polymers

Article
Variations in Wettability and Interfacial Tension
during Alkali–Polymer Application for High and Low
TAN Oils
Vladislav Arekhov 1 , Rafael E. Hincapie 2, * , Torsten Clemens 2 and Muhammad Tahir 3
1 OMV Russia Upstream GmbH, 197046 St. Petersburg, Russia; Vladislav.Arekhov@omv.com
2 OMV Expl. & Production GmbH, New Technologies, Trabrennstraße 6-8, 1020 Vienna, Austria;
Torsten.Clemens@omv.com
3 Institute of Subsurface Energy Systems, Clausthal University of Technology, 38678 Clausthal-Zellerfeld,
Germany; muhammad.tahir@tu-clausthal.de
* Correspondence: RafaelEduardo.HincapieReina@omv.com; Tel.: +49-176-3049-0541




Received: 4 September 2020; Accepted: 28 September 2020; Published: 29 September 2020


Abstract: The injection of chemicals into sandstones can lead to alterations in wettability, where oil
characteristics such as the TAN (total acid number) may determine the wetting state of the reservoir.
By combining the spontaneous imbibition principle and the evaluation of interfacial tension index,
we propose a workflow and comprehensive assessment to evaluate the wettability alteration and
interfacial tension (IFT) when injecting chemical-enhanced oil-recovery (EOR) agents. This study
examines the effects on wettability alteration due to the application of alkaline and polymer solutions
(separately) and the combined alkali–polymer solution. The evaluation focused on comparing the
effects of chemical agent injections on wettability and IFT due to core aging (non-aged, water-wet and
aged, and neutral to oil-wet), brine composition (mono vs. divalent ions); core mineralogy (~2.5%
and ~10% clay), and crude oil type (low and high TAN). Amott experiments were performed on
cleaned water-wet core plugs as well as on samples with a restored oil-wet state. IFT experiments
were compared for a duration of 300 min. Data were gathered from 48 Amott imbibition experiments
with duplicates. The IFT and baselines were defined in each case for brine, polymer, and alkali for
each set of experiments. When focusing on the TAN and aging effects, it was observed that in all
cases, the early time production was slower and the final oil recovery was longer when compared to
the values for non-aged core plugs. These data confirm the change in rock surface wettability towards
a more oil-wet state after aging and reverse the wettability alteration due to chemical injections.
Furthermore, the application of alkali with high TAN oil resulted in a low equilibrium IFT. By contrast,
alkali alone failed to mobilize trapped low TAN oil but caused wettability alteration and a neutral–wet
state of the aged core plugs. For the brine composition, the presence of divalent ions promoted
water-wetness of the non-aged core plugs and oil-wetness of the aged core plugs. Divalent ions act as
bridges between the mineral surface and polar compound of the in situ created surfactant, thereby
accelerating wettability alteration. Finally, for mineralogy effects, the high clay content core plugs
were shown to be more oil-wet even without aging. Following aging, a strongly oil-wet behavior was
exhibited. The alkali–polymer is demonstrated to be efficient in the wettability alteration of oil-wet
core plugs towards a water-wet state.

Keywords: EOR; interfacial tension; recovery factor; polymer flooding

1. Introduction
Enhanced oil-recovery (EOR) methods affect reservoir rock and/or reservoir fluids to increase the
displacement and sweep efficiency of oil [1,2]. Different EOR methods are described in the literature,

Polymers 2020, 12, 2241; doi:10.3390/polym12102241 www.mdpi.com/journal/polymers

Polymers 2020, 12, 2241 2 of 28

focusing, for instance, on chemical methods (e.g., involving polymers and alkali materials) and more
specifically, on wettability alteration during alkali–polymer flooding.
A set of laboratory methods is available to define the wettability of core plugs, e.g., contact angle
measurements, the Amott–Harvey method, and the U.S. Bureau of Mines (USBM) method [3]. One of
the most well-known and widely used methods to deduce or assess wettability is the Amott imbibition
test, which is applied not only to sandstones but also carbonates [4,5]. Amott spontaneous imbibition
tests have been widely used in the industry for wettability evaluation [6]. The imbibition process is
governed by the capillary suction phenomenon which, in turn, is directly related to the wetting state of
the system and the interfacial tension (IFT) between fluids [7]. Hence, measuring both parameters
(wettability and IFT) can help determine the relative changes in wettability following the application
of chemicals. Selected works from the literature are summarized in Table 1.

Table 1. Overview of selected AP flooding evaluations reported in the literature.

Experimental Recovery
No. Chemicals Insightful Outcome Reference
Approach Mechanisms
Channeled Improved mobility Plugging and diverted
1 A/P/AP Wu et al. [8]
sandpack flooding ratio flow
Viscosity of displacing At same capillary
Alzahir et al.
2 A/AP/ASP Microfluidics chip fluid + pore-scale number + mobility
[9]
morphology number
Ultra-low interfacial Weak alkali in ASP
Daqing oilfield
3 ASP tension (IFT) under worked better than Sun et al. [10]
tests
oil-wet state strong alkali in ASP
Improved sweep
Book chapter with Low adsorption +
4 AP efficiency + in situ Sheng.J. [11]
field applications better injectivity
soap generation
Polymer mobility
Field projects +
control + soap
laboratory + Mixed outcomes from
5 AP improved Sheng, J. [12]
simulation field tests
displacement
Summary
efficiency
Effect of pressure,
IFT study for Fang Lower IFT + improved Maneeintr et al.
6 AP temperature, and
oilfield test mobility ratio [13]
salinity on IFT
Sandpack slap
Slug viscosity + Optimum initiation Aitkulov et al.
7 ACP flooding +
ultra-low IFT time in heavy oil [14]
simulation
Unsteady state
AP + In situ soap generation, Higher oil relative Mortazavi et al.
8 displacement
Nanoparticles pressure increment permeability values [15]
experiments
Improved sweep Low adsorption, better
Micromodels, core Schumi et al.
9 ACP/AP efficiency + in situ sweep efficiency and
flood [16]
soap generation cost efficiency
A = alkali; P = polymer; S = surfactant; AP = alkali–polymer, ACP = alkali–cosolvent–polymer.

The role of interfacial tension (IFT) in wettability evaluation has been widely reported in the
literature (e.g., Schechter et al. [17], Sharma et al. [18]). To recover residual oil, studies reported by
Skripkin et al. [19], Tong et al. [20], and Arihara et al. [21] have shown that IFT should be reduced
to ultra-low values in the order of 10−3 N/m. Under low IFT, irremovable oil with large forces
at the interface is turned into movable oil that allows easy deformation [22]. Furthermore, it was
demonstrated that transient IFT plays a larger role than equilibrium IFT in the release of residual
oil [20]. A rapid change in local IFT might induce deformation of the interfacial films and, combined
with the help of fluid-driven shear forces, the residual oil will start moving forward [23].
Many laboratory investigations have been performed to identify alkali-flooding effects on
incremental oil recovery. Various authors (e.g., Ehrlich et al., [22]; Emery et al., [24]; Skripkin et al., [19])
have reported the effectiveness of using alkali solutions for flooding purposes to increase oil
production. In addition, full field studies of alkali, alkali–polymer, and alkali–surfactant–polymer
(ASP) injections have provided promising results. For instance, as reported by Yuan et al. [25], the ASP
Polymers 2020, 12, 2241 3 of 28

flooding implementation in China’s oil fields has shown an average 15% increase in oil recovery.
Skripkin et al. [19] also reported a 38% increase in oil recovery via ASP flooding at the White Castle
field. A field pilot test was performed by Shell in 1989 in several wells. Additional oil production
during alkaline flooding is attributed to two main mechanisms: the low IFT between fluids and the
wettability alteration [5,25]. Both effects promote an increase in the capillary number, leading to
incremental oil recovery. The reduction in interfacial tension with the addition of an alkali solution
mainly occurs due to in situ soap generation mechanisms. The composition of crude oil plays an
important role during alkaline flooding. Its efficiency mainly depends on the amount of natural acids in
the oil, which can be neutralized by alkali. This finally leads to in situ soap creation and, consequently,
to a decrease in IFT [20,26,27]. A number of research projects have focused on confirming IFT reduction
during alkali application.
Several different parameters can be used to describe or determine the potential for alkali flooding,
such as the total acid number (TAN) of crude oil as measured using titration techniques. Although
recent studies could not find a correlation between incremental oil recovery due to alkali application
and TAN, Sheng [28] considers the effect of this correlation to be indisputable. Furthermore, it is
known that the brine composition and mineralogy of a sample determine the extent of wettability
alteration [3,29–31].
In this work, we investigate the wettability alteration and interfacial tension changes due to the
application of alkali–polymer. This investigation was performed by varying different parameters with
a focus on (1) the total acid number of the oil; (2) the influence of the aging of the core plugs; (3) changes
in brine composition, and (4) variations in mineralogy (clay%).
Note that, oil, brine composition and, core plugs were chosen to mimic rock-fluid properties of
the 16 TH reservoir of Matzen field (Austria), where the field-scale alkali-polymer application is under
consideration, as described by Schumi et al. [16].
The paper is organized into four main sections: First, the overall methodology and approaches
are described, follow by a detailed description of data for the fluids and core samples in the second
section. Third, the methods for IFT and Amott spontaneous imbibition are described. The results are
subsequently presented and discussed based on defined cases. Finally, we draw conclusions regarding
the observations.

2. Materials and Methods

2.1. Methodology and Approach

Here, we present a methodology to evaluate and further determine the wettability changes and
interfacial tension reduction when applying alkali–polymer flooding using high and low TAN oils.
For this process, the following workflow was adopted:

1. Phase experiments to define chemical blend concentrations. Leitenmüller et al. [32],

Schumi et al. [16], and Neubauer et al. [33] reported these experiments.
2. The selection and characterization of brines that differ in ion content to define the influence
of monovalent and divalent ions on IFT and wettability. According to Awolayo et al. [30] and
Mohnot et al. [31], brine composition can determine the extent of wettability alteration.
3. For a potential field pilot, we chose to use oil from a defined reservoir; hence, oils with high and
low TAN values were selected and further studied.
4. Interfacial tension was measured as a function of time over 300 min at a temperature of 60 ◦ C
for the defined chemicals and oils. The evaluation was based on the assessment proposed by
Sharma et al. [18].
5. Sandstone core plugs that clearly differ in clay content (2.5% and 10%) were selected, and routine
core analysis was performed. Both outcrops resemble the permeability of the envisaged reservoir.
The mineralogy of the sample may determine the extent of wettability alteration [3,29].
Polymers 2020, 12, 2241 4 of 28

6. Core plugs were saturated to determine irreducible water (Swirr) and initial oil saturation (Soi).
Permeability to water and oil were defined during the saturation process and cross-analyzed.
7. Two groups of cores were considered during the process, aged and non-aged, to assess any
wettability shift at reservoir temperature. Core aging at reservoir temperature for around 800 h
was reported to lead to a wettability shift from a purely water-wet state of the cleaned core
samples to a neutral or oil wet state [3,34,35].
8. Amott spontaneous imbibition experiments were performed for different defined cases considering
the influence of TAN, core plug aging, brine composition, and clay rock content. The results were
assessed by a detailed analysis of oil production with time dependency and final oil recovery.

