Journal of Petroleum Science and Engineering 189 (2020) 106864

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Journal of Petroleum Science and Engineering

journal homepage: http://www.elsevier.com/locate/petrol

Experimental investigation and development of correlation for static and

dynamic polymer adsorption in porous media
Sameer Al-Hajri a, b, **, Syed M. Mahmood a, *, Saeed Akbari a, Hesham Abdulelah a, b,
Nurudeen Yekeen a, b, Nabil Saraih c
a
Department of Petroleum Engineering, Universiti Teknologi PETRONAS, Seri Iskandar, 32610, Perak, Malaysia
b
Shale Gas Research Group (SGRG), Institute of Hydrocarbon Recovery, Universiti Teknologi PETRONAS, Seri Iskandar, 32610, Perak, Malaysia
c
College of Petroleum and Geoscience, King Fahd University of Petroleum and Minerals, Dhahran, 34463, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: Part of the injected polymer during polymer flooding is lost in porous media by adsorption, mechanical
Polymer flooding entrapment, and hydrodynamic retention. Therefore, having a clear understanding of polymer losses/retention is
Polymer static adsorption very important for designing a technically and economically successful polymer flooding project. Polymer losses
Polymer dynamic adsorption
are traditionally modeled using Langmuir Isotherms, requiring costly and time-consuming dynamic corefloods to
obtain fitting parameters. This research suggests a faster and low-cost method for first-order approximation of
polymer adsorption in porous media without conducting corefloods. The proposed technique uses the results of
polymer adsorption on the crushed core in the static test that can be used in a lookup table in the simulator
instead of Langmuir Isotherms Equation. Mercury injection (MICP) was used to find a cut-off molecular size
based on the hydrodynamic size of the polymer calculated using the Flory-Fox equation. Brunauer-Emmett-Teller
(BET) tests are used to measure the specific surface area of the crushed core. These three tests determine the
equivalent weight of crushed core to be used for static adsorption tests that would represent the specific surface
area of the core. Seven high permeability Bentheimer core plugs from outcrops were used to perform polymer
corefloods to determine polymer adsorption, followed by seven static adsorption tests performed at similar
conditions to compare the results. Polymer adsorption tests showed that 1-h residence time, 0.5 solid-to-liquid
ratio, and pre-saturating crushed core with brine before starting static adsorption were important to map
static to dynamic polymer adsorption. Other important observations were the increase in polymer adsorption
with increasing polymer molecular weight, polymer concentration, and NaCl salinity in order of descending
significance of the effect. The proposed method gave a reasonable statistical correlation between static and
dynamic polymer adsorption with a coefficient of determination (R2) of 0.97, and Pearson’s correlation coeffi­
cient (r) of 0.98. The maximum deviation between static and dynamic result was 34% for cores of similar flow
zones, and 48% for cores of dissimilar flow zones.

1. Introduction
The polymer solution is injected into oil reservoirs to reduce the
water-oil mobility ratio (Lyons, 2010; Morelato et al., 2011). The
mechanism of polymer injection is to increase the viscosity of the
injected phase (Akbari et al., 2019a; Al-Hajri et al., 2019b; Chen et al.,
2017). By reducing mobility ratio, the sweep efficiency increases, and
hence, the oil recovery is enhanced (Chatterji and Borchardt, 1981; de
Melo et al., 2002; Needham and Doe, 1987; Zhang et al., 2019).
However, the interactions between the injected polymer molecules and
the reservoir rock are significant and may cause polymer retention in the
reservoir rock. Thus a bank of injection fluid that is wholly or partially
denuded of the polymer will form (Al-Hajri et al., 2018; Cheraghian
et al., 2014). The viscosity of this fluid bank will be much lower than the
injected polymer solution. Generally, this will reduce the efficiency of
the polymer flood.
Polymer retention includes adsorption, mechanical entrapment, and
hydrodynamic retention (Akbari et al., 2019b; Al-Hajri et al., 2018;

* Corresponding author.
** Corresponding author. Department of Petroleum Engineering, Universiti Teknologi PETRONAS, Seri Iskandar, 32610, Perak, Malaysia.
E-mail addresses: ensamyo87@gmail.com (S. Al-Hajri), mohammad.mahmood@utp.edu.my (S.M. Mahmood).

