SPE-197647-MS

Extending Polymer Flooding Towards High-Temperature and High-Salinity

Carbonate Reservoirs

Shehadeh Masalmeh and Ali AlSumaiti, ADNOC; Nicolas Gaillard and Frederic Daguerre, SNF; Tormod Skauge,
Energy Research Norway; Arne Skuage, University of Bergen

Copyright 2019, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference held in Abu Dhabi, UAE, 11-14 November 2019.

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
Polymer flooding is a mature EOR technique successfully applied in both sandstone and carbonate
reservoirs. ADNOC has developed a new EOR roadmap with the objective to identify and mature EOR
options to improve displacement and sweep efficiency in carbonate reservoirs. Polymer based EOR was
identified as one of the main EOR options. These options include polymer injection, simultaneous injection
of miscible gas and polymer (SIMGAP), simultaneous injection of water and polymer (SIWAP), low salinity
polymer, etc. However, the conditions of the reservoirs in Abu Dhabi are beyond the industry experience
for the application of polymer which pose a significant challenge to polymer based EOR processes. The
reservoirs are at high temperature (~100-130 °C), the formation brine is of high salinity (~200,000 ppm),
the brine also has high concentrations of divalent ions (~18,000 ppm of Ca++ and Mg++) and the reservoir
formation is carbonate where there is little experience in the industry for polymer injection. The stability
of polymers is known to be severely affected at such conditions of high temperature, salinity and divalent
ions concentration. Therefore, the main challenge for polymer based EOR processes in ADNOC reservoirs
(such as polymer flooding, SIMGAP, SIWAP, etc.) is to find a polymer that are stable under such extreme
conditions and can be injected in carbonate reservoirs.
ADNOC has lunched a number of studies to experimentally investigate 1- the stability of polymers at
such adverse conditions of high salinity, high temperature and high divalent ions, 2- injectivity of polymers
in carbonate rocks using both outcrop and reservoir core plugs, 3- bulk and in-situ rheology of polymers,
4- effects of various parameters on the polymer performance, such as polymer concentration, shear rate and
presence of oil on polymer retention and in-situ rheology and 5- impact of H2S and Oxygen on polymer
stability.
In this paper, we report the results of these different studies that can enlarge the application envelope
of polymer flooding to high-temperature, high-salinity and light oil Middle Eastern carbonate reservoirs.
The main conclusions of the studies are: 1- A polyacrylamide based polymer with high content of ATBS
(SAV 10) was identified as stable at Abu Dhabi reservoir conditions, 2- SAV 10 polymer is also stable in the
presence of H2S (500 ppm) and/or Oxygen up to 150 ppb, 3- The polymer has good injectivity in a wide range
of injection rates ranging from 1ft/day to 120ft/day and wide range of permeability, 4- The polymer showed
2 SPE-197647-MS

a shear thickening behavior with an increase in flux without any signs of mechanical degradation, noted by
the stable viscosities of the effluents, 6- The presence of crude oil had significant impact on injectivity, in-
situ rheology and adsorption in carbonate core material.
In summary, the ATBS polymer showed a promising injectivity behavior which can be modulated for
injection in the target reservoirs. In addition, as the required viscosity increase for both SIMGAP and SIWAP
processes to work is moderate, we find the results to be very promising and they open the door for field
testing and piloting.

Introduction
Carbonate reservoirs contain more than 50% of world's hydrocarbon reserves and on average have recovery
factors between 30-40%. With the insight that the growth rate of "easy oil" supplies (conventional oil and
natural gas that are relatively easy to extract) will struggle to keep up with accelerating demand, enhanced
oil recovery (EOR) becomes increasingly important in reservoir development.
ADNOC has recently developed an EOR roadmap in which we have reviewed the available EOR
concepts, their maturity and applicability to Abu Dhabi carbonate reservoirs. Carbonate reservoirs are, in
general, geologically more complex than clastic reservoirs as they have more complex pore systems, highly
heterogeneous and often have dual porosity systems (in addition to fractures). Most carbonate reservoirs
also show mixed to oil-wet characteristics. Both geological heterogeneity and wettability have strong impact
on remaining oil saturation and its distribution and hence on oil recovery and sweep efficiency and on the
choice of EOR options to be applied in such reservoirs.
A recent literature review has revealed that most EOR applications have been in sandstone reservoirs.
Based on an international EOR project database containing 1507 projects (Manrique et.al., 2010, SPE
130113), only 18% of the EOR projects have been implemented in carbonates and most of them are gas
EOR in the US (either continuous miscible gas or WAG). While gas injection has very high displacement
efficiency, it suffers from poor sweep efficiency due to geological heterogeneity and gravity override.
Moreover, recent studies focused on Abu Dhabi reservoirs showed that for reservoirs of high heterogeneity,
water flooding can be more attractive than either continuous CO2 or CO2 WAG injection (Masalmeh et. al.
2014, SPE 171900). Therefore, in these cases gas EOR needs to be combined with mobility control options.
The specific properties of the reservoirs in Abu Dhabi makes EOR more challenging. The oil in these
reservoirs is light with API mainly between 35 to 40 which excludes any thermal based EOR concepts.
Chemical EOR options have large potential to either target remaining oil saturation or oil bypassed in low
permeability layers or small pores. However, the harsh conditions of the carbonate reservoirs in Abu Dhabi
(high temperature and salinity) pose a major challenge to chemical EOR. The reservoir conditions in Abu
Dhabi are beyond the industry experience for the application of chemical EOR. The reservoirs are at high
temperature (~100-130 °C), the formation brine is of high salinity (~200,000 ppm), the brine also has high
concentrations of divalent ions (~18,000 ppm of Ca++ and Mg++) and the reservoir formation is carbonate
where there is little experience in the industry for both surfactant and polymer injection. The stability of
chemicals (surfactant and polymer) is known to be severely affected at such conditions of high temperature,
salinity and divalent ions concentration.
Polymer flooding is the only chemical EOR method that have been tested successfully in carbonate
formations, both in light and medium oil reservoirs. However, carbonate reservoirs have made a relatively
small contribution to polymer flooding in terms of total oil recovery. Many papers referred to laboratory
studies for polymer flooding in carbonate reservoirs (REF) but only few refer to implementation on the field
[Bennetzen, et. al. 2014, Ghosh, et. al. 2017]. An April 2004 Oil and Gas Journal EOR survey, reports that
only four chemical EOR projects were still active in the US (Moritis 2004). According to Manrique et. al.
(2010), only two chemical EOR projects have been reported in 2008 and that Chemical EOR methods are
not expected to make an important contribution in oil production from carbonate reservoirs in the next one
SPE-197647-MS 3