2.2. Fluids and Core Sample Data

2.2.1. Brines
Two synthetic brines were prepared to investigate the influence of brine composition on the
spontaneous imbibition process and IFT. First, a simplified brine was used without divalent cations,
which is named here as test water. This simplified brine was used to mimic the salinity and buffering
capacity (e.g., pH and alkalinity) of the reservoir water. Note that, the buffering capacity (NaHCO3 )
helped having a controlled pH environment. Nevertheless, as reported by Schumi et al. [16] the pH
value was controlled between 9.6 to 9.8. Second, a brine with similar composition to that of the 16 TH
reservoir was prepared (formation brine). The composition and main parameters of the brines can be
seen in Table 2.

Table 2. Brine properties and composition used for the evaluations included in this work. Note that
test water is the same formation of brine but softened to only NaCl, including a buffer for pH control
of NaHCO3 .

Test Water Formation Brine

Parameter Units
Mean SD * Mean SD *
Density, 25 ◦C 1011.700 0.000 1012.000 0.000
Kg/m3
Density, 60 ◦ C 997.100 0.100 1012.000 0.000
Shear Viscosity, 25 ◦ C 0.964 0.032 0.954 0.030
mPa·s
Shear Viscosity, 60 ◦ C 0.571 0.023 0.592 0.054
Components Units Formation Brine Test Water
NaCl g/L 19.750 18.960
NaHCO3 g/L - 1.850
CaCl2 ·2H2 O g/L 0.400 -
MgCl2 ·6H2 O g/L 0.660 -
NH4 Cl g/L 0.170 -
SrCl2 ·6H2 O g/L 0.060 -
BaCl2 ·2H2 O g/L 0.030 -
* SD—standard deviation.

As background information, this study complements previous studies performed for similar
purposes. Previous studies performed by Leitenmüller et al. [32], Schumi et al. [16], and Neubauer et al.
showed an in-depth investigation on the possible effect of pH for the used alkali–polymer solutions
here presented.

2.2.2. Oil Samples

Two types of crude oil were used in this work: one from the 16 TH reservoir of Matzen field
(Austria, well Bo-112) and another from the St. Ulrich reservoir. On the one hand, the 16 TH oil was
moderately degraded oil with a composition characterized by 39% saturated compounds, 20% aromatic
compounds, and 39% bearing compounds such as nitrogen, sulfur, and oxygen, with the asphaltene
content being ~2% [36]. On the other hand, the St. Ulrich oil was characterized by 6% polar compounds,
Polymers 2020, 12, 2241 5 of 28

17% aromatics, 76% paraffin compounds, and asphaltene content of <1% [37]. Both crude oils were
chosen for the comparison of their behavior based on the TAN (total acid number). The 16 TH crude
oil possesses a high TAN, whereas the St. Ulrich crude oil has only a small amount of acid (Table 3).
Although it is already known that a high acid value is generally preferred for alkali flooding, the main
reason for comparing high and low TAN oil is to better capture the differences or influences—if any—of
low TAN oils.

Table 3. Properties of the oils used in this work.

16 TH St. Ulrich
Parameter Units
Mean SD * Mean SD *
Density, 25 ◦C 907.30 0.10 866.60 0.20
Kg/m3
Density, 60 ◦ C 884.30 0.20 842.60 0.60
Shear Viscosity, 60 ◦ C mPa·s 11.90 0.10 6.00 0.10
TAN (total acid number) mg KOH/g 1.61 0.18 0.17 0.08
* SD—standard deviation.

2.2.3. Chemical Solutions

Chemicals selection and the optimization and definition of the concentrations were previously
performed and reported by Schumi et al. [16]; subsequently, the phase behavior experiments were
complemented by Neubauer et al. [33]. The evaluation was performed based on phase behavior,
micro-model, and coreflooding experiments, where an optimum alkali and polymer concentration and
the type of alkali and polymer to be used were defined. Sodium carbonate Na2 CO3 at a concentration
of 7000 ppm was considered as the alkali solution, and FLOPAAM 3630S (a hydrolyzed polyacrylamide,
HPAM polymer) from SNF Floerger was dissolved in the specific brine at a concentration of 2000 ppm.
The alkali–polymer solution was defined as a combination of its constituent solutions (concentrations).
The main properties of the chemical solutions can be found in Table 4.

Table 4. Properties of the chemical solutions used in this work.

Alkali Polymer AP Solution

Parameter Units
Mean SD * Mean SD * Mean SD *
Density, 25 ◦C 1020.00 0.000 1013.00 0.00 1018.70 0.100
Kg/cm3
Density, 60 ◦ C 1005.20 0.10 998.50 0.00 1004.20 0.000
Viscosity @7,94 s−1 , 25 ◦ C 0.99 0.02 27.78 0.002 25.910 0.001
mPa·s
Viscosity @7,94 s−1 , 60 ◦ C 0.55 0.02 19.54 0.002 18.050 0.002
deviation
* SD—standard.

2.2.4. Core Samples

During the investigation, a total of 48 core samples were used (40 Nordhorn, a Bentheimer-like
outcrop, and 8 Keuper core plugs). Two different rock types were considered to study the effect
of mineralogy during the imbibition process. Nordhorn (NH) Core Figure 1a shows a similar
Bentheimer-like outcrop rock from Germany. The sample can be described as fine–medium-grained
porous sandstone that consists of quartz (96.6%), potassium feldspar (0.9%), and kaolinite (2.5%).
Due to its mineralogical composition, the sandstone can be referred to as quartz arenite weakly
cemented by quartz and clay materials. The quartz grains exhibit well-developed quartz cement
overgrowths (see Figure 1a). Nordhorn was chosen for the following reasons:
1. The permeability of the core plugs resemble the permeability ranges of the 16 TH formation
where alkali–polymer flooding is under investigation for possible implementation [16].
2. The core plugs are highly similar in their properties (their observed ranges and differences in
porosity and permeability values are narrow).
to its mineralogical composition, the sandstone can be referred to as quartz arenite weakly cemented
by quartz and clay materials. The quartz grains exhibit well-developed quartz cement overgrowths
(see Figure 1a). Nordhorn was chosen for the following reasons:
1. The permeability of the core plugs resemble the permeability ranges of the 16 TH formation
Polymers 2020, 12, 2241 6 of 28
where alkali–polymer flooding is under investigation for possible implementation [16].
2. The core plugs are highly similar in their properties (their observed ranges and differences in
3. porosity
The rockand mineralogy is simple,
permeability values thereby simplifying any additional uncertainties during the
are narrow).
experimental analysis and facilitating data
3. The rock mineralogy is simple, thereby simplifying acquisition.any additional uncertainties during the
experimental analysis and facilitating data acquisition.

a.1 Nordhorn a.2 SEM Nordhorn b.1 Keuper b.2 Thin Section Keuper

Figure 1. Images
Images ofof the
the outcrop
outcrop core used in this work: Nordhorn
Nordhorn (a.1
(a.1 and
and a.2)
a.2) and
and Keuper
Keuper (b.1 and
SEM refers
b.2). SEM refers to
to scanning
scanning electron
electron microscope.

2.2.5. Keuper
2.2.5. Keuper CoreCore
Keuper is
Keuper is an
an outcrop
outcrop from
from Germany
Germany and and was
was selected
selected due
due toto its
its high
high heterogeneity
heterogeneity and and high
high
content of
content ofclay
claymaterial.
material.These
Thesefeatures enable
features the observation
enable of theof
the observation possible influence
the possible of clay particles
influence of clay
on the wettability alteration process (see Figure 1b). Keuper is a reddish-brownish
particles on the wettability alteration process (see Figure 1b). Keuper is a reddish-brownish fine-grained
fine-
sandstone and black spots can be observed in some specific areas. Thin-section
grained sandstone and black spots can be observed in some specific areas. Thin-section analysis analysis revealed that
the sample is a well-sorted sandstone arenite composed of quartz (88%), feldspar
revealed that the sample is a well-sorted sandstone arenite composed of quartz (88%), feldspar (1%), (1%), kaolinite (10%),
and other(10%),
kaolinite materials (1%) (see
and other Figure
materials 1b).(see
(1%) TheFigure
porous space
1b). is predominantly
The porous primary interparticle
space is predominantly primary
porosity. Only a minor part of the porous space originated due to secondary porosity
interparticle porosity. Only a minor part of the porous space originated due to secondary porosity in in the feldspar.
A summary of the routine core analysis (RCA) and further saturation data are listed in
the feldspar.
TableA5.summary
Measuring theroutine
of the permeability to gas(RCA)
core analysis (N2 ) provided
and further consistent
saturationdata
datawhen comparing
are listed in Tablethe5.
porosity–permeability
Measuring correlation
the permeability (see(N
to gas Figure 2). The average permeability of the Nordhorn core plugs
2) provided consistent data when comparing the porosity–

permeability with a ±7% (see

was 2313 mD,correlation standard
Figure deviation,
2). The whereas
average for the Keuperofcores,
permeability this value was
the Nordhorn coresignificantly
plugs was
lower with a higher standard deviation of 1327 mD ± 24%. This again highlights
2313 mD, with a ±7% standard deviation, whereas for the Keuper cores, this value was significantly the highest level of
lower with a higher standard deviation of 1327 mD ± 24%. This again highlights the highest levelthe
heterogeneity in the Keuper core plugs and the similarity of Nordhorn cores. Note that although of
log scale ranging
heterogeneity between
in the Keuper 1000
coreand 10,000
plugs andsuggests large variability,
the similarity of Nordhorn the cores.
valuesNote
obtained for each core
that although the
set were
log scalewithin
ranging thebetween
range of 1000
acceptable error. suggests
and 10,000 Gas permeability was measured
large variability, in single-phase
the values obtained flow and
for each
corrected by Klinkenberg effects, while the water permeability (using test water)
core set were within the range of acceptable error. Gas permeability was measured in single-phase was defined prior to
oil saturation
Polymers
flow 2020,
and 12,in
corrected a single-phase
x FOR PEER REVIEW flow. effects, while the water permeability (using test water)7 was
by Klinkenberg of 28
defined prior to oil saturation in a single-phase flow.
Nordhorn core plugs Keuper core plugs
10000 10000
Permeability to N2, mD

Permeability to N2, mD

y = 6.7712x1.8377
R² = 0.1528

y = 1861x-0.114
R² = 0.0002

1000 1000
23.0 23.5 24.0 24.5 25.0 22.0 22.5 23.0 23.5 24.0
Porosity, % Porosity, %

(a) (b)

permeabilitycross-plot
Figure 2. Porosity-N22 permeability cross-plot for
for the
the Nordhorn
Nordhorn (a)
(a) and
and Keuper
Keuper core
core plugs (b).