https://doi.org/10.1016/j.petrol.2019.106864
Received 26 July 2019; Received in revised form 23 December 2019; Accepted 23 December 2019
Available online 28 December 2019
0920-4105/© 2020 Elsevier B.V. All rights reserved.
S. Al-Hajri et al.
Riahinezhad et al., 2017; Zhang and Seright, 2014). Evaluation of
polymer retention is important before polymer flood implementation in
a field. It is mostly inferred from dynamic tests using core flooding ex­
periments. The dynamic tests need to be performed under conditions
which reflect those prevailing in the reservoir (Broseta et al., 1995). 10s
of polymer core floods need to be conducted under steady-state condi­
tions to extract model parameters to be fitted into the modified Lang­
muir isotherm equation for simulation study for a certain field (Sheng,
2010; Sheng et al., 2015). In addition to the time and cost needed for
dynamic adsorption tests, the validity of these results is still question­
able because Modified Langmuir Isotherm considers the effect of
salinity, polymer concentration, and permeability to some extent, but
many other parameters are still ignored, such as pH effect, aging time
and so on. These parameters can seriously affect polymer retention in
porous media. Moreover, Langmuir Isotherm assumes that adsorption is
reversible, whereas polymer adsorption is instantaneous and irrevers­
ible (Green and Willhite, 1998; Lee and Fuller, 1985; O’Shaughnessy
and Vavylonis, 2003).
Static test, on the other hand, is used to screening, optimization, or
investigate the feasibility of a polymer/surfactant adsorption processes
in porous media and their effect on fluid flow properties (Chiappa et al.,
1999; Lv et al., 2011). Results of the static tests are not representative of
the dynamic tests for several reasons, such as the difference in specific
surface areas in core and crushed core and adsorption conditions
(adsorption residence time, solid to liquid ratio, and crushed core
pre-saturation with brine).
The most significant reason for the difference between static and
dynamic results is because of the extensive difference in surface areas
available for adsorption for disaggregated sand and consolidated rock
(de Melo et al., 2002; Masoud et al., 2009). Szabo (1979, Part II), re­
ported uniform retention of the 2-acrylamide-2-methylpropane sulph­
onate (AMPS) polymer of 1.2–1.5 μg/g. This value was well correlated
with the adsorption of 22.5 μg/g in a silica flour, which has a specific
surface area of about 16 times higher than that for the sand in sandpack
(Sorbie, 2013; Szabo, 1979). Interestingly, the adsorption was almost 16
times higher in the silica flour than in the sandpack. Thus, finding a
method that will estimate the specific surface areas in the consolidated
and unconsolidated sand might assist in estimating the dynamic
adsorption from static adsorption (Caenn et al., 1989). Such a method
will require to consider the effect of the polymer hydrodynamic size,
which in essence defines the accessible surface for the polymer, which
indicates how much of polymer will be adsorbed (Yin et al., 2014).
The process of building up of a polymer layer near a solid interface
goes through a series of nonequilibrium states. The extent of an adsorbed
polymer layer ability to relax at an equilibrium structure is complex and
still under investigation (Gregory, 1995). However, as the polymer to
surface interaction becomes stronger, relaxation becomes more difficult.
Molecules which arrive earlier for adsorption will flatten and promote a
fraction of polymer surface contacts, while a significant number of
molecules arriving at later stages will adsorb with a low bound fraction
(Schneider et al., 1996). As a consequence, the rate at which polymer
molecules arrive at an interface should affect the adsorbed amount (van
Eijk and Cohen Stuart, 1997). Therefore, the adsorption time in static
and dynamic is important when correlating both adsorption results.
Moreover, solid to liquid ratio controls how much polymer will be
adsorbed at the solid surface (Argillier et al., 1996; Masoud et al., 2009).
Pre-saturating the crushed core with brine before starting the static test
is also important to yield a similar adsorption environment since the
core is pre-saturated with brine before injection with the polymer
solution.
Static and dynamic adsorption of polymer in porous media has been
widely investigated in previous works (Abidin et al., 2012; AlSofi et al.,
2017; Alvarado and Manrique, 2010; Amirian et al., 2018; Cheraghian
et al., 2014; Choi et al., 2016; Dang et al., 2014; Li et al., 2016, 2017).
Unlike static tests, dynamic adsorption tests are costly and
time-consuming. No method is currently available method that
2
Journal of Petroleum Science and Engineering 189 (2020) 106864
correlates static adsorption of polymer to dynamic adsorption. The main
objective of this work is to propose a method which can correlate static
to dynamic adsorption. The proposed method is faster and less expensive
as it uses a static polymer adsorption test. It is based on the idea that we
can measure the adsorption per unit surface area and the inaccessible
pore volume separately and combine the results to give us values that
are practically representative of the dynamic test. Materials and
Methods.
1.1. Polymer and brine
A partially Hydrolyzed Polyacrylamide (HPAM) Flopaam 3230 S and
sulfonated polyacrylamide polymers (AN 113 VLM and AN 113 VHM)
were used in this research. The three polymers are provided by SNF
Floerger Group as white granular powders. The molecular weight of
HPAM is estimated at approximately 6–8 million Daltons with a hy­
drolysis degree of about 30%. The molecular weight of AN 113 VLM is
estimated at approximately 0.5–1 million Daltons with a sulfonation
degree of 13% and AN 113 VHM of approximately 11–12 million Dal­
tons with a sulfonation degree of 13%. The polymer solution was pre­
pared using the magnetic stirrer vortex method. Ultra-pure water was
used with three Sodium Chloride (NaCl) salinities (1000, 5000 and
15,000 ppm). The rheology of HPAM, AN 113 VLM, and AN 113 VHM
polymers was determined using TA Rheometer (Thermal Analysis and
Rheology Instruments) at a shear rate ranges between (0.1–500 S 1), the
viscosity measurement was conducted at the room temperature (25 � C).
Nicolet iS10 (Atkinson, NH, USA) was used for Fourier Transform
Infrared Spectroscopy FTIR measurements.
1.2. Dynamic adsorption measurement
Bentheimer sandstone core samples have proven to be ideal for
laboratory studies because of their block scale homogeneous nature and
lateral continuity. They have been widely utilized to study reservoir
issues for passive and active properties of oil, gas, water, rock in­
teractions, and processes to flow and transport. The physical properties
of seven Bentheimer cores used for core flooding experiments are shown
in Table 1. The porosity of the seven cores was slightly similar, ranging
from 19.8 to 22.3%. Similarly, BH-4 had the highest permeability of
3150 md; permeability ranged from 1932 md to 2344 md for the other 6
cores.
Solutions of Flopaam 3230 S, AN113 VLM, and VHM are prepared by
mixing and dissolution. Ultra-pure water was stirred in a beaker by a
magnetic stirrer at 720 rpm, and 1000, 5000 and 15,000 ppm of NaCl
were added to the ultra-pure water to make the base solution. Finally,
dry polymer powder was slowly introduced to avoid the formation of
fish-eyes, which can be formed if the powder is not wetted evenly. The
solution was then stirred slowly for almost 24 h to ensure complete
dissolution. The compositions and concentrations of all samples pre­
pared are shown in Table 2.
A similar base solution (having the same NaCl concentration) was
prepared and vacuumed from the air using a desiccator. After the core
was weighed in its dry state, it was saturated with the degassed brine
and vacuumed in the desiccator for 24 h. The core was then weighed
again to determine its pore volume using the gravimetric analysis.
Benchtop Permeability System (BPS) manufactured by Coretest
Systems Corporation was used in performing the core flood for dynamic
adsorption in the porous media. We used the extended injectivity
method used by Lotsch and Law for the dynamic adsorption test
(Al-Hajri et al., 2018; Lotsch et al., 1985). In this method, two polymer
solution slugs of the same composition are injected into the core and
separated by an extended brine injection. 4 ml of the effluent polymer
samples were collected every 4 min. Polymer adsorption was deter­
mined from the area under the two curves of the normalized concen­
tration of the polymer plotted versus injected pore volume. A schematic
of the unit used in the dynamic adsorption test is shown in Fig. 1.
S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

Table 1
Core sample properties.
Core ID Lithology Length (cm) Weight (g) Porosity (%) Permeability (md) Pore Volume (cc)

BH-1 Sandstone 7.6 170 20.0 2057 17.0

BH-2 Sandstone 7.4 167 19.9 2233 17.2
BH-3 Sandstone 7.4 166 20.5 2344 17.5
BH-4 Sandstone 7.4 169 22.3 3150 18.7
BH-5 Sandstone 7.4 170 19.8 2093 17.3
BH-6 Sandstone 7.6 169 19.5 1991 17.2
BH-7 Sandstone 7.6 170 19.2 1932 17.1

Table 2
Polymer solution composition.
Sample ID Polymer type Polymer Concentration (ppm) Molecular Weight (million Dalton) Salinity (ppm)

P1 Flopaam 3230 S 400 6 1000

P2 Flopaam 3230 S 1000 6 1000
P3 Flopaam 3230 S 2000 6 1000
P4 Flopaam 3230 S 1000 6 5000
P5 Flopaam 3230 S 1000 6 15,000
P6 AN113 VLM 1000 1 5000
P7 AN113 VHM 1000 12 5000

1.3. Polymer concentration measurement
UV–Vis method has proven to be trusted and convenient for
measuring the concentration of polymers (Hunt et al., 1988; Wei et al.,
2014; Yekeen et al., 2019). Agilent Cary 60 Spectrophotometer with a
wavelength between 1100 and 190 nm (Agilent Technologies) was used
to determine the polymer concentration in both dynamic and static tests.
Cary 60 was utilized to measure the absorbance of the polymer as a
function of the wavelength (peaking at 330-300 nm) of the electro­
magnetic spectrum. Polymer concentration was determined using a
calibration curve of the absorbance created from a known polymer
concentration.
1.4. Amount of crushed core determination for static adsorption
To determine the weight of the crushed core required to represent
the same specific surface area as of the core, a cut-off specific surface
area was obtained from MICP based on the hydrodynamic size of the
polymer. BET was used to measure the crushed core-specific surface
area. The following steps were then followed to estimate the crushed
core amount required to represent the adsorption in the core;
- The MICP cut-off surface area was multiplied with the weight of the
core to obtain the surface access, as shown in Eq. (1);
Surface access ðm2 Þ ¼ MICP cut
�
off surface area ðm2 gÞ X Weight of core ðgÞ (1)
- The surface access was then divided by the crushed core-specific
surface area. The amount of crushed core in grams, which will give
the same specific surface area as the core was estimated, as shown in
Eq. (2);
�
Estimated crushed core weight ðgÞ ¼ Core surface access ðm2 Þ
� (2)
Crushed core surface area ðm2 gÞ
Secondly, since the objective is to correlate the adsorption in the core
by the adsorption of the crushed core. The same weight of the injected

Fig. 1. Schematic for experimental set-up used for polymer adsorption determination.