or two decades. Moreover, so far no polymer flooding has been performed at high temperature and high
salinity conditions in carbonate reservoirs.
As part of the ADNOC EOR roadmap, polymer based EOR was identified as one of the main EOR
options. These options include polymer injection, simultaneous injection of miscible gas and polymer
(SIMGAP) (Masalmeh et. al. 2010), simultaneous injection of water and polymer (SIWAP) (Masalmeh et.
al 2011), low salinity polymer, etc. This shows that polymer flooding has large potential in carbonates, but
it needs to climb the learning curves similar to sandstone. Challenges like polymer adsorption, injectivity,
in-situ rheology in carbonate rock and stability at high temperature and salinity and hardness of water needs
to be investigated. In addition, some of the polymer applications will involve the injection of CO2 and the
reservoir fluid has CO2 and H2S which may affect the performance and stability of the polymer.
Therefore, in this paper the long term thermal stability of polymers is evaluated at high temperature (105
to 130 °C) and high salinity brines with divalent ions concentration up to 20,000 ppm in the presence of
H2S. In addition the paper will also present data on polymer in-situ rheology, injectivity in carbonate rock
and polymer adsorption. All these parameters were evaluated in the presence and absence of oil.
The experimental program reported has quantified the physico-chemical properties of SuperpusherTM
SAV range of polymers. In the present paper, those polymers will be named A, B an C with A having the
highest amount of ATBS (referred as polymer D in Dupuis, et. al., 2017). The results qualify this polymerA
for polymer flooding in formation water at 120 °C. Injectivity properties are excellent and retention is within
an acceptable range. The data provides all required input for reservoir simulation studies.

Polymer Thermal Stability

In the last decade interest in research to develop polymers that are stable at high temperature and salinity
has increased significantly, see Vermolen et. al. 2011, Dupuis et. al. 2017, Rodriguez et. al 2019.
Polymer flooding is widely applied as a tertiary oil recovery technology for improved mobility control
and sweep efficiency. The application range of polymer as a viscosifier is currently limited by the reservoir
temperature and the make-up brine salinity and hardness due to chemical degradation of the polymer.
Synthetic polymers such as partially hydrolyzed polyacrylamide (HPAM) are not thermally stable at
temperatures above 60 or 70 °C. The thermal stability of the synthetic polymers can be imporved by
incorporating monors such as Sodium Acrylamido tertiobutyl Sulfonate (ATBS) and N-vinylpyrrolidone
(NVP). In previous years, terpolymers were developed incorporating NVP which effectively protects the
acrylamide groups against thermal hydrolysis and improved thermal stability up to 120 °C. However, NVP
increases the cost of the polymer, limits its molecular weight and impairs injectivity in low permeability
carbonates. The price of these terpolymers to a achieve a certain viscosity is approximately 3 times higher
compared to HPAM, see Gaillard et. al., 2014.
In a recent publication, NVP-free polymers were developed incorporating different mol percentages of
ATBS which are cheaper than NVP polymers, enable dosage reduction of up to 50% to obtain the same
viscosity, improves injectivity and further improves thermal stability up to 120 °C, Dupuis et. al. 2017 (SPE
188479). In this study we present new data on thermal stability of the ATBS based polymers at different
temperatures (105 and 130 °C) and in the presence of contaminants such as H2S and O2.
Three ATBS based polymers have been selected for these conditions, they will be named polymers
A, B and C. These polymers are selected for their compatibilities with the reservoir conditions towards
temperature, salinity and the permeability of the reservoir, and for cost interests.
The polymer solutions were prepared using a glove box that works in fully or partially anaerobic
conditions. Polymer solutions have been aged in stainless steel containers at the target temperature (i.e.,
105 and 130 °C) and all these ampoules were conditioned to prevent the effect of corrosion before use.
The synthetic brine was prepared outside the glove box. Then the brine was introduced inside and sparged
with N2 to reach less than 10 ppb of oxygen before the preparation of polymer dissolution. Regarding the
4 SPE-197647-MS

partially aerobic experiments (O2 > 10ppb), the oxygen content was adjusted inside the glove box just before
sealing the ampoules. The additive and contaminant such as H2S were added directly into the brine before
polymer dissolution.
The effect of chemical degradation on the polymer solution was determined by measuring the viscosity
of the solution before and during the test. The rheometer used is a Brookfield viscometer (with UL adaptor
at 6 rpm, 7,34 s-1 shear rate). Viscosities were measured in the anaerobic glove box so that no oxygen was
introduced in the aging containers when opened especially during measurement. Viscosity measurements
were performed at 25°C. The stability tesst were carried out for a period of 6 months with regular samplings
after one week and then every month up to 6 months.

Polymer Thermal Stability in the absence and presence of H2S in anaerobic conditions
Figure 1 shows the relative viscosity of the 3 polymers for 6 months measured at 105 °C in anaerobic
conditions (O2 < 10ppb) with and without H2S. As described above 500 ppm of H2S was added into the
brine before polymer dissolution. As shown in the figure polymer A is stable for 6 months in the absence
or presence of H2S. On the contrary, polymer C is not considered as stable in the same conditions. The
thermal stability limit for polymer C, usually recommended at around 105 °C, is affected by the combined
presence of both oxygen traces and 500ppm H2S. Moreover, the polymer solution loses around 35-40% in
absence of this contaminant. This degradation is attributed to the hardness of the brine, especially the R+
(ratio between total divalent cation & total cations). Regarding polymer B, the polymer is only degraded
in presence of H2S at 105 °C.