A summary of the relevant core data and mean values of two-phase analysis is presented in
Table 5. The results obtained from the RCA indicate a reasonable standard deviation. A large number
of core plugs were analyzed, which boosts confidence in the reliability of the data. When referring to
saturation data, the irreducible water saturation in the Keuper cores was significantly larger than that
in the Nordhorn core plugs. This could be the result of a more complex porosity distribution within
the core plug. Despite differences in the irreducible water saturation values, the end-point relative
Polymers 2020, 12, 2241 7 of 28

A summary of the relevant core data and mean values of two-phase analysis is presented in
Table 5. The results obtained from the RCA indicate a reasonable standard deviation. A large number
of core plugs were analyzed, which boosts confidence in the reliability of the data. When referring to
saturation data, the irreducible water saturation in the Keuper cores was significantly larger than that
in the Nordhorn core plugs. This could be the result of a more complex porosity distribution within
the core plug. Despite differences in the irreducible water saturation values, the end-point relative
permeability levels were shown to be similar. Note that oil saturation was assessed at 5 different
rates to ensure uniform saturation and minimize the capillary end effect. Rates were chosen to avoid
the destruction of pore throats. An example of the oil permeability evaluations is shown in Figure 3.
Good correlation was observed between the permeability to oil and N2 .

Table 5. Overall core and saturation data for the outcrop samples used in this work.

Nordhorn Keuper
Parameter Units
Mean SD Mean SD
Length 8.010 0.110 8.120 0.090
cm
Diameter 2.960 0.010 2.980 0.010
Bulk volume 54.420 0.870 55.760 0.730
Pore volume cm3 13.070 0.260 12.750 0.220
Grain volume kg/m3 41.360 0.700 42.980 0.670
Porosity % 23.960 0.350 22.790 0.340
N2 permeability 2313.000 162.000 1327.000 186.000
mD
Water (test water) permeability 1500.000 190.000 902.000 198.000
Irreducible water saturation % 25.600 4.000 32.500 4.400
Oil permeability mD 314.000 79.000 178.000 51.000
End-point oil relative permeability - 0.210 0.060 0.200 0.070
Polymers 2020, 12, x FORoil
Initial PEER REVIEW
saturation % 74.400 4.000 67.500 4.400 8 of 28

Nordhorn core plugs Nordhorn core plugs

600 600
y = 0.1553x - 41.35 y = 0.1553x - 41.35
500 R² = 0.0916 500 R² = 0.0916
Permeability to Oil, mD
Permeability to Oil, mD

400 400

300 300

200 200

100 100

0 0
2000 2100 2200 2300 2400 2500 2000 2100 2200 2300 2400 2500
Permeability to N2, mD Permeability to N2, mD

(a) (b)
Figure 3. Cross-plot
Figure 3. Cross-plot of
of permeability
permeability to
to gas
gas and
and oil
oil without
without outliers
outliers for
for the
the Nordhorn
Nordhorn (a)
(a) and
and Keuper
Keuper
samples
samples (b).
(b).

2.3. Interfacial Tension (IFT) Evaluations

2.3. Interfacial Tension (IFT) Evaluations
For interfacial tension, a KRUSS spinning drop tensiometer was used. The heavy fluid (e.g., brine,
For interfacial tension, a KRUSS spinning drop tensiometer was used. The heavy fluid (e.g.,
brine + alkali + polymer) was placed into the vessel using a piston and a rod. A droplet of oil was used
brine, brine + alkali + polymer) was placed into the vessel using a piston and◦a rod. A droplet of oil
to fill an oil holder, which was then fixed onto a vessel. IFT was measured at 60 C and 7000 rpm based
was used to fill an oil holder, which was then fixed onto a vessel. IFT was measured at 60 °C and 7000
on the principles suggested by Sharma et al. [18]. Each solution was measured two to three times until
rpm based on the principles suggested by Sharma et al. [18]. Each solution was measured two to three
the standard deviation was fairly low to define/ensure a low uncertainty range. Notably, the obtained
times until the standard deviation was fairly low to define/ensure a low uncertainty range. Notably,
results indicate the complexity of measuring IFT and the high associated uncertainty, especially for
the obtained results indicate the complexity of measuring IFT and the high associated uncertainty,
IFT systems with a >1 mN/m range. For the 16 TH oil, Arnold [38] gathered similar observations.
especially for IFT systems with a >1 mN/m range. For the 16 TH oil, Arnold [38] gathered similar
Although the exact values of the measured IFTs might not be strictly representative, they provide
observations. Although the exact values of the measured IFTs might not be strictly representative,
enough information for fluid comparison based on IFT indicators.
they provide enough information for fluid comparison based on IFT indicators.
Overall Observations for IFT Data Interpretation
The changes in IFT were recorded and observed over 300 min, revealing both instant IFT values
(right after the start of the experiment) and the equilibrium period for IFT (expected to be established
Polymers 2020, 12, 2241 8 of 28

Overall Observations for IFT Data Interpretation

The changes in IFT were recorded and observed over 300 min, revealing both instant IFT values
(right after the start of the experiment) and the equilibrium period for IFT (expected to be established
after the reaction between fluids). The observed standard errors during the experiments were possibly
due to the following reasons:

1. Different algorithms considered for the measurement based on drop shape and fluid characteristics.
Two different algorithms were available for the measurements (Vonnegut and Young–Laplace).
For systems with an interfacial tension greater than 1 mN/m (test water and polymer solutions),
the Vonnegut algorithm could not be applied because of the oil droplet shape. Therefore,
the Young–Laplace algorithm was used. At the same time, for systems with an IFT lower than
1 mN/m (alkali and alkali–polymer solutions), the Young–Laplace method could not be used
because of the highly elongated shape of the oil droplet. Hence, the Vonnegut method was
implemented in these cases.
2. Lack of proper temperature stabilization leading to a malfunction of the device. From time to
time, the recording camera stopped responding, which led to missing data for this period until
the camera was set up again.
3. The collapse and/or conjunction of multiple oil droplets. Some errors due to collision and
separation of multiple oil droplets were observed. In the case of low IFT (alkali and alkali–polymer
solutions), the droplets were especially unstable over time. Due to separation/collision of the
droplets, the volume changed and, consequently, the IFT measurement was affected.

2.4. Contact Angle Measurements

Contact angle measurements were performed using a high pressure view cell (HPVC)
40-MD (Novis DN15, PN40; maximum operating conditions (Pmax/Tmax): 40 bar/200 ◦ C).
A piston accumulator was connected to the inlet of the cell for the injection of a heavy fluid
“alkali–polymer/alkali/brine/polymer” and pressure exertion. On the bottom of the view cell, a capillary
that dispenses oil was connected (16 TH/St.Ulrich) for the analysis of the contact angle. The cell was
exposed to a light source to enable camera recording on the other side of the cell for taking high-contrast
images. The temperature inside the view cell was controlled with a fluid-circulated heating jacket.
The fluid temperature was monitored using a thermocouple (thermocouple type K with resolution of
0.1 K and accuracy of ±1 K).
A graphical representation of the experimental setup is included in Figure 4. Contact angle
measurements were performed prior to the aging process of both core sample types, with some
additional points measured after. Oil drops of both oil samples (mentioned in Table 3) were produced
in various aqueous phases (brine, alkali, polymer, and alkali–polymer).
resolution of 0.1 K and accuracy of ±1 K).
A graphical representation of the experimental setup is included in Figure 4. Contact angle
measurements were performed prior to the aging process of both core sample types, with some
additional points measured after. Oil drops of both oil samples (mentioned in Table 3) were produced
inPolymers
various2020, 12, 2241phases (brine, alkali, polymer, and alkali–polymer).
aqueous 9 of 28

Figure 4. A high pressure and temperature KRUSS spinning drop tensiometer high pressure view cell
Figure 4. A high pressure and temperature KRUSS spinning drop tensiometer high pressure view cell
(HPVC) 40-MD for contact angle measurements.
(HPVC) 40-MD for contact angle measurements.
2.5. Spontaneous Imbibition Evaluations
2.5. Spontaneous Imbibition Evaluations
Amott cells were used for spontaneous imbibition experiments. The design of the cell is simple
andAmott cellsofwere
consists usedwhere
a vessel for spontaneous
the sampleimbibition
is placed experiments.
and covered Theby adesign
top with of the cell is simple
a graduated tube
and
forconsists of a vessel
oil production where the
recording. Asample is placed
schematic and covered
representation by aAmott
of the top withcellaisgraduated
shown intube for 5.
Figure
oilThe
production
experimentalrecording. A schematic
principle representation
is straightforward: of the
the core Amott cell
saturated withis oil
shown
until in Figure 5. water
irreducible The
experimental principle is straightforward: the core saturated with oil until irreducible
saturation is submerged into the displacing fluid. The oil production over time is recorded by measuring water
saturation
the volume is in
submerged into pipette.
the graduated the displacing fluid.temperature
To replicate The oil production over time is
reservoir conditions, recorded
Amott by
cells were
measuring the
placed 2020,
in the volume in the◦ graduated pipette. To replicate temperature reservoir conditions, Amott
Polymers 12,oven
x FORat a 60REVIEW
PEER C temperature. 10 of 28
cells were placed in the oven at a 60 °C temperature.

(a) (b)
Figure
Figure5.
5. Schematic
Schematicrepresentation
representationof
ofthe
theAmott
Amottimbibition
imbibitioncell
cell(a)
(a)and
andthe
theset
setexperiments
experimentsplaced
placedin
in
theoven
the oven(b).
(b).