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S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

liquid in the dynamic adsorption test was used as the weight of the liquid
in the static adsorption test.
From the estimated crushed core weight and liquid weight, an esti­
mation of the S/L ratio was determined for each adsorption test inde­
pendently, as shown in Table 3.

1.5. Static adsorption measurement

The crushed core was prepared by crushing the Bentheimer core for
static adsorption test. Particles were sieved to sizes of 150–212 μm.
Special care and treatment were carried out for the crushed core to
reduce the crushed core’s fine particles and released carbons. This was
done by adding the sands into the brine in a beaker and shacked for 10
min, then mud-like phase at the top part of the bottle was separated from
the sand. This process was repeated and carried out until the brine at the
upper part of the sand was clear and free of mud-like phase. The esti­
mated amount of crushed core was then dried and saturated with brine
for 24 h. The following steps were followed to conduct the static
adsorption test;
Fig. 2. X-Ray Diffractometer data of the Bentheimer core and crushed core.
- The estimated amount of crushed core was added to the polymer
solution. was used for quantitative estimations of the minerals detected in the
- A bottle containing the adsorbent and adsorbate was placed and rock and crushed core. The standardless option was used, which does not
agitated on a shaker for 1 h for adsorption at room temperature. require comparison with an internal standard.
- The solid and liquid were separated. However, some solid particles The XRD results shown above indicate that the mineral contents for
remained in the liquid. Thus, a centrifuge was used to remove the both the core and crushed core are quite similar though the intensity of
rest of the sand particles from the liquid. some peaks varied negligibly (not detectable by RockJock software)
- The collected polymer solution was then taken for UV-VIS mea­ between the core and crushed core. Because of the identical mineralogy,
surements and converted into concentrations using a calibration it can be expected that the adsorption behavior of both rock and crushed
curve of concentration versus absorbance. Polymer adsorption was core will be similar.
then calculated using Eq. (3); Table 4 shows the minerals contents and their estimated percentage
for the core and crushed core samples. The XRD results show that quartz
V * ðCi Cf Þ
q¼ (3) is the dominant mineral in the core (Bentheimer outcrop). A small
Wp
fraction of carbonate (as dolomite) and feldspars (as K-feldspar and
Albite) also exist, the latter indicating that a breakdown and recrystal­
where; q is the polymer adsorption in μg/g; V is the polymer solution
lization of feldspar to clays and quartzes has taken place. The clay
volume in mL; Ci is the initial polymer concentration in μg/mL; Cf is the
contents are relatively low and mostly consisting of kaolinite, illite,
final polymer concentration in μg/mL; and Wp is the weight of the
crushed-core in grams.
Table 4
2. Results and discussion Quantitative estimations of the minerals detected in the rock and crushed core
using the standardless option of the ROCKJOCK Program.
2.1. Rock characterization Type Mineral Weight %

Silica Quartz 88
2.1.1. X-ray diffraction Carbonate Dolomite 1.4
The Malvern PanAlytical’s X’Pert3 multipurpose X-ray diffraction Feldspars K-feldspar 4.7
system was used for advanced powder X-ray diffractometer (XRD) an­ Albite 1.2
Clay Kaolinite 2
alyses of the outcrop core and its crushed core sample to study differ­ Illite 1.8
ences in mineralogy that could have affected adsorption characteristics. Chlorite 0.7
Fig. 2 shows the XRD data on a semi-log plot. RockJock, a computer Montmorillonite 0.2
program that determines quantitative mineralogy in powdered samples,

Table 3
Calculated solid to liquid ratio for the static adsorption test.
Sample Specific Surface Area by Cut-off Specific Surface Area by Hydrodynamic size of the Amount of Crushed Solid to Liquid Amount of
ID BETa (m2/g) MICPb (m2/g) polymer (nm) Core (g) Ratio Liquid (g)

BH-1 0.327 0.040 424 2.5 0.517 4.8

BH-2 0.327 0.040 424 3.0 0.791 3.8
BH-3 0.327 0.040 426 2.0 0.414 4.8
BH-4 0.327 0.085 352 3.0 0.630 4.8
BH-5 0.327 0.044 311 3.0 0.727 4.1
BH-6 0.327 0.064 144 3.0 0.706 4.2
BH-7 0.327 0.043 420 2.5 0.512 4.8
a
Three samples were measured, and the average value is shown.
b
BH-2 was used for MICP determination, and its value was used for all the samples due to their close match with permeability except for BH-4, whose value was
independently determined. The values are differing due to the variation in the molecular size due to polymer type and concentration, salinity, and MW, as shown in
Table 2.

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S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

chlorite, and montmorillonite in descending order of contribution. The

core appears to be relatively free of smectite, a more problematic type of
clay. The overall mineral contribution indicates that the Bentheimer
core sample is clean quartz sandstone.

2.1.2. Scanning electron microscopy

Fig. 3 shows four carefully selected SEM images to provide a
comprehensive overview of pore throats, surfaces, and exemplary min­
eral phases. Results show few and locally distributed clay accumula­
tions, which possibly consist of illite. Clay accumulations form low and
interconnected porosity in small spatial areas.
Fig. 3a and b shows the distribution, shape, and size of the quartz
matrix. SEM results agree with the XRD results, which shows quartz
dominating the mineral content. Most of the quartz grains are well-
sorted and have almost similar size and shape, indicating isotropic
physical behavior suggesting that the flow adsorption physics is ex­
pected to be distributed evenly throughout the porous media. Fig. 3c
shows feldspar mineral dissolved in porous media and forming intra­
granular porosity. Fig. 3d shows clay agglomerations indicating a local Fig. 4. The pore size distribution of Bentheimer core sample.
reduction in pore space and an increase in specific surface area of the
adsorbate.
distribution indicates that the size of the majority of pores is in the range
SEM images show that the Bentheimer sandstone pores are well
of 8000–60,000 nm, which contribute to most (>80%) of the
interconnected. The large pores contribute most of the pore space (80
permeability.
μm), whereas small pores are few and can be related to the accumula­
The low number of pores smaller than 8000 nm is an indication of
tions of the clay minerals. Feldspars are partially dissolved and
low clay content confirming the results of SEM imaging analysis. By the
contribute to the total porosity, albeit its porosity is more complex and
same token, the shape of the MICP curves is consistent with SEM images
local. No cementation minerals were observed, which may be a signif­
in suggesting that the Bentheimer sandstone sample has a dominant and
icant reason for the high permeability in the Bentheimer core.
well-connected pore system with a few secondary networks related to
small clay agglomerations.
2.1.3. Pore size distribution and pore surface area
When the hydrodynamic polymer size is known, MICP results can be
Mercury Injection Capillary Pressure (MICP) tests were carried out
used to determine the cut-off value for the specific surface area of a core
on two Bentheimer core samples to investigate the pore size distribution.
sample (Bentheimer) that is accessible by the polymer solution. This is
Fig. 4 shows the MICP results for the Bentheimer core. The pore size

Fig. 3. SEM image of Bentheimer sandstone showing (a) distribution and shape, (b) pores size, (c) feldspar mineral, and (d) Clay agglomerations.