Figure 1—Thermal stability of different polymers at 105 °C in presence and absence of H2S after 180 days

At 130°C, polymers B and C are degraded much faster. At this temperature, these two polymers are not
stable in the absence or presence of H2S and viscosity loss is almost linear for 6 months. In the meantime,
polymer A remains stable in the two conditions, i.e., viscosity loss is less than 20%.
SPE-197647-MS 5

Figure 2—Thermal stability of different polymers at 130° C in presence and absence of H2S after 180 days

Polymer Thermal Stability in the absence of H2S and 150 ppb of O2

The objective of this measurement is to simulate a potential oxygen ingress in case of H2S is not present
and to assess the polymer degradation after 180 days period at 105 & 130°C. Figure 3 shows the relative
viscosity of the same 3 polymers at the above conditions.

Figure 3—Thermal stability of the three polymers in the absence of H2S and 150 ppb of O2

At 105°C, the presence of 150 ppb of oxygen does not seem to affect the polymer stability of polymer
A and B more than in presence of oxygen traces. Only 15-25% of viscosity loss is measured. As observed
above with oxygen traces, polymer C loses more than 35% of viscosity, but increasing oxygen level from
less than 10 ppb to 150 ppb does not change polymer stability. At 130°C, polymer A remains the only
polymer stable under these conditions with less than 20% of viscosity loss after 6 months aging. When
comparing the viscosity of the three polymers in presence of oxygen traces to 150 ppb (Figure 4), we can see
that in the presence of 150 ppb O2, the polymer solution viscosity decreases only slightly by 5% maximum.
In other words, 150 ppb of oxygen can be tolerated without impacting significantly the polymer stability.
6 SPE-197647-MS

Figure 4—relative viscosity comparison for the three polymers in the absence of H2S and 150 ppb of O2

Polymer Thermal Stability in the presence of 500 ppm of H2S and 150 ppb of O2
The aim of these experiments is to simulate closely the field conditions (H2S, with 150 ppb oxygen)
and to assess the polymer degradation after 180 days period. The combined presence of H2S and oxygen
could be detrimental for the polymer. The experimental procedure followed the one described above for
anaerobic conditions. A known amount of NaSH is added directly into the brine, previously chemically
and/or physically deoxygenated, to reach the right H2S dosage (500 ppm). The whole handling is conducted
inside the glove box. The oxygen was added into the diluted polymer solution just before aging.
As shown in Figure 5, at both 105 & 130°C we observe the same behaviour for the three polymers.
In each case, polymer A is stable where 65% of the viscosity is retained in the harshest conditions i.e. in
combination with oxygen & H2S at 130°C. Regarding, the two polymers B & C, both are not stable, even
at 105°C when H2S and O2 are present.
SPE-197647-MS 7

Figure 5—Thermal stability test for the three polymers in presence of O2 and H2S at 105°C and 130°C

Figures 6 represents a comparison of the viscosity of the three polymers at 105°C and 130 °C under all
conditions tested in this study. The presence of H2S in combination with oxygen is detrimental to the polymer
stability. At 105 °C, polymer B can be selected if and only if H2S is not present, otherwise Superpusher
polymer A is highly recommended. Polymer C loses only 35% of viscosity after 6 months depending on
the conditions, however polymer B remains cautiously suggested. At 130 °C, polymer A is thermally and
chemically stable.

Figure 6—Relative viscosity comparison between three polymers at various O2 and H2S concenrations at 105°C
8 SPE-197647-MS

Figure 7—Relative viscosity comparison between three polymers at various O2 and H2S concenrations at 130°C

The thermal stability of Polymer A was also tested in other work under anaerobic conditions in the
absence of H2S (reference as polymer D in Dupuis, et, al., 2017). Polymer A was also tested in this work
and has shown superior stability compared to other polymers over more than 1 year at ADNOC reservoir
condition, see Figure 8. The plan is to continue studying these polymers for several years more to ensure
the long-term stability at reservoir conditions.

Figure 8—Thermal stability test of polymer A using different brine salinities, see Table 1

Based on this data, Polymer A is selected to be used in pilot tests in ADNOC reservoirs for both SIWAP
and SIMGAP. For field application the polymer needs to satisfy the following:
SPE-197647-MS 9

1. Have good injectivity.

2. Provides the desired viscosity inside the reservoir for mobility control and improved sweep efficiency.
3. Propagates through reservoir with limited losses (adsorption/retention).
4. Maintains its viscosity while traveling through the reservoir.
The rest of the paper will focus on describing the physical properties of polymer A, as it is the only one
that demonstrated sufficient thermal stability at the harsh reservoir conditions in Abu Dhabi.