To better
To better structure
structurethe
theevaluation
evaluation andand
gathering of data,
gathering we setwe
of data, different scenarios
set different which allowed
scenarios which
us to cross-analyze
allowed and understand
us to cross-analyze the effects
and understand theof each of
effects parameter: (1) total(1)
each parameter: acid number
total of the oil;
acid number of
(2) the
the oil; influence of core plug
(2) the influence aging;
of core plug(3)aging;
changes
(3)inchanges
brine composition; and (4) variation
in brine composition; and (4)invariation
mineralogy
in
mineralogy (clay%). A schematic representation of the cases is shown in Figure 6. Experiments werea
(clay%). A schematic representation of the cases is shown in Figure 6. Experiments were conducted
minimum aofminimum
conducted two timesoftotwo
assess thetouncertainty
times range related
assess the uncertainty to the
range test procedure.
related The error The
to the test procedure. bars
shown in the diagrams represent the measurement uncertainties.
error bars shown in the diagrams represent the measurement uncertainties.
High TAN
Oil Composition
Low TAN

Non-aged (Water-wet)
Ageing Stage
Aged (Neutral to Oil-wet)
 To better structure the evaluation and gathering of data, we set different scenarios which
allowed us to cross-analyze and understand the effects of each parameter: (1) total acid number of
the oil; (2) the influence of core plug aging; (3) changes in brine composition; and (4) variation in
mineralogy (clay%). A schematic representation of the cases is shown in Figure 6. Experiments were
Polymers
conducted2020,a12, 2241
minimum 10 of
of two times to assess the uncertainty range related to the test procedure. The28
error bars shown in the diagrams represent the measurement uncertainties.
High TAN
Oil Composition
Low TAN

Non-aged (Water-wet)
Ageing Stage
Aged (Neutral to Oil-wet)
Cases
Without divalents ions
Brine Composition
With divalent ions

~ 2.5 % Clays
Mineralogy Variation
~ 10 % Clays

Figure 6. Cases/scenarios and parameters used to understand the data gathered from the Amott
Figure 6. Cases/scenarios and parameters used to understand the data gathered from the Amott
spontaneous imbibition tests.
spontaneous imbibition tests.

According to the defined cases, the behavior of oil production due to imbibition was studied
According to the defined cases, the behavior of oil production due to imbibition was studied
based on two factors:
based on two factors:
1. Oil production
1. Oil production with
with time
time dependency
dependency (revealing
(revealing how
how capillary
capillary forces
forces will
will perform
perform over
over time);
time);
2. Final
2. Final oil
oil recovery,
recovery, which
which represents
represents the
the total
total amount
amount of
of oil
oil trapped
trapped in
in the
the system.
system.
Note that
Note that the
the Amott
Amott imbibition
imbibition test
test can
can potentially
potentially only
only provide
provide aa partial
partial picture
picture of
of wettability
wettability
compared to the complete overview given by Amott–Harvey wettability index or USBM, in which
spontaneous and
spontaneous andforced drainage
forced and imbibition
drainage are performed.
and imbibition Force evaluations
are performed. Force and interpretations
evaluations and
are presented inare
interpretations Schumi et al. in
presented [16].
Schumi et al. [16].

3. Results
3. Results and
and Discussion
Discussion

3.1. Interfacial Tension Observations

3.1. Interfacial Tension Observations
The reported data are in good agreement with those previously reported by Leitenmüller et al. [32],
Schumi et al. [16], and Neubauer et al. [33], considering that all these data were measured in different
periods. Each of the experiments (the tested kinds) is described in detail using images of the droplet
sizes and the measured IFT over time during the same periods (see from Figures 7–11). In Figure 7,
it can be observed that in the case of both high and low TAN oils, the effect of alkali on lowering
interfacial tension is clear. However, the decrease in IFT for high TAN oil is more significant, and the
final equilibrium value reaches a low IFT in the range of 0.05 mN/m. For all cases, the measured values
of interfacial tension between the oils and test water stay constant over time, ranging between 1 and
3.5 mN/m for high TAN oil and 2 to 4.5 mN/m for low TAN oil.
droplet sizes and the measured IFT over time during the same periods (see from Figure 7 to 11). In
Figure 7, it can be observed that in the case of both high and low TAN oils, the effect of alkali on
lowering interfacial tension is clear. However, the decrease in IFT for high TAN oil is more significant,
and the final equilibrium value reaches a low IFT in the range of 0.05 mN/m. For all cases, the
measured values of interfacial tension between the oils and test water stay constant over 11time,
Polymers 2020, 12, 2241 of 28
ranging between 1 and 3.5 mN/m for high TAN oil and 2 to 4.5 mN/m for low TAN oil.

(a) (b)
Figure 7.
Figure 7. Interfacial
Interfacial tension
tension(IFT)
(IFT)measurements
measurementsfor forhigh
hightotal
totalacid
acidnumber
number(TAN)
(TAN)
(a)(a)
andand low
low TAN
TAN oil
◦
(b) with test water at 60 C. oil (b) with test water at 60 °C.

The addition
additionofofa apolymer
polymer caused
caused a slight increase
a slight in theinmeasured
increase IFT values
the measured IFT (Figure
values 7), whereas
(Figure 7),
the highest
whereas the reduction in IFT was
highest reduction in IFTcaused
was causedby thebyalkali’s interaction
the alkali’s withwith
interaction highhighTAN TANoil oil
(Figure
(Figure8).
The application of the alkali together with the polymer resulted in slightly
8). The application of the alkali together with the polymer resulted in slightly higher interfacial higher interfacial tension
values (Figure
tension values 8). Presumably,
(Figure the higher
8). Presumably, theinterfacial tension observed
higher interfacial for the alkali–polymer
tension observed compared
for the alkali–polymer
to the puretoalkali
compared solution
the pure alkaliindicates
solutionaindicates
lower concentration of alkali (due
a lower concentration to the(due
of alkali additional volume of
to the additional
the polymer)
volume of theand a slowerand
polymer) diffusion of Na
a slower 2 CO3 molecules
diffusion of Na2COinto the oil due into
3 molecules to higher polymer
the oil due tosolution
higher
viscosity. solution
polymer Anotherviscosity.
relevant observation
Another relevant is the low instantaneous
observation is theIFTlowobserved for theIFT
instantaneous caseobserved
of the alkali
for
and
the alkali–polymer
case2020,
Polymers of the solution
12, xalkali with
and REVIEW
FOR PEER high TAN oil. As per repeated experiments, the
alkali–polymer solution with high TAN oil. As per repeated experiments, oil droplet elongated
12 of 28
drastically
the within
oil droplet the firstdrastically
elongated minutes ofwithinthe measuring period (right
the first minutes of theafter the startperiod
measuring of the (right
measurement),
after the
followed
start bymeasurement),
of the
investigation a with
shrinking period,
an almost again
followed
linear delivering
by
trend. a higher
a shrinking
Such results value
period,
can of IFT.
beagain Similar
delivering
explained by thebehavior
higher was
a interactions
value observed
of IFT.
between
during
Similar the spontaneous
the alkalibehavior
and natural imbibition
wasacids
observed evaluations,
of the during
oil. which will be discussed further.
the spontaneous imbibition evaluations, which will be
discussed further.
Figure 7 shows the behavior of the oil droplet during the IFT measurements with test water for
both oils. The droplet shape remains almost constant over the 300 min of the experimental period.
Only a slight increase in IFT was observed at approximately minute 50 for the experiment with low
TAN oil. Comparing the repeated measurements for the same solution helped in clarifying the effect
of the droplet size (oil) on the IFT value outcome. During the second measurement for high TAN oil,
the oil droplet with a smaller volume was formed. This led to lower measured values of the IFT and
resulted in a high range of uncertainty for the experiment.
For alkali solutions (Figure 8), very different behavior was observed for both high and low TAN
oil. First, the instantaneous IFT for the high TAN oil reached very low values. As soon as the
experiment started, the droplet quickly elongated, showing small interfacial tension. After a few
minutes, the droplet started to shrink again, increasing the IFT until it reached a peak. After passing
the highest value, the IFT started (a) to decrease again, reaching equilibrium (b) at a value of around 0.05
mN/m. Similar behavior of interfacial tension was observed by Sharma et al. [18]. Using low TAN oil
Figure 8.
8. IFT measurement for high TAN (a) and low TAN oil oil (b)
(b) with
with the
the alkali
alkali solution
solution at 60 ◦°C
led toFigure
a different outcome. The initial low value of IFT monotonically increased over theat300
60 C of
min
(alkali: 77g/L
(alkali: g/L Na
Na22CO
CO33).).

Figure
After a7very
shows the
fast behavior
reaction onof thesurface
the oil droplet
of theduring the IFTthe
oil droplet, measurements with test
interfacial tension water the
between for
both
fluidsoils. The droplet
dropped shape(Figure
very quickly remains almost
8a). Thereconstant
were many overanionic
the 300 min of theonexperimental
surfactants the interface,period.
which
Only
sloweda slight
alkali increase in IFTThere
consumption. was observed
were not at approximately
enough minute
natural acids 50 interface
on the for the experiment
to continuewith low
creation
TAN
of the surfactants. Hence, the IFT increased shortly after the reaction. The observed data suggestofa
oil. Comparing the repeated measurements for the same solution helped in clarifying the effect
the droplet size (oil) on
diffusion-dominated the IFT
system in value
whichoutcome. During theofsecond
the neutralization measurement
organic acids occursforfaster
high than
TAN the
oil,
the oil droplet
molecular with aofsmaller
diffusion volume
alkali into wasof
the bulk formed. This led
the solution. to lowerdue
However, measured valuesdiffusion,
to molecular of the IFTwhen
and
resulted
the alkaliincontacts
a high range
“fresh”of oil
uncertainty
from the for thenew
bulk, experiment.
anionic surfactants are created. By rearranging the
molecules, the concentration of surfactant equalizes, leading to a decrease in IFT until reaching the
equilibrium value where all the natural acids are consumed. For the case of the St. Ulrich oil (low
TAN) shown in Figure 8b, the amount of natural acids was not sufficient for efficient IFT decrease.
The initially created surfactants caused a decrease in IFT to its minimum value. However, due to the
lack of natural acids and the small concentration of the surfactants after rearrangement, the interfacial
tension started to increase again over time.
Polymers 2020, 12, 2241 12 of 28

