguiendo un procedimiento recomendado.

Palabras clave: Yacimientos Hostiles, Inyección de Polímeros, Selección en el Laboratorio, Recuperación Mejorada de Crudo
(EOR), Yacimientos de Alta Temperatura y Salinidad.

Cita: Araujo, Y.C. & Araujo, M. (2018). Polymers for application in high temperature and high salinity reservoirs – critical
review of properties and aspects to consider for laboratory screening. Revista Fuentes: El reventón energético, 16(2), 55-71.

DOI: http://dx.doi.org/10.18273/revfue.v16n2-2018004 55
REVISTA FUENTES, El Reventón Energético Vol. 16 n.º 2

Introduction in-situ temperature and brine salinity, and for the high
cost involved.
The increasing global energy demand relies heavily on
the use of hydrocarbons; however, the discovery of oil Polymer flooding is one of the most attractive chemical
and gas deposits is becoming increasingly difficult with enhanced oil recovery techniques. Its successful
findings in complex and challenging environments. application has been related to the existence of favorable
Most of the easily accessed oil is already depleted, and reservoir conditions. Most applications have been done
approximately 50% of the initial hydrocarbons remain in clastics reservoirs, although a few projects were
trapped in the reservoirs. These facts are promoting the implemented in carbonates. The main reason on the
evaluation of enhanced oil recovery (EOR) methods as a limited application in carbonates is due to challenges
way to sustain operations and satisfy the energy demand. preserving the polymer properties at the in-situ high
temperatures, and high salinity. Benefits of polymer
EOR technologies refer to a variety of methods aiming flooding reported in the literature (Abidin, Puspasari
to recover stranded oil on partially depleted reservoirs. & Nugroho, 2012) refer to the use of Xanthan Gum,
Some of the methods involve the injection of agents, a PAM (polyacrylamide), HPAM (partially hydrolysed
fluid or a combination of fluids into the reservoir (e.g.: polyacrylamide), and sodium acrylate as co-polymer,
chemical, gas, thermal and microbial). The injected fluid for applications where the in-situ reservoir temperature
enhances the oil displacement resulting in lowering of was below 70°C. In general, these polymers enhance
the residual oil saturation. The injected fluids interact the rheological properties of the displacing fluid since
with the in-situ rock-fluid system (brine, oil, gas) and the water-soluble polymers can improve the water-oil
may generate conditions favorable for oil recovery, mobility ratio (Pinto, Herrera & Angarita, 2018), leading
like lowering of the interfacial tension (IFT), inducing to enhanced oil recovery. However, the properties of
wettability alteration, developing preferential phase the polymeric solution render it to be very sensitive to
behavior, etc. changes such as temperature and salinity, thus when
exposed to such harsh conditions as frequently present
Chemical EOR methods have a long history of field in some oil reservoirs, new problems and limitations
implementation dating back to 1970’s. The most arise when using such standard chemicals (Quadri,
popular of these methods is polymer flooding in use Shoaib, AlSumaiti & Alhassan, 2015).
in several countries for over 40 years with various
degree of success (Needham & Doe, 1987). Most Polymers and co-polymers such as PAM, HPAM and
polymer flooding field applications to date were done sodium acrylate have been successfully used in certain
in reservoirs with in situ-temperature in the range countries like China, India and Oman. Their popularity
8°C-110°C, formation permeabilities values between is associated to the thickening ability, the flocculation
1 mD and 15 D, brine salinities ranging from 0,1 to and rheological behaviour in the tested formations
30 % TDS, and oil viscosities in the range of 0,01 cP (Sheng, 2011). In Daqing, China, water-soluble
to 2.000 cP. Polymer flooding is frequently done after polymers are in use for over 30 years. The introduction
waterflooding, attempting to address two types of of new polymers, co-polymers and other chemicals
problems: 1) low volumetric sweep and displacement made Daqing an excellent place for extensive field
efficiency, and 2) high residual oil. trials providing significant learnings on the technology
performance to the oil and gas industry, including the
The implementation of chemical EOR technologies ability to use alkali to significantly reduce the amount of
is always a challenge since they involve multiple surfactants needed in an ASP project and associated cost
processes frequently addressed by several disciplines. savings. In the Mangala field, India, ASP floods have
In the last three decades, the most significant advances been extensively implemented allowing the operator to
in the development of chemicals for EOR applications maintain the target production levels. ASP formulations
are found in the manufacturing of surfactants, polymers, have been also successfully used in both sandstone and
co-solvents and gels. In fact, more new polymers carbonate reservoirs in China and Oman.
were created in the last 10 years than in the previous
30 years for other oil production applications. Such a More recently, Oil and Gas Majors have started to
development has enabled the industry to consider the use use polymer flooding in offshore areas like the North
of such chemicals for EOR with incremental recovery in Sea, where new polymers specially designed for high-
the range of 20-30%; however, the range of application temperature and high salinity environments are being
is quite limited based on the reservoir characteristics, deployed (Hinkley & Brown, 2017)

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 Polymers for application in high temperature and high salinity reservoirs – critical review
of properties and aspects to consider for laboratory screening