Experimental Procedure Core Flood Experiments

Polymer preparation: Polymers were prepared by a modified version of the API RP-63 procedure. A
stock solution was prepared on a magnet stirrer and left overnight to complete hydration. The subsequent
day, a dilution was made to the final concentration. The solution was left overnight at low stirring rate for
homogenization. All solutions were filtered by 1 bar overpressure through 5 um cellulose filters. Polymer
solutions were degassed with Argon gas and thiourea scavenger was added to prevent oxidation.
Core preparation: A number of core floods were performed on reservoir cores. Core lengths were 4 – 9
cm with a diameter of 3.8 cm. Cores were cleaned by toluene and methanol to get rid of mud contamination,
then dried and re-saturated with synthetic formation water. For experiments performed in the presence of
oil, the cores samples were drained with mineral oil and subsequently exchanged with crude oil and aged
at 120 °C to restore wettability. The residual oil saturation was established either by flooding or by forced
imbibition in the centrifuge. Initial water saturation was in the range of 0.09 to 0.23 and remaining oil
saturation was between 0.08 and 0.41. Including all cores with and without oil the absolute permeabilities,
Kwabs, were in the range 29 – 3606 mD as shown in table 3. Experiments were performed at 50 °C in a
heating chamber. Differential pressure was measured and viscosity of the effluent samples was determined
by rheometer and/or in-line viscometer.
Retention experiments were performed by injecting two slugs of polymer, using LiCl as the passive tracer
(concentration measured by ICP-OES) and polymer as the active tracer. Polymer was detected by both in-
line viscometer and carbon detection (TOC). Given that the inaccessible pore volume (IPV) is the same for
both slugs, the delay of the first slug (retention occurring) compared to the second slug (no further retention)
gives the retention value.
Injectivity experiments were performed using well relevant rates calculated from a generic well model.
This resulted in injection rates up to 30 ml/min (38 m/day) for the high permeable (multi-Darcy) cores.
For the low permeable cores, the injection rates were about 3-5 ml/min (3.8-6.3 m/day). These were the
maximum rates into a layer of low permeable rock in a multilayered well with higher permeabilities. A
minimum of 70 PV were injected to evaluate possible face plugging and/or in-depth filtration.
In-situ rheology experiments were performed on polymer pre-saturated cores to ensure that retention was
satisfied. Injection rates were varied from high to low, then increased back to high rates to evaluate possible
hysteresis. Effluent viscosity was measured by in-line viscometer and/or rheometer.

Polymer Bulk Rheology

The objective is to measure bulk rheology as a function of concentration, temperature and brine composition.
Bulk rheology measurements are used for screening polymers and for relative comparison of viscosifying
properties with regard to concentration and brine composition. Reference shear rheology was measured
for all polymers at 22 °C on a Malvern Kinexus Pro rheometer equipped with Titanium 2/50 cone-plate
geometry. Measurements at higher temperatures were performed both on the rheometer and in closed coil
systems. By using a capillary of ~6m in a heating cabinet, controlled anaerobic flow conditions up to 120
°C could be applied.
10 SPE-197647-MS

Brine recipies: The formation water (AFW) has a TDS of 180 000 mg/L with a hardness of 17 750
mg/L (see Table 1). Combined with high reservoir temperature, 120 °C, these are extreme conditions for
polymers for EOR. Polymer A, a polymer with very high ATBS content from SNF Floerger, was shown
through initial screening to have the best stability in formation water.

Table 1—Brine composition for various salinities

Concentration [mg/L]
Ions ALS ASW AFW NAFW

Na+ 87 13404 49898 49898

K+ 4 483 0 0
Mg 2+ 2 1623 3248 3248
Ca 2+ 1 508 14501 14501
Cl - 143 24141 111812 111906
SO4 2-
2 3384 234 234
HCO3 -
2 176 162 0

TDS 241 43719 179855 179787

Impact of Polymer Concentration on Viscosity: Viscosity as a function of concentration was performed

at 22 °C and can be scaled to reservoir temperature. The viscosity as a function of shear rate for different
polymer concentrations is shown in Figure 9 and the viscosity dependence on concentration at at 10 s-1, 22
°C is plotted in Figure 10.

Figure 9—Shear viscosity of polymer A in AFW brine at different concentrations measured at 22° C
SPE-197647-MS 11

Figure 10—Shear viscosity of polymer A in AFW brine plotted as a

function of concentrations from 500 – 5000 ppm measured at 10 s-1, 22 °C.

Table 2 shows the viscosity of the polymer solutions at different concentrations measured using different
brine salinities. Similar viscosity is obtained when the make up brine is sea water or formation water.
However, siginifcantly higher viscosity is obtained when using low salinity water. This shows that
combining low salinity with sea water could lead to significant reduction in the amount of polymer to be
used in the reservoir. More work is ongoing on the polymer stability in the presence of low salinity water.

Table 2—Shear viscosity for polymer A in different brines as a function of concentration. Values measured in mPas at 10 s-1, 22 °C

Conc. [ppm] polymer AALS [cP] polymer AASW [cP] polymer AAFW [cP]

500 14.48 2.33 2.80

1000 36.64 4.18 4.68

2000 101.80 9.64 10.24

3000 183.40 17.87 18.14

5000 394.00 43.62 43.38

Both SIMGAP and SIWAP concepts requires the injection of a polymer solution with a factor of 10
higher viscosity compared to water, see Masalmeh et. al. 2014. Based on measurements presented above, a
polymer concentration of 950 ppm and 2500 ppm is required to obtain a bulk viscosity 3 times and 10 times
the one given by brine, respectively. However, the final selection of the polymer concentration should be
based on in-situ rheology as it is more representative to polymer flow in the reservoir.

Polymer In-Situ Rheology Using Reservoir Carbonate Cores

The objective of this section is to determine the in-situ rheology, resistance factor (RF) and the residual
resistance factor (RRF), for relevant reservoir flow rates in reservoir and outcrop carbonate rock at relevant
permeabilities.
The rheological properties of polymers are strongly dependent on the flow conditions. Polymer flowing
through a porous media will experience contraction-expansion flow, which leads to a different rheology
than in pipe or bulk flow. In many cases, the rheological properties will change from shear thinning in bulk
12 SPE-197647-MS

to near-Newtonian in porous media. At higher flow rates shear thickening may be observed which is not
present in bulk flow. It is therefore important to determine the in-situ rheological properties of polymers in
the reservoir rock or in representative outcrop material if reservoir core material is sparse. However, all the
data discussed in this paper were measured using reservoir core samples.
All measurements were performed at 50 °C in a heating cabinet, see core flood design in Figure 11. The
reason for using 50 °C as opposed to the reservoir temperature of 120 °C was that effluent sampling is
difficult at 120 °C due to the pressure required to avoid boiling. The results at 50 °C are easily scalable
to elevated temperatures and verification experiments will be performed at reservoir temperature. The
standard test condition of injecting 1000 ppm of polymer A in formation water (NAFW) was used in
most experiments. Complementary experiments with concentration variations between 500 ppm and 3000
ppm were performed to determine apparent viscosity as a function of concentration. The influence of oil
was evaluated in experiments where the cores were drained and aged with reservoir crude oil at 120 °C
for 1 week. All polymer solutions were prepared to be oxygen free (using oxygen scavenger and Argon
blanketing) and all lines and the cores were preflushed with oxygen free brine prior to start. Core properties
are given in Table 3.