For alkali solutions (Figure 8), very different behavior was observed for both high and low
TAN oil. First, the instantaneous IFT for the high TAN oil reached very low values. As soon as the
experiment started, the droplet quickly elongated, showing small interfacial tension. After a few
minutes, the droplet started to shrink again, increasing the IFT until it reached a peak. After passing the
highest value, the IFT started to decrease again, reaching equilibrium at a value of around 0.05 mN/m.
(a) (b)
Similar behavior of interfacial tension was observed by Sharma et al. [18]. Using low TAN oil led
to a Figure
different outcome.
8. IFT measurement The initial
for high lowTANvalue of IFT
(a) and low monotonically
TAN oil (b) withincreased over theat300
the alkali solution min of
60 °C
investigation with
(alkali: 7g/L Na2an
COalmost
3). linear trend. Such results can be explained by the interactions between
the alkali and natural acids of the oil.
After
After aa very
very fast
fast reaction
reaction on on the
the surface
surface of of the
the oil droplet, the
oil droplet, interfacial tension
the interfacial tension between
between the the
fluids dropped very quickly (Figure 8a). There were many anionic surfactants
fluids dropped very quickly (Figure 8a). There were many anionic surfactants on the interface, which on the interface, which
slowed
slowed alkali
alkali consumption.
consumption. There There were
were not not enough
enough natural
natural acids
acids onon the
the interface
interface to
to continue
continue creation
creation
of
of the
the surfactants.
surfactants. Hence,
Hence,the theIFTIFTincreased
increasedshortly
shortlyafter
afterthe
thereaction.
reaction.The Theobserved
observed data
data suggest
suggest a
diffusion-dominated system in which the neutralization of organic
a diffusion-dominated system in which the neutralization of organic acids occurs faster than the acids occurs faster than the
molecular
molecular diffusion
diffusionofofalkali
alkaliinto thethe
into bulkbulkof the solution.
of the However,
solution. However,due toduemolecular diffusion,
to molecular when
diffusion,
the alkali contacts “fresh” oil from the bulk, new anionic surfactants are created.
when the alkali contacts “fresh” oil from the bulk, new anionic surfactants are created. By rearranging By rearranging the
molecules, the concentration of surfactant equalizes, leading to a decrease
the molecules, the concentration of surfactant equalizes, leading to a decrease in IFT until reaching in IFT until reaching the
equilibrium
the equilibriumvalue where
value whereall theall natural
the naturalacidsacids
are consumed.
are consumed. For theForcase of theofSt.
the case theUlrich oil (low
St. Ulrich oil
TAN) shown in Figure 8b, the amount of natural acids was not sufficient for
(low TAN) shown in Figure 8b, the amount of natural acids was not sufficient for efficient IFT decrease. efficient IFT decrease.
The
The initially
initially created
created surfactants
surfactants caused caused aa decrease
decrease in in IFT
IFT to
to its
its minimum
minimum value. value. However,
However, due due toto the
the
lack of natural acids and the small concentration of the surfactants after rearrangement,
lack of natural acids and the small concentration of the surfactants after rearrangement, the interfacial the interfacial
tension
tension started
started to
to increase
increase again
again overover time.
time.
To facilitate the
To facilitate ease of
the ease of understanding
understanding Figure Figure 99 shows
shows aa schematic
schematic that that attempts
attempts to to explain
explain the
the
interfacial tension changes that occurred for high
interfacial tension changes that occurred for high and low TAN oil. and low TAN oil.

Figure 9. Schematics explaining the process of IFT change for high and low TAN oils.
Figure 9. Schematics explaining the process of IFT change for high and low TAN oils.
During the interfacial tension measurements with polymer solutions, no significant changes in oil
During
droplet shapethewere
interfacial tension
observed, measurements
as can be seen fromwith polymer
Figure solutions,tono
10. Compared thesignificant
test water,changes in
a slightly
oil droplet shape were observed, as can be seen from Figure 10. Compared to the test water,
higher interfacial tension was measured. The uncertainty range of the evaluated data could be related a slightly
higher interfacial
to the chosen tension wasalgorithm
measurement measured.orThe
the uncertainty range of the
devised stabilization. evaluated data
Nevertheless, could
taking thebeaverage
related
to the of
value chosen measurement
IFT can algorithm
offer a reliable or the devised
approximation stabilization.system.
for an oil–polymer Nevertheless, taking the average
value of IFT can offer a reliable approximation for an oil–polymer system.
Polymers 2020,12,
Polymers2020, 12,2241
x FOR PEER REVIEW 13
13 of
of 28
28
Polymers 2020, 12, x FOR PEER REVIEW 13 of 28

(a) (b)
(a) (b)
Figure 10. IFT measurement for high TAN (a) and low TAN oil (b) with the polymer (P) at 60 ◦°C
Figure 10.
Figure 10. IFT measurement
measurement for
for high
high TAN (a) and low TAN oil (b)
(b) with
with the
the polymer
polymer (P)
(P) at
at 60
60 °C
C
(polymer: 2000 ppm FLOPAAM 3630S).
(polymer: 2000 ppm FLOPAAM
(polymer: FLOPAAM 3630S).
3630S).
Alkali–polymer solutions delivered similar results to those of alkali-only solutions (see Figure
Alkali–polymer
Alkali–polymersolutions
solutionsdelivered
deliveredsimilar
similarresults to to
results those of of
those alkali-only solutions
alkali-only (see(see
solutions Figure 11).
Figure
11). The instantaneous IFT for high TAN oil was very low, which can be observed by the elongated
The
11). instantaneous
The instantaneousIFT forIFThigh
forTAN
highoil wasoil
TAN very low,
was which
very low,can be observed
which by the elongated
can be observed structure
by the elongated
structure of the oil droplet (Figure 11a). Subsequently, the droplet started to shrink, indicating a
of the oil droplet
structure (Figure
of the oil 11a).(Figure
droplet Subsequently, the droplet started
11a). Subsequently, to shrink,
the droplet indicating
started a higher
to shrink, value ofa
indicating
higher value of interfacial tension. Towards the end, the tension between the fluids decreased again
interfacial
higher value of interfacial tension. Towards the end, the tension between the fluids decreased of
tension. Towards the end, the tension between the fluids decreased again because the
again
because of the rearrangement of surfactant molecules in the droplet. The addition of polymer to the
rearrangement of surfactant molecules
because of the rearrangement in the
of surfactant droplet. The
molecules in theaddition
droplet.ofThepolymer
additionto the alkali solution
of polymer to the
alkali solution led to a diminishing effect of IFT reduction and an increase in the observed IFT peak
led to asolution
alkali diminishing
led toeffect of IFT reduction
a diminishing and
effect of anreduction
IFT increase inand thean
observed
increaseIFTin peak value. This
the observed IFTmight
peak
value. This might have occurred for two reasons: 1) a lower concentration of alkali due to the
have occurred for two reasons: (1) a lower concentration of alkali due to
value. This might have occurred for two reasons: 1) a lower concentration of alkali due to the the additional volume of
additional volume of the polymer and 2) the delayed diffusion of Na2CO3 molecules into the oil due
the polymer
additional and (2)ofthe
volume thedelayed
polymerdiffusion
and 2) theofdelayed
Na2 CO3diffusion
molecules of into
Na2CO the3 molecules
oil due to larger
into thepolymer
oil due
to larger polymer molecules. Low TAN oil resulted in very similar behavior to the alkali–oil system.
molecules. Low TAN oil resulted in very similar behavior to the alkali–oil system.
to larger polymer molecules. Low TAN oil resulted in very similar behavior to the alkali–oil system. The initial low
The initial low value of IFT gradually increased over time due to a lack of anionic surfactants on the
value of IFTlow
The initial gradually
value ofincreased over time
IFT gradually due to over
increased a lacktime
of anionic
due tosurfactants on the surfactants
a lack of anionic interface between
on the
interface between the oil and the second fluid.
the oil and
interface the second
between fluid.
the oil and the second fluid.

(a) (b)
(a) (b)
Figure 11.
Figure 11. IFT
IFT measurement
measurement for
for high
high TAN
TAN (a)
(a) and
and low
low TAN
TANoil oil(b)
(b)with
withthe
thealkali–polymer
alkali–polymer at 60◦°C
at 60 C
Figure 11. IFT measurement for high TAN (a) and low TAN oil (b) with the alkali–polymer at 60 °C
(alkali:
(alkali: 77g/L
g/L Na22CO
CO33; ;polymer:
polymer:2000
2000ppm
ppmFLOPAAM
FLOPAAM3630S).3630S).
(alkali: 7g/L Na2CO3; polymer: 2000 ppm FLOPAAM 3630S).
3.2.
3.2. Contact
Contact Angle
Angle Results
Results
3.2. Contact Angle Results
The
Thecontact
contactangle
angleresults illustrated
results a water-wet
illustrated statestate
a water-wet of both
of core
bothplugs
core prior
plugstoprior
the aging
to theprocess,
aging
as The contact
shown in Table angle
6. The results
contact illustrated
angle a water-wet
values were state over
measured of both core
time plugsofprior
intervals 20 to the
min, as aging
shown
process, as shown in Table 6. The contact angle values were measured over time intervals of 20 min,
process,
in Figure as
12.shown
As in Tablebased
predicted 6. Theoncontact
our angle values
previous work were measured
[34,39–41], there over
was time
no intervals
change in of 20
the min,
contact
as shown in Figure 12. As predicted based on our previous work [34,39–41], there was no change in
as shown in Figure 12. As predicted based on our previous work [34,39–41], there was no change in
the contact angle due to the strong hydrophilic characteristics of the porous media. However, the
the contact angle due to the strong hydrophilic characteristics of the porous media. However, the
Polymers 2020,
Polymers 2020, 12,
12, 2241
x FOR PEER REVIEW 14 of
14 of 28
28
Polymers 2020, 12, x FOR PEER REVIEW 14 of 28
aging process altered the rock surface, which became hydrophobic, resulting in oil polar compounds
angle
agingdue
attaching tothe
to
process the strong
rock
altered hydrophilic
surface.
the rockThe characteristics
wettability
surface, of the
which alteration
became toporous
oil-wetmedia.
hydrophobic, (shown However,
in oil the
in Figure
resulting 13),aging
polar based process
on our
compounds
altered
previous the
attaching torock
work surface,
the[35,42], which
confirmed
rock surface. became
The hydrophobic,
the change
wettability in contact
alteration resulting
angle
to toin41.
oil-wet oilThe
polar
(shown incompounds
wettability attaching
alteration
Figure 13), based to
of our
on the
the
Berearock
andsurface.
previous Bentheimer
work The wettability
[35,42], sandstone
confirmedcorealteration
theplugs
change toinoil-wet
through (shown
a two-
contact in 41.
Figure
or three-week
angle to The 13),
agingbased
process
wettability on our previous
has also
alteration been
of the
work
Berea[35,42],
established byconfirmed the change
many researchers
and Bentheimer sandstone in plugs
contact
[43–47].
core aangle
Onthrough to
similar 41. The
note,
a two- orwewettability
suspect that
three-week alteration
theprocess
aging aging of process
the
hasBerea and
alsoofbeen
the
Bentheimer
core plugs in
established sandstone
bythis study
many core plugs through
changed
researchers the aOn
two-
wettability
[43–47]. or
to three-week
mix-wet
a similar note,orweaging
oil-wet,process
suspect thathas
thealso
especially for been
aging established
theprocess
Keuper ofcore
the
by
plugmany
core withresearchers
plugs higher
in thisclay [43–47].
studycontent.
changedOn the
a similar note, to
wettability wemix-wet
suspector that the aging
oil-wet, process
especially forofthe
theKeuper
core plugs
core
in thiswith
plug study changed
higher clay the wettability to mix-wet or oil-wet, especially for the Keuper core plug with
content.
Table 6. Contact
higher clay content. angle results before aging the core plugs under various aqueous/oil conditions.
Table 6. Contact angle results before aging the core plugs under various aqueous/oil conditions.
Contact Angle—16 TH Contact Angle—St. Ulrich
Contact
Table 6.Time
Core angle results before aging the core plugs under various aqueous/oil conditions.
(Min)
TW * Contact
AlkaliAngle—16 TH
Alkali–Polymer TW Contact
* AlkaliAngle—St. Ulrich
Alkali–Polymer
Core Time (Min)
0 TW
60.0* Contact
Alkali Alkali–Polymer
57.8 Angle—16 TH
43.7 TW * Alkali
62.7Contact Alkali–Polymer
Angle—St.
38.1 Ulrich
61.8
Nordhorn
Core Time (Min)
300
0 58.7
60.0
TW * 57.2
57.8
Alkali 57.8
43.7
Alkali–Polymer 60.7
62.7*
TW 42.7
38.1
Alkali 59.8
61.8
Alkali–Polymer
Nordhorn
00
300 49.1
58.7
60.0 53.3
57.2
57.8 60.7
57.8
43.7 45.2
60.7
62.7 51.9
42.7
38.1 34.6
59.8
61.8
Keuper
Nordhorn
300
0300 50.4
49.1
58.7 54.2
53.3
57.2 56.1
60.7
57.8 50.0
45.2
60.7 47.8
51.9
42.7 55.9
34.6
59.8
Keuper 0 49.1 53.3 60.7 45.2 51.9 34.6
Keuper 300 50.4 54.2 TW * test water.
56.1 50.0 47.8 55.9
300 50.4 54.2 56.1 50.0 47.8 55.9
TW * test water.
TW * test water.