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S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

because the remaining pore volume is inaccessible to the polymer; thus,

it is occupied by water, which stays in equilibrium with the polymer
solution.

2.1.4. Crushed core surface area by Brunauer–Emmett–Teller (BET)

The adsorption in porous media is a function of the total surface area
of the grains because of the molecular interactions between polymer and
rock, notwithstanding the interaction between the molecules of the
polymer itself. Therefore, finding a specific surface area of a porous
medium is very important for estimating the polymer adsorption.
Brunauer–Emmett–Teller (BET) is an important analysis technique
for the measurement of the specific surface area of materials. Table 5
shows the surface areas obtained from the three samples using the BET
surface area analyzer (Model: Micrometrics ASAP, 2020) at low-pressure
nitrogen gas adsorption. Before placing the samples into the surface area
analyzer for testing, these samples of 150–212 μm grain sizes were
placed in an oven-controlled at 150 � C under a vacuum of 10 6 Pa for
more than 24 h to degas the samples and remove moisture from them.
This value was compared and agreed to the reported surface area of the
Bentheimer sandstone from literature, which ranges between 0.2 and Fig. 5. Rheology of “Flopam 3230 S, AN 113 VHM and AN 113 VLM” at a
0.8 m2/g (Halisch, 2013; Peksa et al., 2015). concentration of 1000 ppm and salinity of 5000 ppm.

2.2. Polymer solution characterization

2.2.1. Rheology
Fig. 5 shows data from the rheological study at 1000 ppm concen­
tration and 5000 ppm salinity of three polymers, namely: Flopaam 3230
S, AN 113 VLM, and AN 113 VHM. All three polymer solutions exhibited
shear-thinning behavior for the range of shear rate tested (0.1–500 s 1).
The decrease in polymer solution viscosity was significant with
increasing shear rate. The highest reduction (400 times) was encoun­
tered by AN 113 VHM. However, the other two polymer solutions also
exhibited a significant reduction.
This behavior was expected since most polymer solutions exhibit
shear-thinning because of the greater breakage/destruction of the en­
tanglements between the polymer molecules at a higher shear rate.
Consequently, a decrease in the hydrodynamic size of the polymer and
thereby a reduction in polymer viscosity (Lu et al., 2016; Wei, 2015).
This implies that an increase in shear rate will result in higher adsorp­
tion as more porous media will be exposed to the polymer solution due
to the reduced hydrodynamic size of the polymer.
Fig. 6. Fourier Transform Infrared Spectroscopy (FTIR) of Flopaam 3230 S, An
2.2.2. Chemical composition 113 VLM, and AN 113 VHM at a polymer concentration of 1000 ppm and
salinity of 5000 ppm.
Fig. 6 shows the results for Fourier Transform Infrared Spectroscopy
for the three polymers showing the chemical composition and the in­
teractions between its functional groups. The polymers were loaded as a respectively. The –SO3 group might result in peaks at 1320, 1426, and
powder in the Nicolet iS10 FTIR system. 1550 cm 1 (Akbari et al., 2017; Dai et al., 2017).
The FTIR test was conducted in this study as a routine character­
ization test to confirm the existence of the polymer molecules in solu­
2.3. Dynamic adsorption tests by coreflooding
tion. The polymer molecules can usually be detected through variation
in transmittance at various wavenumbers. For a particular wavenumber,
Polymer solutions of different molecular weights, polymer concen­
the transmittance peaks due to stretching vibrations of the amide group
trations, and salinity were injected at a rate of 1 cc/min into seven cores
of the polymer molecules.
from Bentheimer sandstone outcrop formation.
The peak at a wavenumber of 1650 cm 1 is assigned to the
There are several methods to determine the retention of polymers,
stretching vibrations of C–
– O in the amide group –CONH2. By the same
such as Single Polymer Injection, Extended Injectivity, and Concentra­
token, wavenumbers 3340 and 2960 cm 1 are caused by the stretching
tion Profile methods (Al-Hajri et al., 2018). However, the dynamic
vibrations of the N–H in the amide group –CONH2 and –CH3,
retention values were obtained in this study by using the extended
injectivity method.
Table 5
Bentheimer crushed core surface areas determined by BET analysis.
2.3.1. Effect of polymer concentration on dynamic adsorption
Sample ID BET Surface Area (m2/g) Deviation from Average (%) The effect of polymer concentration on dynamic polymer adsorption
S1 0.23 30 in porous media was investigated using three Bentheimer sandstone
S2 0.31 5 samples (BH-1, BH-2, and BH-3). The salinity and molecular weight
S3 0.44 þ30 were fixed at 1000 ppm NaCl and 6 million Dalton, respectively. The
Savg 0.326
three polymer concentrations selected for this study were 400, 1000,
–

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Fig. 7. Breakout curve profile for Flowpaam 3230 S at polymer concentration of: (a) 400 ppm, (b) 1000 ppm and (c) 2000 ppm. Bentheimer core samples; 1000 ppm
NaCl; and 6 million Dalton Molecular Weight.

and 2000 ppm. Fig. 7 shows the results as normalized polymer con­
centration vs. pore volume (PV) injected.
At around 2.3 PV of injection (Fig. 7a), the curves of both first and
second slugs merged, indicating that full adsorption has been achieved
at this point. Similar behavior was noticed for first and second polymer
slugs in 1000 and 2000 ppm polymer concentration with variations on
merging of both slugs at the end of adsorption, as shown in Fig. 7b and c.
The area between the two curves reflects the adsorption in the cores.
By a visual inspection of the separation area between the curves of all
three plots, it is apparent that the lowest adsorption (9.34 μg/g)
occurred with 400 ppm polymer concentration, the highest adsorption
(12.86 μg/g) at 2000 p.m., and 1000 was in between (11.3 μg/g).
Table 6 lists the adsorption results, as discussed above.
To see if there is any correlation between the polymer concentration
and dynamic adsorption, the data in Table 6 are plotted in Fig. 8. A
somewhat linear relationship is observed with an R-squared error of
96%.
Eq. (4) was used (Yekeen et al., 2017a, 2017b) to verify if the effect
of concentration on polymer adsorption agreed with the Langmuir
model.
qmax KL CE Fig. 8. Computed dynamic adsorption vs. polymer concentration of Flopaam
qe ¼ RL (4) 3230 S polymer in Bentheimer cores at 1000 ppm salinity.
1 þ KL CE

where; qe is the amount adsorbed (mg/g); qmax is the maximum

Table 6 adsorption capacity (mg/g); CE is the equilibrium polymer concentra­
Computed dynamic adsorption of Flopaam 3230 S at different polymer con­ tion (mg/L); KL is the Langmuir constant (L/mg), and RL is the Separa­
centrations and 1000 ppm salinity in Bentheimer cores. tion factor or equilibrium parameter for Langmuir isotherm.
Polymer Polymer Adsorption Polymer Adsorption Sample Fig. 9 shows the results of the dynamic experiments agreeing with
Concentration (ppm) (μg/g) (μg/m2) ID the Langmuir isotherm when fitted with the model.
400 9.34 236 BH-1
1000 11.30 283 BH-2 2.3.2. Effect of salinity on dynamic adsorption
2000 12.86 322 BH-3 The effect of salinity on polymer dynamic adsorption was another