Figure 11—Core flood design for in-situ rheology measurements.

Table 3—Core properties for in-situ rheology experiment

Kw,abs Swi Sor Kw(So) Kw,end RRF/ II* [m3/ Q [ml/ dP

Core ID L [cm] φ [%PV]
[mD] [frac.] [frac.] [mD] [mD] RRF* d/bar] min] [mbar]

C1 4.30 26.0 3606 0.2 0.38 803 1587 – 422 30 768

C2 4.15 26.0 1616 – – – 849 1.9 116 30 2784

C3 3.77 24.4 538 – – – 192 2.8 9 20 26200

C4 5.64 29.1 412 0.23 0.41 107 73 1.5* 11 30 29343

C5 5.16 26.2 263 0.093 0.159 184 29 6.3 – – –

C6 6.62 30.4 121 – – – 33 3.7 3 20 75709

SPE-197647-MS 13

Kw,abs Swi Sor Kw(So) Kw,end RRF/ II* [m3/ Q [ml/ dP

Core ID L [cm] φ [%PV]
[mD] [frac.] [frac.] [mD] [mD] RRF* d/bar] min] [mbar]

C7 6.10 31.9 75 – – – 19 3.9 1.9 4 25800

C8 4.80 31.0 70 0.12 0.47 47 9.8 4.8 3 20 79400

C9 8.86 26.9 70 – – – – – 1 4 50500

C10 4.98 29.6 45 – – – 10.2 4.4 – – –

C11 5.13 30.7 29 – – – 13.2 2.2 – – –

RRF for oil saturated cores is calculated as RRF*=Kw,Sorw/Kw,end, while it is RRF=Kw,abs/Kw,end for water saturated cores. II* = (Q/dP) × (Awell/Acore)
where Awell I calculated from a well radius of 7" and length of 50 ft.Core C1 produced oil and reduced oil saturation during polymer flood and has therefore
higher Kw,end than Kw,ROS.

Polymer solution behavior in 100% water saturated cores

The in-situ rheology for water saturated cores is shown in Figure 12 where resistance factor (RF) is plotted
as a function of flow velocity. Resistance factor is defined as RF = dPpolymer/dPbrine and is proportional to
the apparent viscosity of the polymer in the porous media. Both reservoir cores show a near-Newtonian
behavior at reservoir relevant flow rates, i.e. ~0.05 – 0.5 m/day. At higher rates shear thickening is observed
until a maximum is reached at ~12-30 m/day. Beyond this point, mechanical degradation leads to a reduction
in viscosity, however, the viscosity reduction is low, more details will be discussed below. The flow rate for
the lowest permeability sample was limited to less than 10 m/d as the pressure drop increased significantly.
The RF for this sample almost reached maximum at the maximum rate that was applied in the experiment.
The onset of shear thickening is dependent on several factors such as polymer molecular weight, rock and
pore size distribution.

Figure 12—In-situ rheology for 1000 ppm polymer A in NAFW in water saturated reservoir cores.

As can be seen in Figure 12, in general the onset of shear thickening and the maximum RF occur at higher
flow velocities for the higher permeable core. Sample C3 (permeability is 538 mD) does not follow the same
trend. This could be due to more heterogeneous pore size distribution of this sample, further investigation
is ongoing to explain the RF behavior of this sample. For 1000 ppm of polymer A, the reservoir flow can
be modeled as a near-Newtonian fluid. The RF difference at reservoir flow for the different samples can
be explained by different permeability reduction (RRF) for the three experiments (RRF = 3.9, 3.7 and 1.9
14 SPE-197647-MS

for Kw = 75, 121 and 1616 mD, respectively). Note that RF values measured in these experiments for
1000 ppm of polymer is more than 10, even for the highest permeability sample. This is much higher than
what is expected from the bulk viscosity measured with rheometer which is only a factor of 3 higher than
water viscosity for the same concentration of 1000 ppm of polymer. Partly, the difference is explained by
the permeability reduction cause dby polymer adsorption and retention. As discussed above, a factor of 10
increase in the polymer viscosity would need a polymer concentration of 2500 ppm. This is very positive
for the economics of the project as the required mobility reduction of the fluid injected in the upper zone
of the reservoir is achieved at lower polymer concentration, i.e., 1000 ppm of polymer instead of 2500.
However, the data measured so far is done in the absence of oil. The impact of residual oil on the in-situ
rheology is investigated here below.
The influence of polymer concentration on in-situ rheology is investigated in two experiments, see
Figures 13 and 14. Figure 13 shows the in-situ rheology for 4 different concentrations in a reservoir core
which has a permeability of 121 mD (C6). At high concentrations, 2000 – 3000 ppm, the shear thinning
behavior at low flow velocities becomes more dominant while it is near-Newtonian at lower concentration,
500 to 1000 ppm, as shown above. For all concentrations, the resistance factor at reservoir rate is between
15 to 50, where it increases with polymer concentration. As the polymer concentration increases, the onset
of the shear thickening occurs at lower flow rate. This is contrary to that observed for water wet sandstone
experiments (Skauge et al. 2015) and may be explained by internal redistribution of oil by polymer. The same
trend is also observed with the maximum RF, where it also occurs at lower flow rate as the concentration
increases.