Figure 12. Contact angle measurements performed for the Keuper core plug in contact with the St.
Figure 12. Contact angle measurements performed for the Keuper core plug in contact with the
Ulrich
Figureoil.
12.The alkaliangle
Contact solution is the aqueous
measurements phase. for the Keuper core plug in contact with the St.
performed
St. Ulrich oil. The alkali solution is the aqueous phase.
Ulrich oil. The alkali solution is the aqueous phase.

Figure 13.
Figure Contact angle
13. Contact angle confirming
confirming the
the wettability
wettability alteration
alteration to
to oil-wet
oil-wet after
after the
the aging
aging process
process [34].
[34].
Figure 13. Contact
3.3. Spontaneous angle
Imbibition confirming the wettability alteration to oil-wet after the aging process [34].
Observations
3.3. Spontaneous Imbibition Observations
3.3. Spontaneous
3.3.1. Non-Aged Imbibition
NordhornObservations
Core Plugs—Oil Type Comparison
3.3.1. Non-Aged Nordhorn Core Plugs—Oil Type Comparison
3.3.1.Figure 13 illustrates
Non-Aged Nordhorn the Core
oil production
Plugs—Oil behavior over the first 24 h. According to the observations
Type Comparison
Figure 13 illustrates the oil production behavior
in this work, this time period is the most representative. over the 24
After first 24 imbibition,
h of h. According to the
only smallobservations
changes in
in this work,
Figure 13this time period
illustrates the is
oil the most
production representative.
behavior over After
the 24
first h
24ofh.
oil production were observed until ultimate recovery was reached. The ultimate recoveryimbibition,
According only
to the small changes
observations
values for
in
in oil
thisproduction
work, this were
time observed
period is until
the ultimate
most recovery
representative. was
After reached.
24 h of The ultimate
imbibition,
each case are presented on the bottom-right part of each graph. Note that, ultimate recovery (UR) wasonlyrecovery
small values
changes
for each
in oil
estimated case
as aare
production presented
wereof
volume onwhich
observed
oil, theuntil
bottom-right
ultimate
was part of each
recovery
recovered duringwasgraph.
the Note
reached.
Amott that,
The ultimate
ultimate
imbibition recoveryby
test,recovery
divided (UR)
values
the
was estimated
for each
initial case are
volume as presented
of a volume
oil (initial of
oiloil,
on the which wasItrecovered
bottom-right
saturation). part
can be of during
each
seen the
graph.
from Amott
Note
Figure imbibition
14that,
that ultimate test,
regardless divided
recovery
of by
(UR)
the TAN
the
wasinitial volume
estimated as aof oil (initial
volume of oil,oilwhich
saturation). It can beduring
was recovered seen from Figureimbibition
the Amott 14 that regardless of the
test, divided by
the initial volume of oil (initial oil saturation). It can be seen from Figure 14 that regardless of the
Polymers 2020, 12, 2241 15 of 28

Polymers 2020, 12, x FOR PEER REVIEW 15 of 28

of the oil, the imbibition rate was larger using the test water. The observed imbibition rate for the
TAN of the oil, the imbibition rate was larger using the test water. The observed imbibition rate for
polymer was slowed due to the large molecules in the solution. Molecules moved slowly into the pore
the polymer was slowed due to the large molecules in the solution. Molecules moved slowly into the
system, which led to a lower imbibition rate. For the alkali and alkali–polymer solutions, the slower
pore system, which led to a lower imbibition rate. For the alkali and alkali–polymer solutions, the
imbibition can be explained by the reduction in IFT. Due to small interfacial tension, the capillary
slower imbibition can be explained by the reduction in IFT. Due to small interfacial tension, the
forces were reduced, which led to a slower process of imbibition.
capillary forces were reduced, which led to a slower process of imbibition.
High TAN Oil Non-Aged Nordhorn Cores 100 Low TAN Oil Non-Aged Nordhorn Cores
100
90 Test Water 90 Test Water
80 80

Recovery, %
Recovery, %

70 62±6 70 56±8 56±7 57±7 57±7 57±6 57±6 60±3

53±1 54±0 55±1 56±2 57±2 51±9 55±8
60 49±4 51±3 53±1 60
44±13
50 43±2 50
40 40 27±12
24±4 30
30
20 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(18) (16)
Sqrt (Hours) Sqrt (Hours)

(a) (b)
100 100
Polymer Polymer
90 90
80 63±9 80
54±8 56±8 58±8 59±9 60±9
Recovery, %

Recovery, %
70 70 58±1
50±8 52±8 50±3 51±3 52±2 53±1 53±1
60 60 47±3 49±4
50 42±5 50 42±2
40 40 31±1
27±2
30 30
11±4 14±3
20 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (21) Sqrt (Hours) (18)

(c) (d)
100 94±2 100
Alkali Alkali
90 90
80 68±6 69±7 80
Recovery, %

Recovery, %

70 63±6 70
57±6 55±9 57±8 58±7 58±7
60 51±6 60 49±11 52±10
50 39±6
45±6
50 43±13 47±13
31±5 34±12
40 40
30 21±5 30 23±9
20 10±2 20 10±2
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (20) Sqrt (Hours) (16)

(e) (f)
100 88±8 100
Alkali-Polymer Alkali-Polymer
90 90
80 67±4 69±3 80
62±9
Recovery, %

Recovery, %

70 62±2 70 58±11 59±1260±12

55±3 54±8 56±10
60 48±3 60 48±6 51±7
50 41±4 50 41±1
40 33±5 40 29±2
24±4
30 30
15±4 13±1
20 7±2 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (24) Sqrt (Hours) (19)

(g) (h)
Figure14.
Figure 14.Percent
Percent of
of production
production versus
versus thethe square
square root
rootof
ofthe
thetime
timeplot
plotforforthe
theNordhorn
Nordhornnon-aged
non-aged
coreplugs
core plugsusing
usinghigh
highTAN
TANoil oiland
and low
low TAN
TAN oil
oil at 60 ◦°C
at 60 (alkali: 7 g/L Na22CO
C (alkali: CO3;3 ;polymer:
polymer:2000
2000ppm
ppm
FLOPAAM3630S).
FLOPAAM 3630S).High
HighTANTANoiloildata
data(a,c,e,g)
(a,c,e and
are g) are presented
presented on theonleftthe leftwhereas
side side whereas
low TANlowoil
TAN
data
oil data (b,d,f and h) on the right side. Black-colored data refer to Test water, Blue-colored
(b,d,f,h) on the right side. Black-colored data refer to Test water, Blue-colored data refer to polymer, data refer
to polymer, purple-colored
purple-colored data and
data refer to alkali, refergreen-colored
to alkali, anddata green-colored data refer toUltimate
refer to alkali-polymer. alkali-polymer.
recovery
Ultimate
(UR) refersrecovery (UR) oil
to recovered refers to recovered
divided bv Soi. oil divided bv Soi.

For
Forthe
thelow
lowTANTANoil,
oil,all
allchemical
chemicalsolutions
solutionsprovided
providedsimilar
similartotal
totalrecoveries
recoverieswith
withaasmall
smallrange
rangeof
of uncertainty.
uncertainty. However,
However, forfor
thethe high
high TANTANoil,oil,the
theuse
useof
ofalkali
alkali and
and alkali–polymer
alkali–polymersolutions
solutionsledledtotoaa
largeramount
larger amountofofproduced
producedoil. oil.Similarly,
Similarly, thethe ultimate
ultimate recovery
recovery of of
thethe
testtest water
water andand polymer
polymer waswasvery
very similar.
similar. Theamount
The larger larger amount of total production
of total production in the case inofthe
thecase
alkaliofand
the alkali–polymer
alkali and alkali–polymer
solutions can
besolutions
explained canbybethe
explained by the
lower values oflower values IFT.
equilibrium of equilibrium
Reducing the IFT.IFTReducing the IFT
to low values ledtotolow values
destruction
ofled
thetorigid
destruction
oil films,ofasthe
wellrigid
as theoil stringing
films, as and
welldrawing
as the stringing and drawing
of oil. Under of oil. Under
this mechanism, the oilthis
was
mechanism, the oil was produced slower, but a larger
produced slower, but a larger total amount was released from the core. total amount was released from the core.
Polymers 2020, 12, 2241 16 of 28
Polymers 2020, 12, x FOR PEER REVIEW 16 of 28

As
As shown
shown above,
above, low
low TAN
TAN oil
oil fails
fails to
to reduce
reduce IFT
IFT until
until ultra-low
ultra-low values,
values, which
which is
is the
the primary
primary
reason
reason for
for smaller
smaller ultimate
ultimate recovery
recovery with
with the
the application
application of
of alkali
alkali and
and alkali-polymer solutions.
alkali-polymer solutions.