In this paper, we provide a critical review of significant viscosity loss (You, et al., 2007)
the available polymers for application in high (Levitt, Pope & Jouenne, 2010).
temperature and high salinity reservoirs and
summarize aspects to consider for their laboratory 2. Acrylamide (AM): a highly water-soluble vinyl
monomer formed from the hydration of acrylonitrile
screening through a recommended workflow.
with chemical formula C3H5NO. Its structure
includes one hydrogen bond donor, one hydrogen
Available polymers and suitability bond acceptor, and one rotational bond. AM
for use in harsh environments copolymers can be classified into four categories
based on their ionic characteristics as non-anion,
In polymer flooding, a water-soluble polymer is added anion, cation, or zwitterionic compounds (Pei, et
to the injected water during a waterflood. The objective al., 2016). The anionicity (degree of hydrolysis)
is to increase the viscosity of the water phase to improve of AM monomers varies from 15% to 40% for
the efficiency of the displacement.   There are three commercial AM (Borthakur, Rahman, Sarmah &
potential ways in which a polymer flood can make the Subrahmanyam, 1995) (Levitt & Pope, 2008).
oil recovery process more efficient: a)by decreasing the
water/oil mobility ratio; b)through the effect of polymers a. Acrylamide-based polymers and copolymers
on the fractional flow, and c)by diversion of the injected are unstable at elevated temperatures (>70oC)
water from zones that are already swept. It is well in hard brine (i.e. water saturated with divalent
known that when a polymer is injected into a formation salts (CaCl2)) due to hydrolysis of the amide
containing a stack of heterogeneous layers, crossflow group to carboxylate. The presence of divalent
between the layers improves the polymer allocation so ions promotes the formation of carboxylate
that the vertical sweep efficiency is improved (Sorbie, complexes that lead to polymer precipitation
1991). Another interesting mechanism is related to reducing its useful lifetime (Moradi-Araghi &
the polymer viscoelastic behavior. Due to polymer Doe, 1987). The degree of hydrolysis depends
viscoelastic properties, the normal stress between the oil on the acrylamide and hydroxide concentrations.
and the polymer solution results in a larger pull force on
the oil droplets or oil films. As a result, oil is pushed and b. For pH < 7, non-dissociated acid groups act as
pulled out of dead-end pores or disconnected/stagnant internal catalysts towards acrylamide hydrolysis
pore regions, resulting in a decrease of the oil saturation (Parker Jr. & Lezzi, 1993) and for pH values >
(Sheng, 2011). 7 two opposite effects can occur according to
the pH value: a) an increase in the degree of
Current available polymers and co-polymers for EOR hydrolysis due to the greater number of hydroxide
applications include: ions present, and b) a reduction of the hydrolysis
rate due to the formation of negatively charged
1. Sodium Acrylate (AA): an anionic polyelectrolyte carboxylate residues.
with negatively charged carboxylic groups in
the main chain and molecular formula [−CH2− c. The degree of acrylamide hydrolysis depends on
CH(CO2Na) −]n . It is primarily used as a thickening the temperature and the hydroxide concentration.
agent for its unique ability to absorb and hold Ryles reported that temperatures below 82°C are
onto water molecules, and to combine with other required for acrylamides to remain in brine and
monomers. avoid precipitation in the presence of divalent
cations (Ryles, 1988).
a. AA cannot withstand high salt concentration,
especially in the presence of divalent cations, 3. Acrylamide Co-Polymers: modified versions of
at high temperatures and under long injection acrylamide co-polymers with other monomers
times. synthetized to improve the limit temperature for
precipitation onset in the presence of divalent
b. At temperatures above 70°C, AA moieties cations (Parker Jr. & Lezzi, 1993).
hydrolyze increasing the amount of polyacrylic
acid in the backbone of the polymer making a. Copolymers of N-vinylpyrrolidone (NVP) and
it very sensitive to hardness. The formation acrylamide have improved stability towards
of acrylate groups leads to precipitation and precipitation by divalent cations at elevated

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REVISTA FUENTES, El Reventón Energético Vol. 16 n.º 2

temperatures with respect to polyacrylamides The four polymers were basically sulfonated
(Doe, Moradi-Araghi, Shaw & Stahl, 1987). polyacrylamide copolymers of AM (acrylamide)
Gaillard, et al. (2014) reported that the with AMPS (2-Acrylamido-2-Methylpropane
incorporation of NVP monomers into the Sulfonate). The modified co-polymers showed
polymer chains make it more stable by limiting similar rheological behavior to conventional
the degree of hydrolysis, and by bringing polymers, except one with a unique behavior, a
robustness at high temperatures (120°C). sulfonated polyacrylamide copolymer AM with
However, the NVP molecular weight requires AMPS, with a 32 mol % sulfonation degree and
more polymer per application (about 3 times the high molecular weight found to be less sensitive
amount of conventional HPAM) making the cost to salinity and temperature for temperatures up
of the process not attractive for operations. to 95°C, which could possibly make it as a better
candidate for enhanced oil recovery (EOR)
b. The incorporation of sodium-2-acrylamido-2- application in high salinity conditions.
methylpropanesulfonate, acrylamido-tertio-butyl
sulfonate (ATBS) results in an improvement of b. Wu, Mahmoudkhani, Watson, Fenderson &
the polymer stability up to 120°C (Parker Jr. & Nair (2012) reported the results of a bench-scale
Lezzi, 1993) (Sabhapondit, Borthakur & Haque, development of new PAM-based polymers with
2003). These authors explained the enhancement improved performance in harsh conditions. The
in the hydrolysis when the pH decreased from 8 new polymers were evaluated for their viscosity
to 6, due to a decrease in Coulombic repulsion at various temperatures (up to 120°C) and
between hydroxide and the polymer. Moradi- salinities (up to 180 g/L). After aging at 90°C
Araghi & Doe (1987) found that ATBS does not and 120°C for six months under ultralow oxygen
protect the acrylamide against thermal hydrolysis level (< 5 ppb), the viscosity remained relatively
with consequent precipitation in hard brines. stable for the new polymers solutions.
Even though ATBS bring more robustness at
lower cost, and lower impact on molecular c. Rashidi, Blokhus & Skauge (2010) conducted
weight; the stability of ATBS is limited to the a rheological study of copolymers of AM with
temperature range 95°C to 105°C (Moradi- PAMS, and HPAM in a NaCl solution and
Araghi & Doe, 1987). synthetic seawater (rich in divalent ions). PAMS
showed better high salt tolerance compared
4. Polyacrylamide (PAM): a high molecular weight to HPAM. Also, the viscosity and solubility
(>106 g/mol) polymer formed from acrylamide effects of the PAMS were studied as a function
and its derivates. The PAM used in EOR is of the sulfonating degree and molecular weight.
poly(2-propenamide) with chemical formula PAM with high sulfonating degree was more
-CH2CH(CONH2)-. It is a non-ionic, water soluble, salt tolerant, and the effect of divalent ions on
and biocompatible polymer that can be synthesized viscosity is lower compared to HPAM.
as a simple linear chain or as a cross-linked structure.
The cross-linked polymer can absorb and retain 5. Partially Hydrolyzed Polyacrylamide (HPAM): a
large amounts of water because the amide groups copolymer of AM and acrylic acid (AA) obtained by
form strong hydrogen bonds with water molecules. partial hydrolysis of PAM or by copolymerization of
Even though these polymers are called PAM, they sodium acrylate with AM (Morgan & McCormick,
are often copolymers of acrylamide and one or more 1990). HPAM has a coil conformation making it
other monomers. One of the most common co- extremely sensitive to ionic environments. Two
monomers is acrylic acid or sodium acrylate. Poly broad types of HPAM polymers are found in EOR
(acrylamide-co-acrylic acid) and its sodium salt applications: one has a poly acrylamide backbone
are anionic polymers more effective when used as and the other a sulfonated backbone. HPAM is the
flocculant and water absorbers (polymerdatabase. most widely used polymer in EOR applications
com). (Manrique, Muci & Gurfinkel, 2007).