7
S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

Table 7
Computed dynamic adsorption in Bentheimer cores of 1000. ppm Flopaam
3230S polymer (6 million Dalton molecular weight) in at various NaCl Salinities.
Salinity Polymer Adsorption Polymer Adsorption (μg/ Sample
(ppm) (μg/g) m2) ID

1000 11.30 283 BH-2

5000 16.32 192 BH-4
15,000 13.01 296 BH-5

As illustrated in Table 7, an increase in NaCl salinity from 1000 ppm

to 5000 ppm increased the adsorption from 11.30 to 16.32 μg/g for
Flopaam concentration of 1000 ppm and 6 million Dalton molecular
weight. Surprisingly, for unknown reason(s), the highest NaCl salinity of
15,000 ppm encountered lower adsorption of only 13.01 μg/g. The
salinity vs. Polymer adsorption data shown in Table 7 (Fig. 11) is not
showing any correlation. The reason(s) for the lack of correlation in
dynamic tests is not exactly understood. It could have been due to the
variation in clay content, but Bernheimer cores are known to have very
little if any, clay content. The permeability variation is another possi­
bility since one of the samples (BH-4) had a significantly higher
Fig. 9. Dynamic experiments result agreeing with the Langmuir isotherm.
permeability, but generally, higher adsorption is not expected from a
higher permeability sample because it would encounter lesser me­
important parameter investigated in this study besides the effect of
chanical entrapment if any. The random experimental error could also
polymer concentration. Since the polymer size shrinkage with salinity
be considered as a potential reason.
plateaued at 15,000 ppm of NaCl, 1000, 5000 and 15,000 ppm of NaCl
The data in Table 7 has been plotted in Fig. 11 to give a visual
salinities were selected to allow a better range of molecular sizes up to
impression of the salinity versus adsorption trend and discrepancy at
the minimum polymer hydrodynamic size.
higher salinity can be clearly seen.
Fig. 10 shows the breakout curves for polymer adsorption for a
polymer concentration of 1000 ppm and 6 million Dalton molecular
2.3.3. Effect of polymer molecular weight on dynamic adsorption
weight. The breakout behavior and adsorption results for sample BH-2
The effect of the molecular weight of polymers on adsorption was
with 1000 ppm salinity were highlighted in the previous section. With
investigated for molecular weights of 1, 6, and 12 million Dalton at
higher salinities of 5000 or 15,000 ppm, full adsorption was achieved at
5000 ppm NaCl salinity and 1000 ppm polymer concentration. The re­
2.5 and 2.75 PV, respectively.
sults are plotted in Fig. 12 as breakout curves versus pore volume

Fig. 10. Breakout curve profiles for 1000 ppm polymer concentration and 6 million Dalton molecular weight and NaCl salinity of (a) 1000 ppm, (b) 5000 ppm, and
(c) 15000 ppm.

8
S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

Dalton molecular weight polymer (55.25 μg/g) (Al-Hajri et al., 2019a).

This indicates that molecular weight plays a significant role in polymer
adsorption, although it is one of the least reported parameters in the
literature.
To see if there is any correlation between the polymer molecular
weight and dynamic adsorption, the data in Table 8 are plotted in
Fig. 13. A somewhat linear relationship is observed with an R-squared
error of 90%.

2.4. Test conditions significantly affecting polymer adsorption

After dynamic corefloods and before conducting the static test, we

had to reflect the same adsorption conditions in the static test as in the
dynamic. For obtaining a reasonably accurate adsorption data, it is
essential that the static tests be performed in conditions that closely
represent the would-be dynamic tests. The following section discusses
the conditions that need to be matched.

Table 8
Computed dynamic adsorption of Flopaam 3230 S, AN 113 VLM, and AN 113
Fig. 11. Computed dynamic adsorption in Bentheimer cores of 1000 ppm
VHM polymers in Bentheimer cores at different molecular weights in Ben­
Flopaam 3230S polymer (6 million Dalton molecular weight) in at various
theimer cores.
NaCl Salinities.
Polymer Polymer Polymer Polymer Sample
Molecular Weight Name Adsorption Adsorption ID
injection and show that the full adsorption was achieved at approxi­ (Million Dalton) (μg/g) (μg/m2)
mately 2.6 pore volume in each of the three cores.
1 AN 113 9.26 145 BH-6
Table 8 lists the dynamic adsorption in Bentheimer cores of various VLM
polymers of different Molecular Weights at 1000 ppm polymer con­ 6 Flopaam 16.32 192 BH-4
centration and 5000 ppm NaCl. Adsorption generally increased with 3230 S
increasing molecular weight, wherein it was lowest (9.26 μg/g) for 1 12 AN 113 55.25 1285 BH-7
VHM
million Dalton molecular weight polymer and highest for 12 million

Fig. 12. Breakout curve profiles for 1000 ppm polymer concentration and 5000 PPM NaCl salinity and molecular weights of (a) 1 mD, (b) 6 mD, and (c) 12 million
Dalton. The cores were closely matched in physical properties.