3.3.2.
3.3.2. Nordhorn
Nordhorn Core
Core Plugs—Influence
Plugs—Influence of
of Aging
Aging
The
The results
results ofof the
the experiments
experimentswithwithrestored
restored wettability
wettabilitystate
statecore
coreplugs
plugsareareshown
shownin inFigure
Figure15,
15,
with
with aa comparison
comparison between
between the the production
production of the
the aged
aged and
and non-aged
non-aged Nordhorn
Nordhorn corecore plugs.
plugs. TheTheeffect
effect
of
of aging
aging was
was clearly
clearly deduced
deduced from
from the
the observed
observed oil
oil production
production behavior.
behavior. In
In all
all cases,
cases, the
the early
early time
time
production
production waswas slower
slower compared
compared to to the
the non-aged
non-aged core plugs. However,
However, using
using thethe test
test water
water and
and
polymer as displacing fluids produced a slower production rate only within the
polymer as displacing fluids produced a slower production rate only within the first hour of imbibition first hour of
imbibition
evaluation.evaluation.
All other casesAll other casessignificantly
exhibited exhibited significantly
slower initialslower initialrates.
production production
These datarates.confirm
These
data confirmin
the changes the changes
the in the wettability
rock surface rock surface wettability
towards towards
a more oil-weta state
moreafter
oil-wet state after aging.
aging.

High TAN Oil Non-Aged Nordhorn Cores High TAN Oil Aged Nordhorn Cores
100 100
Test Water 90 Test Water
90
80 80 68±3
62±1 63±1 63±5 64±1 64±1 65±1

Recovery, %
Recovery, %

70 62±6 70 58±4 62±2

53±1 54±0 55±1 56±2 57±2
60 49±4 51±3 53±1 60 46±12
50 43±2 50
40 40
24±4 30 22±10
30
20 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(18) (16)
Sqrt (Hours) Sqrt (Hours)

(a) (b)
100 100
Polymer Polymer
90 90
80 80 65±3 66±2 69±1
54±8 56±8 58±8 59±9 60±9
63±9 57±9 60±8 63±6
Recovery, %

Recovery, %

70 70 54±11
50±8 52±8 49±17
60 60
50 42±5 50 39±20
40 27±2 40
25±15
30 30
20 11±4 20 11±7
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (21) Sqrt (Hours) (16)

(c) (d)
100 94±2 100
Alkali Alkali 99±1
90 90
74±2
80 68±6 69±7 80 69±4
64±5
Recovery, %

Recovery, %

70 63±6 70
57±6 54±4
60 51±6 60
45±6 44±4
50 39±6 50
31±5 34±4
40 40
21±5 25±3
30 30 17±1
20 10±2 20 10±1
4±1
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (20) Sqrt (Hours) (19)

(e) (f)
100 88±8 100 93
Alkali-Polymer Alkali-Polymer
90 90
80 67±4 69±3 80 69
64
Recovery, %

Recovery, %

70 62±2 70
55±3 55
60 48±3 60 46
50 41±4 50 38
40 33±5 40 29
24±4 22
30 30
15±4 15
20 7±2 20 9
4
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (24) Sqrt (Hours) (25)

(g) (h)
Figure
Figure 15.15. Percent
Percent of production
of production versus
versus the square
the square root ofroot of the
the time time
plot for plot for the Nordhorn
the Nordhorn non-agednon-aged
and aged core
andsaturated
aged corewith
plugs saturated ◦ C (alkali: 7 g/L Na CO ; polymer: 2000 ppm
plugs high TAN oilwith
at 60high TAN oil
°C (alkali: at 60
7 g/L Na 2CO3; polymer: 2000 2 ppm3 FLOPAAM 3630S). Non-
FLOPAAM
aged core data3630S). Non-aged
(a,c,e and core dataon(a,c,e,g)
g) are presented the left are
sidepresented on the
whereas aged leftdata
core side(b,d,f
whereas aged
and h) on core dataside.
the right
(b,d,f,h) ondata
Black-colored the right side.
refer to TestBlack-colored data refer
water, Blue-colored data to Test
refer to water, Blue-colored
polymer, datadata
purple-colored refer to polymer,
refer to alkali, and
purple-colored
green-colored datadata
referrefer to alkali, andUltimate
to alkali-polymer. green-colored data
recovery refer
(UR) to alkali-polymer.
refers Ultimatebvrecovery
to recovered oil divided Soi.
(UR) refers to recovered oil divided bv Soi.
The ultimate oil production outcome can be explained by the oil droplet snap-off phenomenon.
Under this phenomenon, when the rock is water-wet, the invading fluid spreads around the surface,
Polymers 2020, 12, 2241 17 of 28

The ultimate oil production outcome can be explained by the oil droplet snap-off phenomenon.
Under this phenomenon, when the rock is water-wet, the invading fluid spreads around the surface,
leading to a large volume of oil being left behind in the middle of the large pores. In the17case
Polymers 2020, 12, x FOR PEER REVIEW of 28
of a
neutral (oil)-wet state, the oil initially covers the mineral surfaces. By submerging more oil-wet core
plugs into different
leading to a largesolutions,
volume ofthe oilinvading
being leftfluid enters
behind themiddle
in the middleofofthe thelarge
porepores.
throat,Inreleasing
the case of a larger
a
neutral
amount (oil)-wet
of oil than in state,
thethe oilofinitially
case covers the
the water-wet mineral
core. Thissurfaces.
explainsBy the submerging
incremental moreoil oil-wet
recovery core
for all
plugs
cases withinto
the different
aged core solutions,
plugs shownthe invading
above. fluid enters the middle of the pore throat, releasing a
larger
The oil recovery of 80% and up tothe
amount of oil than in the case of water-wet
almost 100%core. Thiscase
in the explains the incremental
of alkali implementation oil recovery
suggests
for all cases with the aged core plugs shown above.
reverse wettability alteration from a neutral(oil)-wet state towards a water-wet state. The possible
The oil recovery of 80% and up to almost 100% in the case of alkali implementation suggests
mechanism is the following. Initially, the neutral(oil)-wet core plug is submerged into the alkali
reverse wettability alteration from a neutral(oil)-wet state towards a water-wet state. The possible
solution. Fluid enters the large pores and displaces oil from the core plug. In situ-created surfactants
mechanism is the following. Initially, the neutral(oil)-wet core plug is submerged into the alkali
cause wettability alteration and, consequently, changes in capillary forces. The invading fluid is then
solution. Fluid enters the large pores and displaces oil from the core plug. In situ-created surfactants
sucked
causeinto the corealteration
wettability plug, andand, oil consequently,
is released. Water changesthen starts to forces.
in capillary spreadThe around the inner
invading fluid issurface
then of
the sucked
pore throats.
into theThiscore leads to oil
plug, and oildetachment
is released. Waterfromthenthe starts
mineral surfaces.
to spread Hence,
around the oil
the inner is released,
surface of
despite being trapped in small pores and “sticking” to mineral surfaces.
the pore throats. This leads to oil detachment from the mineral surfaces. Hence, the oil is released,
Similar
despite effects
being wereinobserved
trapped small pores during the lowtoTAN
and “sticking” oil surfaces.
mineral displacement process (see Figure 16).
Similar
The obtained effectsindicate
results were observed
similarduring
behaviorthe low
andTAN oil displacement
confirm the previous process (see Figure
statements. 16).restored
All the The
obtainedcore
wettability results
plugsindicate similar
exhibited behavior
slower and confirmrate
oil production the during
previous thestatements.
first period Allofthe
therestored
imbibition
wettability
process, whichcore plugsoverrode
further exhibitednon-aged
slower oil coreproduction rate during
production the first period
and delivered greaterof ultimate
the imbibition
recovery.
As proven by the IFT measurements, even a small amount of crude oil acid was enoughrecovery.
process, which further overrode non-aged core production and delivered greater ultimate to decrease
As proven by the IFT measurements, even a small amount of crude oil acid was enough to decrease
the interfacial tension between the oil and displacing fluid. The decrease in IFT was not large enough
the interfacial tension between the oil and displacing fluid. The decrease in IFT was not large enough
to cause stringing of the oil in case of a water-wet state. However, the in situ creation of surfactants
to cause stringing of the oil in case of a water-wet state. However, the in situ creation of surfactants
resulted in wettability alteration of the initially aged core plugs. As a result, oil was released not only
resulted in wettability alteration of the initially aged core plugs. As a result, oil was released not only
from the the
from middle
middleof of
thethelarger
largerpores
pores(as (asin
in the
the case of the
case of thetest-water
test-waterand and polymer
polymer imbibition)
imbibition) but also
but also
from the mineral surfaces. This assumption was confirmed by the incremental
from the mineral surfaces. This assumption was confirmed by the incremental oil production while oil production while
using alkali and alkali–polymer displacing fluids for the
using alkali and alkali–polymer displacing fluids for the low TAN oil case.low TAN oil case.

Low TAN Oil Non-Aged Nordhorn Cores 100 Low TAN Oil Aged Nordhorn Cores
100
90 Test Water 90 Test Water
80 80
65±1
Recovery, %

61±2 62±1 63±1 63±1

Recovery, %

70 60±3 70 57±4 59±2 60±2

56±8 56±7 57±7 57±7 57±6 57±6
60 51±9 55±8 60 49±9
50 44±13 50
40 40 30±22
27±12
30 30 16±15
20 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(16) (13)
Sqrt (Hours) Sqrt (Hours)

(a) (b)
100 100
Polymer Polymer
90 90
67±3
80 80 60±9 62±7 64±6 65±4 66±3
Recovery, %

Recovery, %

70 50±3 51±3 52±2 53±1 53±1

58±1 70 55±12 59±10
60 47±3 49±4 60 44±14
50 42±2 50
40 31±1 40 29±11
30 30
14±3 14±4
20 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (18) Sqrt (Hours) (18)

(c) (d)
100 100
Alkali Alkali 81±6
90 90 78±7 79±6
80 80 72±4 76±6
66±1 69±2
Recovery, %

Recovery, %

70 70
55±9 57±8 58±7 58±7 56±6
60 49±11 52±10 60
50 43±13 47±13 50 39±9
34±12
40 40
30 23±9 30 23±6
20 10±2 20 10±3
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (16) Sqrt (Hours) (16)

(e) (f)

Figure 16. Cont.