a. Akbari, Mahmood, Tan, Ghaedi & Ling (2017) a. HPAM has been successfully tested at high
evaluated four sulfonate-based polymers temperatures (Seright, Campbell & Mozley,
(polyacrylamide co-polymers) for stability 2009). In the absence of dissolved oxygen and
under high salinity/high hardness conditions. divalent cations, HPAM solutions can maintain

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 Polymers for application in high temperature and high salinity reservoirs – critical review
of properties and aspects to consider for laboratory screening

almost half of their viscosity for over 7 years aggregate to minimize water exposure. In aqueous
at 100°C, and about 2 years at 120°C. An solutions at a basic pH, hydrophobic groups form
acrylamide-AMPS copolymer (with 25% AMPS) intramolecular and intermolecular associations
showed similar stability to that of HPAM over that give rise to a three-dimensional network that
the same period of time. HPAM polymers can significantly increases the viscosity of the polymer
be used for temperatures up to 120°C if contact solution at high temperature conditions (Caram,
with dissolved oxygen and divalent cations is Bautista, Puig & Manero, 2006). The functional
minimized. In addition, its relatively low cost groups on this polymer are less sensitive to brine
and good tolerance to mechanical stresses during salinity compared to a conventional polymer
injection in the reservoir makes HPAM very solution. AP contains both hydrophobic and
attractive for EOR applications. hydrophilic moieties; therefore, they can resist high
salinities and moderate temperatures in comparison
b. HPAM is very sensitive to the brine salinity to HPAMs.
and hardness. The viscosity enhancement is
significantly reduced when it dissolves in high a. APs including acrylamide-ATBS and
salinity/hard brine, representing a disadvantage acrylamide–ATBS–hydrophobic monomers
for field application. In the presence of high have been developed with good performance
degree of hydrolysis, the electrolytes present (high resistance factor) for T < 95°C at low and
in the brine have a shielding effect on the high salinities.
electrostatic repulsion (Shupe, 1981) (Sukpisan,
Kanatharana & Sirivat, 1998). b. Laboratory evaluation of different APs (Alexis,
Varadarajan, Kim, Winslow & Malik, 2016)
c. High salt concentration and the presence of demonstrated the applicability of these polymers
divalent cations such as Ca+2 and Mg+2 can cause in both unconsolidated and consolidated rocks at
a reduction in the thickening capability of the different temperatures. Experiments indicate that
polymer due to a contraction of the polymer coils APs require a lower polymer concentration to
in solution, and in some cases the presence of generate high resistance factors in porous media
calcium leads to polymer precipitation (Moradi- and have stable long term injectivity behavior
Araghi & Doe, 1987) (Ryles, 1988). in high permeability rocks (> 1 D). Also, in
medium to low permeability rocks (< 300 mD)
6. Salinity Tolerant Polyacrylamide (KYPAM): a AP with HPAM backbone have better filterability
copolymer of HPAM that incorporates a small and injectivity in comparison to polymers with
fraction of functional monomers with acrylamide to HPAM sulfonated backbone.
form comb-like copolymers. These polymers have
in their structure an ionic functional group that is c. AP can promote intermolecular associations, and
tolerant to divalent cations (Luo & Cheng, 1993). thus have enhanced viscosities and resistance
In KYPAM, a functional monomer is introduced, factors (Seright, Fan, Wayrik & Wan, 2011).
and the side chains have both hydrophilic and APs showed low-flux resistance factors two to
hydrophobic groups (Sheng, 2011). The flexible three times the values expected from viscosities.
chains are stretched, and the KYPAM viscosity Displacement experiments in long cores
is relatively higher than the HPAM viscosity in suggest that the unexpected high resistance
more saline waters (Luo, et al., 2002). Laboratory factors could propagate deep into a reservoir
measurements indicate that KYPAM is more supporting enhanced displacement compared to
temperature tolerant, and it has good shear and conventional HPAM polymers. APs also show a
thermal stability (Luo, et al., 2002). significantly higher level of shear thinning at low
fluxes and a lower degree of shear thickening at
7. Associative Water-Soluble Polymers (AP). These high fluxes than HPAM.
polymers consist of a hydrophilic long-chain
backbone, with a small number of hydrophobic 8. Rigid Rod Water-Soluble Polymer: polymers with a
groups localized either randomly along the chain or helical or double stranded conformation which may
at the chain ends (Lara-Ceniceros, Rivera-Vallejo be considered as a truly rigid rod in solution (Sarkar
& Jimenez-Regalado, 2007). In contact with & Kershner, 1996). These polymers are highly
water, APs are dissolved, and hydrophobic groups soluble in water and display a shear stable behavior