9
S. Al-Hajri et al.
Fig. 13. Dynamic adsorption in Bentheimer cores at 1000 ppm concentration
of various polymers of different molecular weights with 5000 ppm NaCl.
2.4.1. The effect of residence time on polymer adsorption
The adsorption kinetics of the polymer was investigated by
immersing Bentheimer sand (crushed core) into 1000 ppm concentra­
tion of Flopaam 3230 S with 1000 ppm NaCl salinity. The ratio of solid
(sand) to liquid was 0.075, which was selected to minimize the amount
of the sand used due to the scarcity of core. Samples were collected for
concentration analysis at intervals of 0.083, 0.166, 0.333, 0.5, 1, 2, 3,
18, 24 h. This interval was selected based on literature reporting in­
tervals in the range of 0.083–24 h. The results are shown in Fig. 14.
The time required for polymer adsorption, when at least 80% of
adsorption has taken place, is an important criterion, and it is generally
close to 1 h. To relate the static adsorption to the dynamic adsorption, it
was important to find a relevant time that could be applied to both the
dynamic as well as static tests.
The adsorption kinetic data of Flopaam 3230 S showed (Fig. 14) that
Polymer adsorption had reached to 313 μg/g in the first 5 min (0.083 h)
then increased to 1567 μg/g in 10 min (0.166 h). Adsorption slowed
down thereafter, reaching approximately 2648 μg/g in 1 h, which was
more than 80% of the maximum polymer adsorption of 3150 μg/g
attained in approximately 18 h.
Fig. 14. Adsorption kinetic for Flopaam 3230 S, AN 113 VLM, and AN 113
VHM in Bentheimer sand.
10
Journal of Petroleum Science and Engineering 189 (2020) 106864
To allow for at least 80% polymer adsorption for our study, a resi­
dence time of at least 1 h was allowed for both static and dynamic
adsorption tests, which corresponded to 3 PV of injection at our desired
rate of polymer injection. A residence time higher than 1 h was not
preferred because it will make comparing adsorption in static tests to the
dynamic tests (for which 3 PV was enough for full adsorption) more
difficult.
Not much discussion will ensue regarding the adsorption kinetics of
the other two polymers (AN 113 VLM and AN 113 VHM) since they
showed similar behavior in terms of adsorption time dependency. As
shown in Fig. 13, AN 113 VLM and AN 113 VHM reached 94% and 86%
adsorption respectively in 1 h.
2.4.2. Effect of solid-to-liquid ratio on polymer adsorption
The adsorption of the polymer molecules at a solid interface is a
complex phenomenon that depends upon the nature of the rock surface
and its interactions with the polymer solution. Both the quantity of
polymer solution and the availability of rock’s surface area dictate the
extent of polymer adsorption.
The effect of Solid-to-Liquid ratio (S/L) on polymer adsorption was
investigated by immersing Bentheimer crushed cores (sand) in a mixture
of 1000 ppm polymer and 1000 ppm NaCl salinity at S/L ratios of 0.001,
0.005, 0.0075, 0.01, 0.05 and 0.075. The results are listed in Table 9 and
plotted in Fig. 15 to show the S/L ratio effect on adsorption isotherm.
Overall, lower polymer adsorption was observed at higher S/L ratios.
From a very small S/L ratio of 0.001–0.01, the adsorption almost line­
arly reduced from 10,300 to 3598 μg/g. At higher S/L’s after 0.05,
adsorption did not change significantly. This shows that S/L is very
important for correctly mapping static to dynamic adsorption charac­
teristics. This suggested that the selected S/L should be � 0.075 (S/L at
stabilization) for our static to dynamic mapping study. In our experi­
ments, the volume of polymer solution throughput required to complete
the adsorption in dynamic was used as the weight of the liquid required
to calculate the S/L ratio for the static test. A pseudo-S/L ratio of 0.5 was
found to yield the best mappings with static tests.
2.4.3. Effect of brine pre-saturation on crushed sand adsorption
Static tests are normally utilized in place of time-consuming, diffi­
cult, and costly dynamic tests to optimize various operating parameters.
In these static tests, the core is crushed, sieved to collect a particular
range of sizes, then washed with distilled (deionized) water and some­
times with brine as well, and then dried before starting the static
adsorption test.
In dynamic tests, on the other hand, cores are initially saturated with
desired brine and vacuumed to remove any gas (air) bubbles trapped in
the pores to ensure that the polymer solution will have better access to
the pore surfaces during polymer flooding.
Since the static and dynamic experiments are started in differing
conditions of either dry or pre-saturated conditions, experiments were
performed to see the effect of pre-saturation with brine versus dry
conditions on static tests. The results are plotted in Fig. 16 showing static
to dynamic (S/D) adsorption ratios at varying S/L for initially dry and
brine pre-saturated crushed core conditions. The plot clearly shows the
importance of pre-saturating the crushed cores before conducting static
adsorption tests. Not only the S/D adsorption ratio is closer in pre-
Table 9
Adsorption at various S/L’s.
S/L Ratio Adsorption (μg/g)
0.001 10,390
0.005 5205
0.0075 4590
0.01 3598
0.05 2702
0.075 2648
S. Al-Hajri et al.
Fig. 15. Effect of S/L ratio on polymer adsorption.
Fig. 16. Comparison of S/D adsorption ratio vis-�
a-vis S/L for initially dry and
brine pre-saturated crushed cores.
saturated condition, but it also becomes insensitive to further increases
in S/L much earlier. Furthermore, the deviation between the S/D
adsorption ratio of dry and pre-saturated conditions was greatest in the
middle of the S/L ratio range of 0.001–0.05, the reason for which is not
known.
The adsorption was lower when crushed cores were pre-saturated
before starting the static tests, possibly because some ions were
already attached to the surfaces, which reduced the adsorption of
polymer molecules. It is therefore concluded that pre-saturating the
crushed core before starting the static tests is important for improved
static to dynamic mapping. This is also intuitively supported by the fact
that having similar initial conditions for both static and dynamic tests
should yield a closer match.
2.5. Bulk static polymer adsorption tests
The effects of molecular weights, polymer concentrations, and
salinity during dynamic adsorption tests were discussed in section 3.3.
The same parameters were tested for polymer adsorption in the static
tests. A brief discussion follows.
11
Journal of Petroleum Science and Engineering 189 (2020) 106864
2.5.1. Effect of polymer concentration on adsorption
To investigate the effect of polymer concentration on polymer
adsorption on Bentheimer crushed cores, Flopaam 3230 S polymer of 6
million Dalton molecular weight with 1000 ppm NaCl salinity was used
with polymer concentrations of 400, 1000 and 2000 ppm. These con­
centrations were chosen because they fall in the semi-dilute region
(intermediate concentration region) at which most variations in poly­
mer adsorption occur (Manichand and Seright; Zhang and Seright,
2014). The results are illustrated in Fig. 17, which shows a high corre­
lation between adsorption and polymer concentration.
The higher polymer adsorption encountered at higher polymer
concentrations is probably because a higher number of polymer mole­
cules are exposed per unit of surface volume, increasing the probability
of adsorption. This result agrees well with the results from the dynamic
tests (as discussed earlier) in which polymer adsorption increased as the
polymer concentration increased.
Table 10 lists the data shown in Fig. 17.
Fig. 18 shows the results of the static experiments agreeing with the
Langmuir isotherm when fitted with the model.
2.5.2. Effect of salinity on adsorption
To investigate the effect of salinity on polymer adsorption on Ben­
theimer crushed cores, 1000 ppm Flopaam 3230 S polymer of 6 million
Dalton molecular weight was used with salinities of 1000, 5000, and
15,000 ppm. The salinities were chosen based on the effect of salinity on
the size of the polymer, as mentioned earlier.
Fig. 19 illustrates the effect of salinity on polymer adsorption. The
overall behavior polymer adsorption increases with increasing salinity.
This can be explained by the fact that polymer chain is flexible, resulting
in more respond to the ionic strength and its solution properties are
sensitive to salinity, which shrinks the polymer and produces more
volume for adsorption.
Table 11 lists the data shown in Fig. 19.
The higher polymer adsorption with increasing salt concentration
(Table 11, Fig. 19) is consistent with the reported literature (Smith,
1970). His data also showed a small increase at lower salinities and a
sudden jump at higher salinities, though his range of salinities was much
higher than ours. He stated, “The obvious effect of increasing salt con­
centration is to increase the amount of polymer adsorbed. At NaCl
concentrations of 10 percent and higher, polymer adsorption becomes
quite high compared with that at low salinities. In going from 0.5
percent to 20 percent NaCI the extent of adsorption increases over 50
Fig. 17. Effect of Flopaam 3230 S polymer Concentration on polymer
adsorption in Bentheimer crushed core with 1000 ppm NaCl salinity and 6
million Dalton molecular weight.
S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

Table 10 times.
Polymer adsorption on Bentheimer crushed core at various concentrations of
Flopaam 3230 S of 6 million Dalton molecular weight with 1000 ppm NaCl 2.5.3. Effect of polymer molecular weight on adsorption
salinity. Although the polymer molecular weight plays a significant role in
Polymer Concentration (ppm) Polymer Adsorption (μg/g) polymer adsorption, it is one of the least parameters reported in the
400 80.34 literature. To investigate the effect of molecular weight on polymer
1000 115.03 adsorption on Bentheimer crushed cores, 1000 ppm of polymers (AN
2000 157.06 113 VLM, Flopaam 3230 S, and AN 113 VHM) with 5000 ppm NaCl
salinity was used with 1, 6, and 12 million Dalton. Fig. 20 shows the
effect of molecular weight on polymer adsorption. Polymer adsorption is
sensitive to the higher molecular weight, which shows how polymer
molecular weight plays a major effect on polymer adsorption.
The main reason for the high adsorption capacity in the high mo­
lecular weight polymer might be due to the nature of the polymer
molecules. Polymer molecules vary in size with molecular weight. At
low molecular weight, the polymer has shorter molecules in length
compared to higher molecular weights, which have extended and longer
molecules. In fact, the length of the polymer determines its weight.
Therefore, even if the number of adsorbed polymer molecules is the
same for high and low molecular weights, the adsorption is reported in
micrograms of the polymer will show higher polymer adsorption.
Table 12 lists the data shown in Fig. 20.