Figure 13—In-situ rheology and residual viscosity of effluents sampled at given

flow velocity for 500 – 3000 ppm of polymer A in NAFW in water saturated core C6.
SPE-197647-MS 15

Figure 14—Resistance factors at reservoir and injection well rates as a function of injected
viscosity for pre-degraded solutions of 1000 ppm polymer A in NAFW brine using reservoir core C2

The effluent viscosity was also monitored during the in-situ rheology measurements. The relative
viscosity is presented in Figure 13. The results show that polymer solution viscosity is retained with a
maximum loss of about 20% for a flow velocity of more than 20 m/d. The viscosity loss is observed at the
velocity just below the velocity where the maximum shear thickening is observed. These results demonstrate
that this polymer is very shear resistant and minor mechanical degradation is expected near the well pore
in case the polymer will experience such a high flow rate.
The influence of pre-degradation is shown in Figure 14. Four solutions with different degree of pre-
degradation were injected in a high permeable water saturated reservoir core (core C2 in Table 3). The
figure shows RF at reservoir and injection well flow rates as a function of the injected viscosity. The injected
viscosity is lowest for the 50 % pre-degraded solution and highest for the non-degraded solution. By pre-
degrading the polymer solution with 30 % viscosity loss, the injection pressure is reduced by a factor of
9 (RF reduced from 61 to 7) when compared to the solution not pre-degraded (highest injected viscosity).
The reservoir flow rate viscosity is reduced by a factor of 2 (RF reduced from 9.8 to 5.0) for the 10% pre-
degraded polymer. This suggests that pre-degradation may be a solution if injectivity is poor in a field case.

Polymer solution behavior in carbonate cores at Sor

The influence of residual oil on in-situ rheology can be seen in Figure 15. The figure shows the in-situ
rheology data of reservoir samples of similar brine permeability, 421 and 538 mD. The second sample
(K=421 mD) was saturated with oil, aged for a week and then flooded to residual oil saturation. The figure
shows that

• Shear thickening is strongly reduced in the presence of oil which will lead to improved injectivity.

• The onset of shear thickening is increased by almost an order of magnitude in the presence of oil.

• At reservoir flow velocities the RF for the crude oil aged core is similar to that of the water saturated
core with the similar initial permeability.
16 SPE-197647-MS

Figure 15—In-situ rheology for 1000 ppm polymer A in NAFW in water saturated (C2 and C6)
and oil saturated (C4) reservoir cores. Note that the permeability of C4 at ROS was 107 mD.

Comparing the in-situ rheology of sample (perm 421 mD) in the presence of oil and sample (perm 1616
mD) in the absence of oil shows that the resistance factor at reservoir rate is similar though there is a factor
of 4 difference in permeability. Moreover, the shear thickening of the lower permeability in the presence
of oil is much less than that of the high permeability plug in the absence of oil, i.e. the maximum RF is 3
times lower in presence of oil for the lower permeability sample.
In summary, the in-situ rheology of polymer A in reservoir rock shows near-Newtonian behavior at
reservoir flow rates. Resistance factors of 10 and higher are achieved with 1000 ppm polymer A in all
permeabilities tested in this study and in presence or absence of oil. The data in presence of oil show much
lower shear thickening which leads to better injectivity when compared to data in the absence of oil. This
may partly explain better injectivity usually encounterd in polymer flooding than expected from in-situ
rheology data measured using plugs saturated with 100% water. It correlates well with the results obtained by
Shiran and Skauge (2015), Dupuis et al. (2017) and in this work, see section on adsorption, where polymer
adsorption was considerably reduced in presence of crude oil. More work is ongoing to study the impact
of the presence of oil on resistance factor using samples of higher permeability, K> 500 mD. Pre-shearing
showed also a much higher influence on the shear thickening behavior where shear thickening is reduced
for the pre-sheared polymer.

Polymer Injectivity
The objective of work presented in this section is to evaluate polymer A injectivity in reservoir rock at
relevant permeabilities. Determination of polymer injectivity in field trials is highly complex. The polymer
exhibits changing rheology while propagating through the first 10 meters from the injector. Polymer
retention may change with flow rate and therefore with distance from the injection well. Well conditions
such as the presence of skin has a large impact. To complicate matters more, the presence of fractures or
micro-fractures may dominate injection pressure relative to these other factors. Therefore, it is important to
screen polymers and determine injectivity properties for the given injection conditions.
In this work, polymer injectivity was evaluated by injecting 100+ pore volumes of polymer at a well
relevant injection rate. A base case of 2000 bbl/day with an injection interval of 50 ft was used. This
is equivalent to about 30 ml/min for a 1.5 inch core when matching the rock face Darcy velocity. Poor
injectivity is primarily observed by logarithmically increasing pressure with volume which is indicative
SPE-197647-MS 17

of filter cake formation and/or by steady increasing pressure with volume which is indicative of in-depth
filtration. The injectivity is therefore evaluated based on the pressure gradient for large volume injections
in reservoir cores. In addition the influence of permeability and wettability has been studied.
In an injection well with several permeability layers, the flux through the lower permeable layers will be
lower than for the high permeable layers. The injection rates have therefore been reduced in the experiments
at lower permeability. In a field injection case, the polymer may experience mechanical degradation topside,
e.g. while passing choke valves and through perforations in the well casing. Laboratory studies with pre-
sheared polymer was performed to evaluate the impact of degradation on polymer injectivity.
Permeability: An example of injectivity for high permeable reservoir rock (K=1616 mD) is shown in
Figure 16. Injection of 10% pre-degraded 1000 ppm polymer A in NAFW brine showed excellent injectivity
as evident from the pressure data showing no significant gradient over 100+ PV injected polymer. Figure 17
shows injectivity data of another high permeability sample (K=3606 mD) at residual oil saturation, polymer
concentration is 1000 ppm similar to all injectivity experiments. The water permeability at remaining oil
saturation was measured to be 542 mD, however, during polymer injection some oil droplets were produced
and the water permeability is expected to increase. Comparing the pressure drop in both experiments show
that the presence of oil improved the polymer injectivity. The pressure drop measured in the presence of oil
(Fig 17) is more than 3 times lower than the one measured in the absence of oil (Fig 16), though the brine
permeability at residual oil of sample C1 (Kw,ROS=803 mD, Fig 17) is lower than the brine permeability
of sample C2 (Kw,abs=1606 mD, Fig 16)