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REVISTA FUENTES, El Reventón Energético Vol. 16 n.º 2

that can deliver high viscosity at low molecular properties, super-high salinity resistance
weight compared to the traditionally used flexible and temperature tolerance in harsh reservoir
chain polymers such a hydrolyzed polyacrylamide. conditions. PAMCS solution exhibited designed
viscosity efficiency and viscoelasticity, and long-
a. Sulfonated water soluble aromatic polyamides, term stability in comparison to HPAM.
polyureas, and polyimides prepared via
interfacial or solution polymerization of b. Amphiphilic polyelectrolytes or polyampholytes
sulfonated aromatic diamines with aromatic can exhibit a combination of the properties listed
dianhydrides, diacid chlorides, or phosgene have in (a). These polymers can have one or two
sufficiently high molecular weight and typically (different) charges and behave as hydrophobes.
display high intrinsic viscosity and can transform The rheological properties of these polymeric
into a helical coil in brine (Sarkar & Kershner, systems can be tailored by careful molecular
1996). design, i.e. by selecting the ratio of the different
monomers in the structure. According to the
9. Zwitterionic Polymers (ZP): polymers characterized molecular design the polymers could be pH-
by having equal anion and cation groups on the responsive, temperature insensitive or salt
molecular chains, making them highly hydrophilic resistant. For certain conditions, i.e. low pH
with antifouling properties. These polymers are and high electrolyte concentration, carboxylic
called polyampholytes; they are pH responsive groups lead to better responsive polymers when
polymers (Laschewsky, 2014). The rheology of these compared to polymers having sulphonic groups.
polymers can be tuned to the desired rheological
properties by changing the pH/ionic strength of the c. An amphiphilic copolymer based on Poly-
solution, and the temperature dependence of the ethylene glycol-methyl-ether acrylate (PEGA)
solution viscosity is minimal. These polymers can was developed by Atomic Transfer Radical
enhance the solution viscosity in salt environments Polymerization (Raffa, Broekhuis & Picchioni,
up to relevant concentrations (e.g. values higher 2016). The measured viscosity and surface
than 100 g/L TDS). At high shear though, a loss in activity of polymers solutions in pure and salty
solution viscosity is observed. water indicate that the new polymer is an effective
surface active viscosyfing agent, so it could be a
a. Alcázar-Vara, et al. (2015) showed that ZP had good candidate as polymeric surfactant for EOR
good performance as a multifunctional agent applications
with asphaltene inhibition-dispersion activity
as well as an agent to promote the alteration of 11. Xanthan Gum: a biopolymer (polysaccharide)
rock wettability and hence relative permeability, produced by the fermentation of glucose or fructose
demonstrating that ZP can be used to modify rock (Leela & Sharma, 2000). The Xanthan molecule
wettability to increase the oil recovery in high displays two glucose units, two mannose units and
salinity environments. Martin & Páez (2017) one glucuronic acid unit (Garcia-Ochoa, Santos,
reported the effect of the salinity on wettability Casas & Gomez, 2000). The side chains of the
alteration and the final recovery performance. Xanthan polymer have charged moieties (pyruvate
groups) allowing the polymer to behave like a
10. Amphiphilic Polymers: are potential candidates polyelectrolyte polymer; however, its thickening
for EOR applications due their viscosity resistance behavior does not have a strong dependence with
in the presence of electrolytes; however, they salinity; it is a consequence of the high molecular
are impacted by temperature. The rheology of weight which range from 2 to 50,000.,000 g/mol.
amphiphilic polymers is highly dependent on
shear forces. a. Xanthan gum can resist temperatures up to 80°C
and relatively high shear forces up to 5000 s-1.
a. A novel amphiphilical grafting natural chitosan Xanthan starts to lose its thickening properties
copolymer (PAMCS) was developed by using above 100°C (Kierulf & Sutherland, 1988)
one step water-free radical polymerization (Chen & Sheppard, 1980) (Seright & Henrici,
(Pu, Liu, Peng, Du & Zhao, 2016). The rigid 1990).
d-glucosamine unit ended having intermolecular
association and hydrogen bonding synergistically b. Xanthan is susceptible to bacterial degradation.
in the PAMCS solution with good rheological Salt tolerant aerobic and anaerobic bacteria