2.6. Correlating static polymer adsorption with dynamic adsorption

Dynamic adsorption tests are more realistic in estimating the

Fig. 18. Static experiments result agreeing with the Langmuir isotherm.
adsorption in porous media. However, they are difficult to conduct,
time-consuming, and expensive. For gross approximations of polymer
adsorption for screening, optimization, or economic feasibility of a
polymer, the simpler static tests are often substituted. Presently, it has
not been ascertained as to how closely the static adsorption results de­
pict the dynamic results. By the same token, no method is currently
available to estimate dynamic adsorption behavior by using static
adsorption tests. This research aims to fill this gap.
The main approach of this research was to perform both static and
dynamic tests using the same polymer solution, residence time, solid to
liquid ratio (S/L), and brine pre-saturation and compare the results of
both tests.
Traditionally, the static adsorption is computed by Eq. (3). A modi­
fication to this equation is proposed in Eq. (5) which includes the
amount of crushed core and S/L consideration:

Fig. 19. Effect of salinity on polymer adsorption in Bentheimer crushed core

with 1000 ppm Flopaam 3230 S and 6 million Dalton molecular weight.

Table 11
Polymer adsorption on Bentheimer crushed core at various NaCl
salinity with 5000 ppm NaCl salinity and 6 million Dalton molecular
weight.
Salinity (ppm) Polymer Adsorption (μg/g)

1000 115.03
5000 118.28
15,000 164.92
Fig. 20. Effect of molecular weight on polymer adsorption in Bentheimer
crushed core with 1000 ppm polymer concentration and 5000 ppm
NaCl salinity.

12
S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

Table 12
Polymer Adsorption on Bentheimer crushed core at various molecular weights
with 1000 ppm polymer concentration and 5000 ppm NaCl salinity.
Molecular Weight (million Polymer Name Polymer Adsorption (μg/g)
Dalton)

1 AN 113 VLM 86.32

6 Flopaam 3230 S 118.28
12 AN 113 VHM 429

Vl *Ab *ðCi Cf Þ
q¼ (5)
Wc *Am

where, Vl is the volume of the injected polymer solution in mL, Ab is the

specific surface area of the crushed core in m2/g, Ci and Cf are the initial
and final polymer concentrations in μg/mL, Wc is the weight of the core
in grams, Am is the cut-off surface area of the core in m2/g.
Both static and dynamic adsorption test data are listed in Table 13.
Static adsorption was higher than dynamic adsorption in Table 13 for
all the samples tested except for BH-2 even after reporting adsorption
results in terms of surface area. This difference may have resulted from Fig. 21. A plot of static vs. dynamic adsorption test data.
the use of different methods (and equipment) for surface area determi­
nation in static and dynamic tests. The surface area for static tests was
determined using BET, whereas MICP was used for dynamic tests. The Table 14
former method can only handle crushed cores, whereas the latter The static and dynamic adsorption data with a deviation of the computed dy­
method requires consolidated cores. We tried to use MICP for crushed namic adsorption.
cores as well but did not succeed due to the lack of pressure buildup Sample Actual Static (a) Actual (b) Calculated Deviation
because of sand migration/movement. ID Adsorption Dynamic Dynamic
(
a b
Þ � 100
(μg/m2) Adsorption Adsorption
The dynamic vs. static adsorption data listed in Table 13 were plotted %
a
(μg/m2) (μg/m2)
in Fig. 21 and shows a reasonable correlation between the static and
dynamic data of Table 12 despite the fact that molecular weight, poly­ P1 246 236 123 48
P2 352 283 235 17
mer concentration, NaCl salinity concentrations were variable. The co­
P3 480 322 371 15
efficient of determination (R2) for the data in Fig. 21 is 0.97, whereas P4 362 192 249 28
Pearson’s correlation coefficient is 0.98. Statistically, these values fall P5 504 296 397 34
under good correlation. Furthermore, the slope was very close to unity P6 264 145 142 2
(�1.06), attesting to the strength of the correlation. P7 1312 1285 1253 2

Table 14 lists the actual static and dynamic data as well as the pre­
dicted dynamic adsorption as computed by the fitting Eq. (6) of Fig. 21.
Ad ¼ 137:54 þ 1:06As
where Ad and As is the dynamic and static adsorption in porous media,
respectively, in (μg/m2).
Fig. 22 was plotted to further highlight the scope of deviations. It
plots the actual results of dynamic adsorption against the predicted
dynamic adsorption and shows a reasonably good correlation (R2 ¼
0.97) (see Fig. 23).
Reservoir rocks are inherently heterogeneous due to the slow sedi­
mentation process taking place over a long period of time, and the
diagenetic changes occur in between. Therefore, no two rock samples
(6) are identical or representative of the entire reservoir. Thus, wide vari­
ation/deviation in physical properties is a very common and inevitable
problem. The general practice in the petroleum industry is to average
the properties to cope with this problem. When the results from the
seven rock samples used in this study are averaged, the deviation be­
comes very small (0.4%).
2.6.1. Effect of reservoir rock hydraulic flow unit (FZI) on static versus
dynamic correlation
The sedimentary rock samples encounter subtle variations in pore

Table 13
The static and dynamic adsorption data.
Polymer Molecular Weight Polymer Concentration NaCl Salinity Static Adsorptiona Dynamic Adsorptionb Static to Dynamic Sample
(million Dalton) (ppm) (ppm) (μg/m2) (μg/m2) Ratio ID

Flopaam 6 400 1000 246 236 1.04 P1

3230 S
Flopaam 6 1000 1000 352 283 1.24 P2
3230 S
Flopaam 6 2000 1000 480 322 1.49 P3
3230 S
Flopaam 6 1000 5000 362 192 1.72 P4
3230 S
Flopaam 6 1000 15,000 504 296 1.70 P5
3230 S
AN 113 VLM 1 1000 5000 264 145 1.82 P6
AN 113 VHM 12 1000 5000 1312 1285 1.02 P7
a
BET surface area was used for calculating polymer adsorption as μg/m2 for static tests.
b
MICP cut-off surface area was used for calculating polymer adsorption as μg/m2 for dynamic tests.