Figure 16—Injectivity of 10% pre-degraded 1000 ppm polymer A in NAFW brine measured
by differential pressure as a function of pore volume of polymer solution injected at
the well equivalent injection rate of 30 ml/min using water saturated reservoir core C2.
18 SPE-197647-MS

Figure 17—Injectivity of 1000 ppm polymer A in NAFW brine measured by differential pressure as a
function of pore volume of polymer solution injected at the well equivalent injection rate of 30 ml/min

Injectivity indices for some of the experiments are summarized in Table 3. Injectivity index is normally
defined as II = Q/dP [m3/d/bar], but in this case it has been scaled to adjust for the difference in injection
area so that II* = (Q/dP) x (Awell/Acore) where a well radius of 7" and thickness of 50 ft has been used. The
injectivity index is strongly dependent on the permeability and is improved in the presence of residual oil.
All the experiments in Table 3 showed good injectivity in terms of a low pressure gradient during injection.
Shear stability in porous media: High flow velocities experienced in the near-well region and
specifically at the rock face may induce shear degradation of the polymer. The consequence is breakage of
the polymer backbone which leads to shorter chains and thereby lower viscosity. To evaluate this, polymer
was injected in reservoir rock at similar flow velocities as in a typical injection well. The injection conditions
(Q = 30 ml/min for high permeable rock) were representative of an injection rate of 2000 bbl/day at an
injection zone of 50 ft in a 7" wellbore. The injected solutions were pre-degraded to various extent to
evaluate the influence of pre-shearing through topside elements such as choke valves and perforations on
the effective viscosity in the reservoir. The bulk rheology of both the original injected fluid and the effluent
was measured and is presented in Figure 18. The data demonstrates that all solutions showed excellent
shear stability at the injection rate of 30 ml/min in the high permeable reservoir rock where there is little
difference in the bulk rheology of original and effluent fluids. The changes in effluent viscosity were within
experimental error. The degree of pre-degradation did not alter the shear stability or the injectivity of the
polymer solutions.
SPE-197647-MS 19

Figure 18—Shear viscosity of injection and effluent solutions with varying degree of pre-
degradation. Effluents were collected at the high rate of 30 ml/min. All solutions are 1000 ppm
of polymer A in NAFW brine and the reservoir core C2, the measurements performed at 22 C.

In summary, polymer A shows excellent injectivity for high permeable rock (>1000 mD) and good
injectivity for intermediate (>100 mD) and low permeabilities (30 < K < 100mD). The shear stability of the
polymer is excellent compared to conventional synthetic EOR polymers.

Polymer Adsorption
Polymer adsorption has in several cases been a show stopper for implementation of polymer flooding in
carbonate reservoirs. Most synthetic polymers are negatively charged which generate high adsorption in
carbonate rock with positive surface charge. With the advent of high ATBS and high NVP based polymers,
the adsorption is strongly reduced, enabling polymer flooding to be applied also for carbonates. There is
also increasing observations that the rock surface in not only positive in carbonates, but more complex
with some sites being negative and some close to neutral charge, changing surface charge with the brine
composition and/or pH of the injected water.
Retention in porous media is complex and is influenced by many factors. In general, polymer retention
is a function of mineralogy, pore structure, flow velocity, polymer molecular structure, polymer molecular
weight, brine salinity and ion composition, pH, temperature, wettability, etc. In carbonates, the wettability is
especially important as the rock surface is typically oil wet. The water wet surfaces are typically positively
charged. The presence of oil wet surfaces will therefore significantly reduce the adsorption of negatively
charged polymers. Experiments were therefore performed both in the presence and absence of oil.
After initial screening, polymer A was selected for retention experiments with reservoir cores in the
presence and absence of oil. Measurements were made by dynamic core floods using effluent analysis of
ideal tracer and polymer concentration. There are several methods for determining the retention value, see
e.g. the discussion in Sorbie (1991). Here we found that using the method based on two slug injections to be
the best suited. The method is described by Lötsch et al. (1985) which again is based on work by Dawson
and Lantz (1972) and Shah et al. (1978). The analysis is based on the difference in production between
the first slug of polymer (irreversible adsorption) and the second slug of polymer (no further adsorption),
see example in Figure 19. Under the assumption that inaccessible pore volume (IPV) and other retention
phenomena such as straining, hydrodynamic retention etc, are not changing between the first and the second
slug, the retention of the polymer in the rock can be calculated from the equation below:
20 SPE-197647-MS

where R is the retention value (in μg/g), PVSlugN@C/C0=0.5 is the pore volume for when the effluent
concentration of polymer is 50% of that injected, VPV is the pore volume of the core, mcore is the mass of the
core and Cpoly is the concentration of the injected polymer solution.

Figure 19—Polymer concentration profiles for injection of 1000 ppm Polymer A in NAFW in reservoir core C5 (263
mD) at Sorw. Effluent concentration was measured by in-line viscometer. Polymer slug 1 in blue, slug 2 in orange.

The polymer concentration profiles for the injection of 1000 ppm Polymer A in NAFWbrine in a 263
mD reservoir core is shown in Figure 19. The first slug is delayed due to adsorption and retention and it
took 2.00 PV of polymer injection to reach 50% polymer concentration in the effluent. As expected, the
second slug elutes much faster as it is not delayed by adsorption and retention and the 50% concentration is
observed at 0.95 PV. Based on the equation above, the retention value for this core is then 115 μg/g. This is
an acceptable value considering the challenges of polymer adsorption in carbonate rock. This core was aged
with crude oil and was partly oil wet. The presence of oil films on the rock surface significantly reduces the
adsorption of the polymer. In Table 4, the retention experiment at Sorw is compared to three experiments
without oil present. The retention values are 2 – 5 times higher for the water wet cases. It is indicated that
there is an inverse relation between core permeability and adsorption.