60
 Polymers for application in high temperature and high salinity reservoirs – critical review
of properties and aspects to consider for laboratory screening

can degrade Xanthan resulting in a loss of its c. Dai, et al. (2017) developed a novel thermal-
thickening ability (Hou, Barnabe & Greaney, resistant and shear-stable amphoteric
1986). Biocides are used with this polymer to polyacrylamide (PASD), using AM, sodium
mitigate degradation. styrene sulfonate (SSS), and acryloxyethyl
trimethylammonium chloride (DAC) monomers,
c.
Scleroglucan: a non-ionic triple helix prepared by free-radical polymerization in high-
polysaccharide produced from the fermentation salinity solution. This amphoteric polyacrylamide
of a pathogen fungus. The backbone consists exhibited excellent salinity and high temperature
of linearly linked β-1,3-D-glucose chains. It tolerance. The reached viscosity retention was
is a class of polymer with good performance near 40% at 120°C.
under harsh conditions, with no change in
viscosity or injectivity at 95°C and only 25% d. A synthetic hydrophobically modified
drop in viscosity after exposure to 115°C for hydroxyethyl cellulose (HEC) was developed
up to six months. Scleroglucan is stable in using Bromo-dodecane (BD-HMHEC) (Liu,
the presence of hydrogen sulfide and ferrous Mu, Wang & Wang, 2017). The rheological
species (Jensen, et al., 2018). A pilot test is properties and oil displacement efficiency was
being conducted to evaluate the long-term tested for Daqing reservoirs. Results showed
stability of the polymer, and to assess the that BD-HMHEC solution had good thermal-
injectivity control and incremental recovery resistance (90°C) and salt-tolerance (up to 100
(Jensen, et al., 2018). g/L), improving the oil recovery by 7–14% in
comparison with HEC flooding at concentrations
12.Other Polymers: of 4 g/L under equivalent conditions.

a. A new class of synthetic polymers NVP-free, e. A class of the water-soluble ZP temperature-

having different content of ATBS and high responsive exhibits a volume phase transition at
thermal stability up to 140°C was designed for a given temperature, causing a sudden change
use in harsh conditions such as those found in in the solvation state with low critical solution
reservoirs in the Middle East characterized by temperature (LCST) and resistance to high
high salinity brines (total dissolved solids, TDS temperatures (90°C); however, these fluids
> 220 g/L) was reported by Dupuis, Antignard, are susceptible to phase separation which may
Giovannetti & Gaillard (2017). These polymers lead to a significant drop in the viscosity. The
were tested in coreflooding experiments showing solubility of these polymers decreases with
good performance. They were more stable than temperature below the LCST (Fan, Boulif &
ATBS or NVP polymers and could be used in Picchioni, 2018).
sandstones and carbonates (permeability in the
range 100-700 mD). The properties of a good polymer have been summarized
by several authors and include Sheng (2011):
b. Quadri, et al. (2015) reported a polymer
screening study for carbonates under harsh a. No –O– in the backbone (carbon chain) for
conditions. They evaluated HPAM, co- thermal stability
polymers of acrylamide and ATBS, terpolymer b. Negative ionic hydrophilic group to reduce
of acrylamide, ATBS and NVP, and one non- adsorption on rock surfaces
ionic, water soluble homoglucan polysaccharide c. Good viscosyfing ability
(biopolymer described by Quadri, et at. (2015). d. Nonionic hydrophilic group for chemical
Polyacrylamide based co-and ter—polymers stability
showed good thermal stability under low salinity
conditions. A biopolymer (polysaccharide) As presented, it is clear that most available polymers
displayed good thermal stability (up to 120°C) can be used in reservoirs with relative mild temperature
and high salinity tolerance (up to 220 g/L) under and salinity conditions. For other reservoirs exposed to
anaerobic conditions for over eight months with more severe conditions (temperature > 95oC, salinity >
non-significant loss in viscosity. In addition, the 90 g/L) standard polymers like AM, PAM, and HPAM
adsorption of the biopolymer decreased with cannot be used, and the promising newly developed
increasing salinity and temperature. polymers include modifications to AP, thermal associate

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REVISTA FUENTES, El Reventón Energético Vol. 16 n.º 2

polymers and HPAM functionalized with AMPS mechanical and chemically stable, and have low
monomers. adsorption to the rock. In this section, we summarize
some of the key aspects to consider when doing a
Polymer laboratory screening laboratory polymer screening. In general, the series
of steps followed for laboratory polymer screening can
EOR candidate polymers must provide the required be summarized in a schematic workflow as shown in
rheology at minimal concentration, be thermal, Figure 1.

Figure 1. Workflow for polymer laboratory screening.

It is assumed that a preliminary EOR screening exercise Step 1: Assessment of the Required Conditions
has been completed at a project level taking into account for Lab Screening and Polymer Pre-Screening.
the reservoir properties, field location and logistics,
and a calculation of the floodable pore volume with a In general, the screening process starts with the selection
high-level economic estimation for the lab screening of commercial available polymers (most laboratories
is available. It is a good practice to consider the basic usually test between 5-6 different types of polymers)
reservoir engineering screening criteria for polymer according to their temperature stability, salinity
field application which includes: a) making sure that the tolerance, quality of mixing brine, and costs. A series
candidate reservoir has a reasonable good waterflood of tests are done to understand the polymer properties
performance, b) actual average permeability > 25 mD at reservoir conditions including evaluation of the fluid
with no extreme variations, c) sufficient remaining oil rheology based on the response of the viscosity vs.
saturation (and a good understanding of its distribution), shear thinning (Veerabhadrappa, Urbissinova, Trivedi
d) water chemistry is known, e) crude oil viscosity < & Kuru, 2011), evaluation of the molecular weight
5,000 cP, f) understanding of the impact of any nearby vs. molecular weight distribution (poly-dispersivity),
aquifers, and g) good understanding of available determination of polymer anionicity, and filtration ratio
facilities (sufficient injection capacity). tests to select the most viable candidates for the formal
screening process that includes the polymer performance
Figure 2 shows a recommended laboratory workflow evaluation through core flood experiments. The results
generated based on best practices from the literature from these tests are analyzed and a candidate ranking
and our own experience. To evaluate polymers is proposed for subsequent evaluation. These tests are
performance, the recommended approach includes: done using standard laboratory protocols not discussed
rock and fluid selection and characterization and the in this article.
execution of displacement experiments at expected
reservoir conditions, here represented by high The conditions at which the injected fluids will be
temperature and salinity. exposed are critical for the success of the process. A