13
S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

samples. All the core samples falling close to the straight line in this
figure is likely to have closer physical properties as compared to the
cores falling away from the line.
The deviation between actual dynamic test results and the calculated
dynamic adsorption from static test results using the fitting equation of
Fig. 21 is plotted as a bar chart in Fig. 24.
As shown in Fig. 24, the maximum deviation for the cores in the same
flow unit was less than 35%, whereas the maximum deviation for the
entire population including all samples (BH-1 and BH-2) belonging to
different flow units is less than 50%, This strongly suggests that the static
adsorption test data can be used for the first-order approximation of
dynamic adsorption. Therefore, static tests could be utilized for pre­
liminary screening and slug optimization of polymer during polymer
flooding in porous media. In future studies, the correlation developed in
this study can be utilized for screening a suitable polymer or optimize
the technical parameters for a sandstone reservoir, performing chemical
combination flooding, such as alkaline surfactant polymer (ASP)
flooding. However, the existence of other chemicals such as surfactants
and alkaline could significantly affect the amount of adsorbed polymer
(Sheng, 2013; Zhong et al., 2019). Hence, the adsorption of polymer in
Fig. 22. A plot of actual dynamic adsorption versus the dynamic adsorption
computed by the fitting equation of Fig. 21.
presence of other chemicals should be investigated during the static and
dynamic tests. A generalized correlation that capture these parameters
can then be developed.
structure along with variation in many other flow physical properties.
Because of these variations, the cores belonging to a different Flow Zone
3. Conclusions
Indicator (FZI) will yield higher variability in flow behavior, including
adsorption.
This study focused on polymer adsorption in porous media. Factors
The Rock Quality Index (RQI) determines a core’s storage and
and adsorption conditions such as adsorption time, solid to liquid ratio,
seepage and is calculated by Eq. (7) (Soto Becerra et al., 2010):
and pre-saturation of the crushed core with brine were investigated and
sffiffiffiffiffi
optimized. The impact of polymer concentration, salinity, and polymer
k
RQI ¼ (7) molecular weight was also investigated. The current study serves to
Φe
ascertain the feasibility of using static tests in lieu of the time consuming
and costly dynamic tests for quick screening and optimization for
where k is the permeability of the core in mD, and Φe is the effective
polymer adsorption. Based on these results, a method was developed to
porosity. The normalized porosity Φz is calculated using Eq. (8) and is
approximately relate the static adsorption tests results to dynamic tests.
subsequently used along with the RQI to compute the Hydraulic Flow
The following conclusions were derived:
Unit of a core, as shown in Eq. (9) (Soto Becerra et al., 2010).
Φe � It is possible to estimate the dynamic adsorption of a polymer in
Φz ¼ ð Þ (8)
1 Φe porous media using static test adsorption results with a reasonable
correlation:
FZI ¼
RQI
(9) o With a maximum deviation of 34% for cores having similar hy­
Φz draulic flow units.
Fig. 23 is a log-log plot of normalized porosity versus RQI for all core

Fig. 23. A plot of normalized porosity vs. RQI showing three hydraulic Fig. 24. A plot of deviation from actual dynamic adsorption based on the hy­
flow units. draulic flow unit.

14
S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

o The maximum deviation increases to 48% for cores that may have
dissimilar hydraulic flow units.
� Significant observations during the course of this research are:
o One hour was found to be an adequate residence time for con­
ducting the polymer adsorption tests under both static and dy­
namic conditions.
o A solid-to-liquid ratio (S/L) of 0.5 was experimentally found to be
ideal for polymer static adsorption tests for mapping the results to
dynamic adsorption test results.
o Pre-saturating the Bentheimer crushed core samples before start­
ing static adsorption tests was found to be significant for reflecting
the dynamic test conditions.
� While investigating the effect of significant parameters on static and
dynamic adsorption of polymer, the following observations were
made;
o Polymer adsorption was highly dependent on Flopaam 3230 S
polymer concentrations in the range tested (400, 1000, and 2000
ppm). This sensitivity was observed in both static and dynamic
tests.
o Salinity had a significant impact on polymer adsorption in porous
media in the range of concentration tests (1000, 5000, 15,000).
Higher adsorption occurred at higher salinities during static
adsorption tests. However, some inconsistency in the adsorption-
salinity relationship was noticed during dynamic core flooding
experiments probably due to experimental error or clay content
difference.
o Polymers of higher molecular weights encountered higher
adsorption during both static and dynamic experiments.
The main purpose and usefulness of this study were to show the
feasibility that a technique exists where a relationship can be established
by performing a limited number of dynamic adsorption tests along with
a series of static adsorption tests. This relationship could be useful for
initial screening of a suitable polymer for the reservoir and the polymer
optimization such as salinity and concentration.
Generally, the approach of this work sets up the basis for further
research on predicting the dynamic polymer adsorption by using the
correlation that could be developed from the results of static adsorption
tests. More sophisticated correlations can also be developed that are
optimized for various adsorption conditions.
4. Recommendation(s)
This study used high permeability Bentheimer sandstones to avoid
the effect of mechanical entrapment. Fortunately, this is not a major
shortcoming since most of the hydrocarbon reservoirs that are candi­
dates for polymer flooding have high permeabilities. Before field ap­
plications, however, it is highly recommended that a correlation be
developed with more parameters and conditions using the proposed
methodology.
Funding
This work was supported by Universiti Teknologi PETRONAS,
Malaysia and Yayasan UTP-Fundamental Research Grant, Malaysia
(Cost Center 0153AA-E84).
Declaration of competing interest
The authors declare no conflict of interest.
CRediT authorship contribution statement
Sameer Al-Hajri: Conceptualization, Methodology, Software, Vali­
dation, Formal analysis, Investigation, Data curation, Writing - original
draft, Visualization, Project administration. Syed M. Mahmood:
Conceptualization, Validation, Resources, Writing - review & editing,
Supervision, Project administration, Funding acquisition. Saeed
Akbari: Methodology, Validation. Hesham Abdulelah: Software, Data
curation. Nurudeen Yekeen: Data curation, Writing - review & editing.
Nabil Saraih: Writing - review & editing.
Acknowledgments
The authors wish to thank Universiti Teknologi PETRONAS for
providing monetary support and an intellectual platform during this
research.

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://doi.org/10.1016/j.petrol.2019.106864.

Nomenclature

ASP alkaline surfactant polymer flooding

MICP Mercury Injection Capillary Porosimeter
BET Brunauer, Emmett, and Teller
R2 Coefficient of determination (unitless)
AMPS 2-acrylamide-2-methylpropane sulphonate
HPAM Partially hydrolyzed polyacrylamide
VLM Very low molecular weight
VHM Very high molecular weight
FTIR Fourier transform infrared spectroscopy
BPS Benchtop Permeability System
UV–Vis Ultraviolet–Visible Spectroscopy
S/L Solid to liquid ratio
MW Molecular weight
q Polymer adsorption (μg/g)
V Polymer solution volume (mL)
Ci Initial polymer concentration (μg/mL)
Cf Final polymer concentration (μg/mL)
Wp Weight of crushed core (g)

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S. Al-Hajri et al. Journal of Petroleum Science and Engineering 189 (2020) 106864

XRD X-ray diffraction

SEM Scanning Electron Microscopy
PV Pore volume
Ce Effluent polymer concentration (ppm)
Cinj Injected polymer concentration (ppm)
r Pearson’s correlation coefficient (unitless)
qe Adsorption amount (mg/g)
qmax Maximum adsorption capacity (mg/g)
KL Langmuir constant (L/mg)
CE Equilibrium polymer concentration (mg/L)
RL Separation factor/equilibrium parameter for Langmuir isotherm
S/D Static to dynamic adsorption ratios
Vl Volume of the injected polymer solution (mL)
Ab BET specific surface area of the crushed core (m2/g)
Am MICP cut-off specific surface area of the core (m2/g)
Wc Weight of the core (g)
Ad Dynamic adsorption in porous media (μg/m2)
As Static adsorption in porous media (μg/m2)
FZI Flow zone index (micron)
RQI Rock quality index (micron)
K Permeability of the core (mD)
Φe Effective porosity (unitless)
Φz Normalized porosity (unitless)

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