Table 4—Retention values for injection of 1000 ppm Polymer A in NAFW in carbonate reservoir cores.

Core Kw,abs (mD) Oil Retention (μg/g) IPV

C6 121 No oil 316 0.25

C10 45 No oil 209 0.0

C11 29 No oil 570 –

C5 263 Sorw 115 –

Field Piloting and Injectivity Tests

As discussed earlier ADNOC is planning to start two polymer based EOR pilots in two reservoirs currently
undergoing waterflooding. The target reservoir, extends across several fields in Abu Dhabi, poses a major
SPE-197647-MS 21

challenge to maximise recovery due to the prevailing high permeability contrast between the upper and
lower zones. It is a layered reservoir, where strata measuring a few feet in thickness can be correlated field
wide, often over several kilometres, see Masalmeh et. al (2012). The overall permeability increases towards
the top of the reservoir. The reservoir can be described at a high level as consisting of two main bodies, i.e.
an Upper zone (high permeable layers inter-bedded between low permeable layers) and a Lower zone of
low permeability layers of relatively uniform permeability distribution. The upper part has permeabilities
ranging from 10 mD to many 100 mD and under water flooding has shown good displacement of oil by
water. The lower part has permeabilities, which are on average considerably lower than in the upper part,
ranging between 1 mD to 10 mD. Recovery from these low permeability reservoirs is low, as conventional
injectants (water and gas) will migrate rapidly to the more permeable Upper reservoir, which overlies the
Lower and is in full pressure communication with it.
Two polymer based EOR concepts were developed for these reservoirs:
a. Simultaneous injection of miscible gas and polymer (SIMGAP): Simultaneous injection of viscosified
water (polymer solution) in the Upper high permeable zone and miscible gas (e.g., H2S/CO2) in the
low permeable Lower zone. As a result, a lateral pressure gradient is maintained in the Upper zone,
providing Lower zone gas confinement.
b. Simultaneous injection of water and polymer (SIWAP): Simultaneous injection of viscosified water
(polymer solution) in the Upper zone and normal water in the Lower zone. As a variation of this
concept, viscosified water alone is injected in the reservoir which also results in similar recovery
factor as SIWAP but requires larger volume of polymer to be injected.
These novel processes have not been applied in the field, however, the industry has broad experience
in water flooding, polymer flooding and miscible gas injection. These processes (SIMGAP and SIWAP)
combine two processes into one feasible recovery mechanism. Positive simulation results are obtained with
both processes. These novel processes have the potential to achieve high recovery factors and significantly
improves the sweep efficiency in highly heterogeneous reservoirs.
The main challenge for these polymer based EOR processes is to identify a polymer that is stable at high
temperature and salinity and has a good injectivity in carbonate rock. The experimental data presented in this
paper demonstrates that an ATBS polymer showed a promising injectivity behavior which can be modulated
for injection in the target reservoirs. In addition, as the required viscosity increase for both SIMGAP and
SIWAP processes to work is moderate, we find the results to be very promising and they open the door for
field testing and piloting. To de-risk these pilots a polymer injectivity test is planned to start in 2019. Once
injectivity of the polymer is demonstrated in the field, ADNOC will be ready to start the two EOR pilots to
demonstrate the potential of the two EOR concepts. It is expected that these concepts to unlock significant
volumes of ADNOC reservoirs, both onshore and offshore.

Conclusion
Polymer flooding is a mature and successful EOR technology and has been implemented in the field for
decades. However, so far no polymer flooding has been performed at high temperature and high salinity
conditions in carbonate reservoirs. All three conditions are challenging for the polymers: high temperature
may lead to thermal degradation, high salinity may lead to precipitation and carbonate reservoirs may
lead to excessive adsorption/retention and poor injectivity. A number of new polymers were screened and
the polymer A (one of SuperpusherTM SAV range of polymers) was selected as the best candidate for the
experimental program.
Thermal stability tests were made at temperatures up to 130 °C both in the presence and absence of H2S
and up to 150 ppb of O2. Polymer A showed good stability at high temperature (130 °C) and in high salinity
(180 000 mg/L TDS formation water) in tests lasting more than 6 months. Stability at 120 °C was more
22 SPE-197647-MS

than 1 year. Rheological studies characterized the viscosifying properties of the polymer in bulk flow. These
studies provided a basis for selecting polymer concentrations for core flooding. Based on bulk viscosity
measurements a concentration of 950 ppm polymer A is required for 3x brine viscosity and 2500 ppm is
required for 10 x brine viscosity in formation water.
Through core flood experiments on reservoir cores the rheological properties of the polymer in porous
media was characterized as a function of concentration and rock permeability. Polymer A showed near-
Newtonian behavior for reservoir flow rates with resistance factors (RF) higher than 10 for concentrations
as low as 1000 ppm. The RF values increased for lower permeability, primarily as a function of increase
in permeability reduction (RRF) of the core. Polymer was injected at well relevant rates and only for cores
with permeabilities lower than 70 mD was shear degradation of the polymer observed. In the planned field
application, the primary reservoir target has permeability of more than 100 mD, suggesting that injectivity
will be good for the field application. All experiments showed that the presence of oil significantly reduced
the pressure build-up at well equivalent injection rates (reducing shear thickening).
Polymer adsorption and retention has been determined in the presence and absence of oil. In the absence
of oil, adsorption is high but is reduced to relatively low values in the presence of residual oil. Based on
these results, polymer adsorption is not a show stopper for polymer flood in reservoir carbonate rock.
The experimental program reported has identified a polymer candidate and verified polymer performance
for polymer flooding in carbonate reservoir rock in high salinity formation water at 120 °C. Injectivity
properties are excellent and retention is within an acceptable range. The data provides all required input
for reservoir simulation studies. Polymer concentration and degree of pre-degradation can be optimized to
achieve the set pilot goals.

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