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 Polymers for application in high temperature and high salinity reservoirs – critical review
of properties and aspects to consider for laboratory screening

good understanding of the reservoir including depth, such as potential injection capacity. If the application
in-situ pressure, temperature, formation properties like is intended to follow a waterflood, it is important to
porosity, permeability, pore size distribution, wettability, analyze the composition of the produced water for use
in-situ fluids play an important role in the process in the testing.
performance. Facilities inputs are also very relevant

Figure 2. Proposed workflow for polymer screening and evaluation.

Step 2. Sample Selection and Rock do wettability restauration is available in the literature
and Fluids Characterization (Araujo, Araujo & Molinaris, 2018).

Reservoir representative fluids should be used in the Step 3: Polymer Solution Preparation
tests wherever possible. Live oil is generally preferred; and Properties Evaluation.
however, if not available, dead oil should be restored
at reservoir conditions. Crude properties like viscosity, For the laboratory tests the polymer solution should
density, composition at in-situ conditions, total acid always be homogeneous According to the nature of
number (TAN), SARA and sand and water content the polymer product for use (fermentation broth, gel or
(BSW) are in general very useful in the interpretation of powder) a slightly different mixing method is used to
the experimental tests. Use of filtered oil is recommended prepare the solution.
to minimize potential plugging. For the brine attention
is needed to make sure it describes the chemistry and Polymer hydration. The preparation of a polymer stock
properties of the produced water (density, total dissolved solution, regardless of polymer type, should follow the
solids (TDS), turbidity, pH, and conductivity). McPhee, API RP 63 (1990). According to this standard, the first
Collin & Zubizarreta (2015) recommend that the brine step is to prepare a stock solution with 5,000 ppm of
be stored if it is not used immediately. polymer concentration followed by dilution to obtain the
desired polymer concentration. Some recommendations
Rock samples should be representative of the reservoir regarding the mixing process to avoid agglomeration of
where the polymers will be applied and be cleaned particles are available in the literature (Rashidi, et al.,
of residual solids and fluids normally done through 2010) (Yerramilli, Zitha & Yerramilli, 2013) (Akbari,
flushing, flowing, or by contacting with various solvents Mahmood, Tan, Ghaedi & Ling, 2017). The polymer
to extract hydrocarbons and/or brine (API RP40, 1998). should be hydrated in a glove box to prevent contact with
Information about properties like porosity, permeability, oxygen. Once prepared the polymer solution should be
mineralogy, and wettability allows to understand the filtered under pressure (usually 15 psi) through cellulose
physics of the flow and transport phenomena during the filters (conventional polymers) or polycarbonate filters
polymer injection. Recommended practices on how to (APs) and properly storaged till its use.

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REVISTA FUENTES, El Reventón Energético Vol. 16 n.º 2

Appropriate storage: Polymers stored at room colloids that remain suspended in solution, giving rise
temperature tend to degrade over time as they deteriorate to turbidity (Kang, et al., 2014).
due to many reasons including bacteriological action
(Escudier, Clement-Evans & Poole, 2005), it is a For viscosity measurements, a high precision instrument
good practice to use a fresh polymer solution for the is recommended, like a low shear rheometer equipped
experiments. The lifetime of storage polymer solution with either an ultra-low adapter or small sample adapter.
is quite variable. Anionic and nonionic polymers It is important to evaluate the viscosity as a function of
last longer once dissolved but the presence of certain polymer concentration and temperature at the optimal
contaminants like ferrous iron can reduce the solution shear rate. The protocol associated to the viscosity
life significantly. Cationic polymers have the shortest measurement depends on the type of instrument used;
storage lives since they can hydrolyze once dissolved. for most common rheometers procedures are described
Attention should be given to hydrolysis since it reduces in the API RP 63 standard (1990).
cationicity. If the polymer samples are dissolved in
advanced of their use, mitigations should be in place to The rheological characterization should be done on
minimize any chemical or physical changes that might selected polymer solutions for a specific concentration
result from their storage (Escudier, Clement-Evans & and filter ratio tests. In general, viscosity is measured at
Poole, 2005). shear rates ranging from 0.1 to 500 s-1 for concentrations
(ppm) ranging from 0 to 5,000. It is also important
to evaluate the effect of brine hardness and pH on
Polymer characterization. Even though polymer
the viscosity. For the brine hardness, the idea is to
properties like molecular weight, anionicity, solubility,
quantify the effect of increasing salinity on the viscosity
etc., are provided by the manufacturer, it is always
according to the degree of hydrolysis.
recommended to validate the data through laboratory
measurements since commercial product properties Polymer solubility can be assessed by: a) low cost visual
may change over time. determination based on visual detection of when the
fluid enters a two phase region, captured as noticeable
Polymer molecular weight (Mw) plays an important cloudiness (Wolf, 1985); b) viscosity measurements
role in the evaluation of the polymer’s performance based on the difference in viscosity between different
in EOR applications since the polymer properties solutions; c) differential scanning calorimetry –a
are influenced by the molecular weight distribution. method that requires high level of expertise for data
A variety of methods are available to measure Mw interpretation; d) gas liquid chromatography has also
including gel permeation chromatography (Holzwarth, been used DiPaola-Baranyi & Guillet (1978) due its
Soni & Schulz, 1986), matrix-assisted laser desorption/ capability of characterize the polymer-solvent system
ionization time-of-flight mass spectrometry (Yalcin, Dai and to investigate the interaction between polymers and
& Li, 1998), and Nuclear Magnetic Resonance (NMR, non-solvents; and e) the fluorescence probe approach
Izunobi & Higginbotham, 2011). based on an aggregation-induced emission (AIE) is
considered as an accurate method for measuring the
Polymer anionicity, also known as hydrolysis degree, solubility parameters of a polymer (Jian, Huang, Wang,
can be evaluated by C13NMR spectroscopy and C, Tanh & Yu, 2016).
N elemental analysis (Zurimendi, Guerrero & Leon,
1984) or colloid titration based on the stoichiometric Filterability is an important test to ensure that a
combination of positive and negative colloids where the polymer solution is free of aggregates which could
endpoint is decided by indicators (Terayama, 1952). lead to formation plugging. The standard procedure to
run the tests is described in the API RP 63 Standard
Polymer concentration and residual monomer content (1990) using a high-pressure filter press. Levitt (2009)
can be measured using several methods including: a) presented an overview of the filtration procedures, filter
SEC-MALS with Mw measurement and NMR, b) UV- size and material adequate according to the polymer
VIS spectroscopy – a fast and simple method (Gibbons type. It is important to consider that filtration ratio tests
& Örmeci, 2013), c) the start tri-iodine method for water are in general not conclusive as screening tests when
soluble polymers containing primary amide groups using associative polymers. Previous findings (Alexis,
(like HPAM) and associative polymers (Scoggins & et al., 2016) indicate that AP can show low filter ratio;
Miller, 1979), or d) the turbidimetric method that uses a however, lower polymer concentration is required to
reagent that react with some polymer components (like generate high resistance factors when used in porous
AMD subunits in PAM/HPAM) to produce insoluble media. For biopolymers, a modified API RP 63 method

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 Polymers for application in high temperature and high salinity reservoirs – critical review
of properties and aspects to consider for laboratory screening

is used for testing at low pressure to get an acceptable transducers should be used to measure the pressure
filtration time (Jensen, et al., 2018). In this method the gradient across the cell. A backpressure regulator (BPR)
pressure is hold between 1.5 to 3 psi to get 2 to 4 minutes is frequently placed on the downstream side of the core
of filtration time with solutions at 50 cP at 10 s-1. to help dissolve any air that may remain within porous
medium before flooding. It is a good practice to remove
Another important aspect to consider is the environment the BPR prior the polymer injection to avoid polymer
where the short/long term thermal stability tests are degradation. In addition, the use of pressure taps along
done, which is recommended to be oxygen free (< 10 the core can provide representative data to assess the
ppb) conditions. Tests are conducted at the selected polymer behaviour.
optimal viscosity and polymer solution concentration.
The degree of compatibility between the polymer and the Important variables to design the polymer flooding at lab
brine is assessed by the change in the appearance of the scale are: flow rate, temperature, confining pressure, back
polymer solution as well as the change in viscosity during pressure, initial water saturation, rock permeability, and
the aging test. A clear single-phase aqueous solution at effluent properties. Very accurate instruments/sensors
both ambient and reservoir temperature are expected for are required to assess the values of these parameters.
the good polymer candidates, and the polymer viscosity Parameters determined through coreflooding include:
should not decrease significantly during the test permeability, initial water and oil saturations, PV and
duration. Since temperature in general has a significant inaccessible PV, injectivity, RF (resistance factor) and
impact on the polymer behavior, thus the tests should RRF (residual resistance factor), adsorption/retention,
be done at reservoir temperature if possible. Two setups slug size, and effluent characteristics.
can be used to minimize testing errors: 1) the polymer
samples are dispensed into air-tight vials (ampoules) Injectivity is measured using the pressure drop when the
inside of an oxygen-free environment created using a polymer is injected into the rock. The selected polymer
glove box, and periodic visual inspections and viscosity must have a good injectivity (minimum pressure-drop)
measurements are recorded at selected time intervals, to allow rapid displacement and recovery of oil. The
and 2) the solution is transferred into small Hastelloy pressure drop is also used to estimate the permeability
cylinders with a large enough volume for the viscosity reduction, and viscosity measurements during flow
measurements at the specific time points of the thermal allows the calculation of RF and RRF. Resistance
stability analysis while all measurements are done in an factors versus polymer solution throughput should be
oxygen-free atmosphere. used to analyze the potential of plugging.

Shear stability can be evaluated in two different ways: i) Polymer retention is another quantity to pay attention
using the API RP 63 (1990) and ii) shearing the polymer since it delays polymer propagation through the porous
solutions at high rpm (usually 30,000) for different time formation. High polymer retention can substantially
intervals at constant temperature. Viscosity monitoring delay oil displacement and thus limit the oil recovery
at each interval allows assessing shear degradation. during a polymer flooding. Two types of adsorption/
retention mechanisms need to be considered: i)
mechanical retention associated with the relative size
Step 4: Setting the Core Initial Conditions
of the polymer molecule and the pore dimensions,
If the field where the polymer flooding is to be applied an irreversible process, and ii) physicochemical
follows a waterflood, the core sample should be adsorption, which is reversible and associated to the
submitted to a similar saturation history by injecting chemical and physico-chemical characteristics of
a similar amount of water (in terms of porous volume the polymer and the rock. Many methods have been
(PV)) as done in the field starting from reservoir native reported in the literature to measure polymer retention
saturation conditions. and inaccessible pore volume (Seright, Seheult &
Talashek, 2008) (Domenico & Schwartz, 1990) (API
Step 5: Evaluation of Polymer Performance RP63, 1990) (Chiappa, et al., 1999).

Polymer performance is evaluated through coreflooding Experimental results are used in numerical simulation
experiments at reservoir conditions. The experimental to design polymers slugs for field application. Molano,
set-up typically consists in an injection system, transfer Navarro & Díaz (2014) developed a methodology to
cylinders, core holder, backpressure regulator and design polymer slugs for polymer injection process based
effluent collector. High precision differential pressure on rock- fluid interactions phenomena in porous media,

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REVISTA FUENTES, El Reventón Energético Vol. 16 n.º 2

focusses on the behavior of the polymer concentration f. For effluent collection, it is recommended to use
on the injected fluid as a function of time and length; accurate fraction collectors and high precision
and how interaction phenomena within reservoir affects instruments for evaluation of dissolved oxygen
its performance. (precision of at least 1 ppb), and accurate titrators for
the polymer concentration. We recommend using
When evaluating polymer flooding performance ion chromatography (IC) instead of an electrode
for harsh reservoirs, the effluent must be analyzed probe to evaluate the salinity when working with
using the appropriate tools. At least the following polymers exposed to a harsh environment.
tests should be completed: TDS, salinity, dissolved
oxygen, pH, conductivity, hardness, polymer Discussion and conclusions
concentration, and viscosity. Effluent analysis is
used to evaluate the polymer retention, inaccessible Identifying a polymer that can withstand high-
pore volume and rheological properties. In addition, temperature and high-salinity conditions is a major step
the effluent parameters can help to identify issues for a successful polymer-flooding application (Hashmet,
or problems early on the study before extensive lab AlSumaiti, Qaiser & AlAmeri, 2017).
work is undertaken.
From the polymers available for EOR, sodium acrylate
The described workflow works well with most of the and polyacrylamide based co-and ter-polymers are
standard polymers presented in the previous section. found to be stable only under low salinity conditions
However, when evaluating polymers for use in hostile and in most cases they can resist temperatures up to
environments of high temperature and high salinity, 70°C. Modified acrylamide co-polymers have improved
further attention is required in particular to the type of stability under harsh conditions, however the amount of
instrumentation used in the laboratory. Some aspects to polymer required to obtain a good recovery is generally
consider include: too high, around 3 times the amount required for
conventional polymers, so their use may be not attractive
a. coreflooding system – the wetted parts (coreholder, for commercial applications. Sulfonate base acrylamide
fluid cylinders, and lines) made from a corrosion co-polymer (ATBS) is an option for temperatures
resistance material like Hastelloy. The high salt below 105°C. PAMs have showed better high salinity
content and the presence of iron in the system could and temperature tolerance than HPAMs which showed
cause corrosion; relatively good stability only when the dissolved oxygen
is extremely low and if divalent cations are minimized.
b. the coreflood system (coreholder, flow lines, A salinity tolerant polyacrylamide has been developed
capillary viscometer, fluid accumulators, etc.) (KYPAM) but requires additional field testing.
placed in a constant temperature environment like Associative polymers seem to be an option for high
the one provided by a convection oven. salinity environments, however further improvement is
needed to increase the temperature application limit.
c. Coreflooding parts like core sleeves and O-rings
need to be compatible with the environment. The Other polymers like zwitterionic polymers are resistant
widely used Viton sleeves and seals made from a to high TDS (~ 100 g/L) and can be used as a wettability
fluorocarbon elastomer perform well in the presence modifier to increase the recovery factor. Biopolymers
of organic fluids like hydrocarbons and other like Xanthan gum can resist temperatures up to 100°C
solvents over the temperature range from -7°C to with limited tolerance to high salt content could be
205°F. For harsh environments the use of AFLAS impacted by bacterial degradation. Scleroglucan has
(a copolymer of tetrafluoroethylene and propylene) high salinity tolerance up to 200 g/L. These types of
material is preferred; polymers are potential candidates for applications
in certain types of reservoirs but they all need to be
d .Injected fluids should be exposed to minimal field tested.
temperature variations; therefore, fluid accumulators
should be placed inside an over and preferably A more promising candidate for harsh reservoir is a
closer to the coreholder. synthetic polymer NVP-free with ATBS content due
its thermal stability up to 140°C and salinity tolerance
e. Viscosity measurements are recommended to be (up to 220 g/L) tested for carbonates with a good
done with a capillary viscometer for the rheological performance. We expect future work to continue on the
evaluation during the polymer flooding improvement of the polymer properties.

66
 Polymers for application in high temperature and high salinity reservoirs – critical review
of properties and aspects to consider for laboratory screening

The laboratory screening process typically starts after reservoir information, have the resources to conduct
a pre-screening phase that provides the required data to all the required tests, perform careful QA/QC of the
understand the behavior of the polymers at the tested results, use best practices to obtain high quality data,
conditions. It is important to consider the polymer to document properly, and to use all the available
chemical structure since the rheological properties are information and results to understand the polymer
affected by the chemical structure and the external behaviour before making a final decision on the
parameters. ranking of the polymers.

When screening for the polymers under harsh References

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Recepción: 26 de septiembre de 2018

Aceptación: 26 de noviembre de 2018

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