Polymers 2020, 12, x FOR PEER REVIEW 18 of 28
Polymers 2020, 12, 2241 18 of 28
100
Polymers 2020, 12, x FOR PEER REVIEW 100 93±2 94±1
18 of 2896±2
Alkali-Polymer Alkali-Polymer 85±6
90 90
62±16
80 80
62±9
Recovery, %

%
70 100 58±11 59±12 60±12 70
100 93±2 94±1 96±2
54±8 56±10
Alkali-Polymer Alkali-Polymer
48±13 85±6
48±6 51±7

Recovery,
60 90 60
90 77±9
50 41±1 50 62±16 69±13
80 80
62±9 32±9
Recovery, %

%
40 70 29±2 58±11 59±12 60±12 40
70
54±8 56±10 48±13
48±6 51±7

Recovery,
30 60 60
30 19±5 77±9
20 50 13±1 41±1 50
20 69±13
9±1 32±9
10 40 29±2 40
10
0 30 300 19±5
13±1
020 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 20
0 9±1
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
10 10
Sqrt (Hours) (19) Sqrt (Hours) (13)
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(g)Sqrt (Hours) (19) Sqrt(h)
(Hours) (13)

(g) (h)
Figure 16. Percent of production versus the square root of the time plot for the Nordhorn non-aged
and Figure
aged
Figure 16.
16.core Percent
Percent of production
plugsofsaturated
production withversus the square
low TAN
versus the square
oil at root
60 °C
root ofof(alkali:
the
thetime 7plot
time g/L for
plotNa the
for2COtheNordhorn non-aged
3; Nordhorn
polymer: 2000 ppm
non-aged
andand
FLOPAAM
agedaged
corecore
3630S).plugs
plugs saturated
Non-aged
saturated corewith
withdata low
low TANand
(a,c,e
TAN oil at
oil g) are◦°C
at 60
60 (alkali:
(alkali:77g/L
presented
C on
g/L Na
theNa CO
2left
2 CO ; polymer:
3side
3 ; 2000
whereas
polymer: ppm
aged
2000 core
ppm
data FLOPAAM
(b,d,f and 3630S).
h) on Non-aged
the right core
side. data (a,c,e
Black-coloredand g)
dataare presented
refer to on
Test the left
water,
FLOPAAM 3630S). Non-aged core data (a,c,e,g) are presented on the left side whereas aged core data side whereas
Blue-colored aged
data core
refer to
data
polymer, (b,d,f and h)
purple-colored
(b,d,f,h) on on
the right side.the right
data side. Black-colored
refer to alkali,
Black-colored dataand data refer
green-colored
refer to
to Test water, Test
datawater, Blue-colored
refer to alkali-polymer.
Blue-colored data refer to
data refer toUltimate
polymer,
polymer, purple-colored data refer to alkali, and green-colored data refer to alkali-polymer. Ultimate
purple-colored
recovery data to
(UR) refers refer to alkali,oiland
recovered green-colored
divided bv Soi. data refer to alkali-polymer. Ultimate recovery
recovery (UR) refers to recovered oil divided bv Soi.
(UR) refers to recovered oil divided bv Soi.
Nevertheless, the effect of TAN is also seen on aged core plugs. Application of alkali and alkali-
Nevertheless, the effect of TAN is also seen on aged core plugs. Application of alkali and alkali-
polymer Nevertheless,
with high the effect
TAN oiloil of TAN is also
results seen on aged core plugs. Application of alkali and
polymer with high TAN resultsininhigher
higherultimate recoveries
ultimate recoveries than
than for
for non-aged
non-aged corecore plugs,
plugs, as well
as well
alkali-polymer
as for with high TAN oil results in higher ultimate recoveries than for non-aged core plugs,
as aged
for agedcorecore
plugs.
plugs. AA higher
higheramount
amountof ofanionic
anionic surfactants (soaps),we
surfactants (soaps), we believe
believe werewere created
created duedue
as the
to well as for aged core plugs. A higher amount of anionic surfactants
to the high TAN oil affecting the wettability change to a larger extent, which is the reason for for
high TAN oil affecting the wettability change to a larger (soaps),
extent, which we isbelieve
the were
reason created
the the
due
bigger to the high
ultimate
bigger TAN
oil oil
ultimate oil
recovery.affecting
recovery. the wettability change to a larger extent, which is the reason for the
bigger ultimate oil recovery.
3.3.3.3.3.3. Nordhorn
Nordhorn CoreCore Plugs—BrineComposition
Plugs—Brine Composition
3.3.3. Nordhorn Core Plugs—Brine Composition
For Forthisthis
case,case, selectspontaneous
select spontaneous imbibition
imbibition tests tests were
were performed
performedwith withthethe cores
coresinitially
initially
For this
saturated case,
with select
brine spontaneous
containing a imbibition
high amount tests
of were
divalent
saturated with brine containing a high amount of divalent ions. Two cases are described—oneperformed
ions. Two with
cases the
are cores initially
described—one saturated
withwith
withtest
test brine
water
watercontaining
and
and the other
the other a high
with amount of divalent ions.
with the alkali–polymer
the alkali–polymer
solution.
solution. TwoFigure
cases17
Figure are described—one
depicts
17 depicts
a comparison
a comparison with test
of the water
oil
of the oil
and production
the other behavior
with the in the non-aged Nordhorn
alkali–polymer solution. core plugs
Figure 17 for brineawith
depicts only monovalent
comparison of the oilions (test
production
production behavior in the non-aged Nordhorn core plugs for brine with only monovalent ions (test
water)inand
behavior one with both mono- core and plugs
divalent ions
brine(formation
with onlybrine). The results (testindicate no and
water) and theonenon-aged
with both Nordhorn
mono- and divalent forions (formation monovalent
brine). The ions water)
results indicate no
one significant
with both changes
mono- in
and the oil
divalent production
ions rate
(formationor ultimate
brine). oil
The recovery
results when
indicatethe formation
no significantbrine or
changes
significant
testoil
waterchanges
were used in the oil
foror production
initial saturation. rate or in
Only ultimate
the case oil low
recovery when the formation brine or
in the
test water production
were used rate
for initialultimate oil recovery
saturation. Only in when
the theof
case of low
TAN oil
formationTAN
wasor
brine
oil
the
was
recovery
test
the water
recovery
higher
were used
higher
when the core was initially saturated with formation brine and subsequently submerged into the
for
when initial saturation.
the core wassolution. Only
initiallyThisin the
saturated case of
with low TAN oil was the recovery higher when the core was
alkali–polymer behavior canformation
be attributed brine
to theanduncertainty
subsequently while submerged
performinginto the the
initially saturated
alkali–polymer with formation
solution. Thisstep, brine and
behavior can subsequently
be attributed submerged into the alkali–polymer
to the uncertainty while performing solution.
measurement. As the next the core plugs, initially saturated with formation brine, were aged the
This behavior
measurement.
under reservoircan be
As the attributed
next step, for
temperatures to the uncertainty
the30coredaysplugs, while
initiallythe
to determine performing
saturated the
influencewith measurement.
formation
of divalent As the next
brine, were aged
ion concentrations step,
the on
under core plugs, initially
wettability
reservoir changessaturated
temperatures during with
foraging.
30 daysformation
to determinebrine, thewere aged under
influence reservoir
of divalent iontemperatures
concentrations for
30 days to determine
on wettability changes the influence of divalent ion concentrations on wettability changes during aging.
High TAN Oilduring aging. Cores
Non-Aged Nordhorn 100 Low TAN Oil Non-Aged Nordhorn Cores
100 Test Water - Test Water
90 Test Water - Test Water 90
80 Low TAN Oil Non-Aged Nordhorn Cores
80 High TAN Oil Non-Aged Nordhorn Cores
%

100 60±3
Recovery, %

100 62±6 70 56±8 56±7 57±7 57±6 57±6

57±7 Water
51±9 Test
55±8 Water - Test
70
Test Water - Test Water
54±0 55±1 56±2 57±2 90
Recovery,

53±1 60
90 60 49±4 51±3 53±1 80 44±13
80 50 43±2 50
%

60±3
Recovery, %

40 62±6 70
40 27±12 56±8 56±7 57±7 57±7 57±6 57±6
70
53±1 54±0 55±1 56±2 57±2 51±9 55±8
Recovery,

24±4 60
30
60 30 49±4 51±3 53±1 44±13
20 43±2 20
50
50
10 10
40
40 0
27±12
30 0 24±4 30
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
20 20
(18) (16)
10 Sqrt (Hours) 10 Sqrt (Hours)
0 0
0 0.5 1 1.5 2 2.5 (a)
3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 (b)
2.5 3 3.5 4 4.5 5 UR
(18) (16)
100 Sqrt
Form. (Hours)
Brine - Test Water 100 Sqrt (Hours)
Form. Brine - Test Water
90 90
80 (a) 80 (b)
70 58 58 59 70 53 53 54 54 54 54 57
Recovery, %

58
Recovery, %Recovery, %

54 55 56 56 57 53
100 60 60
100 49 52
45Form. Brine - Test Water 41 Form. Brine - Test Water
90 50 50
90
80 40 40
80
24
70 30 58 30
70 53 57
58 59 53 54 54 54 54
Recovery, %

20 54 55 56 56 57 58 20
53
60 60 49 52
10 45 10 41
50 50
0 0
40 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 40 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
24
30 (17) 30 (20)
Sqrt (Hours) Sqrt (Hours)
20 20
10 (c) 10 (d)
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (17) Sqrt (Hours) (20)

(c) (d)

Figure 17. Cont.

Polymers 2020, 12, 2241 19 of 28
Polymers 2020, 12, x FOR PEER REVIEW 19 of 28
Polymers 2020, 12, x FOR PEER REVIEW 19 of 28

100 88±8 100

100 Test Water - Alkali-Polymer 88±8 100 Alkali-Polymer
90 Test Water - Alkali-Polymer 90 Alkali-Polymer
90
80 90
80
67±4 69±3 62±9
Recovery,%%

Recovery,%%
80
70 62±2 67±4 69±3 80
70 58±11 59±12 60±12 62±9
70 55±3 62±2 70 54±8 56±10 59±12 60±12
60 48±3 55±3 60 48±6 51±7 54±8 56±10 58±11
41±1 48±6 51±7
Recovery,

Recovery,
60
50 41±4 48±3 60
50
50 33±5 41±4 50 41±1
40 40 29±2
40 24±4 33±5 40 29±2
30 30
30 15±4 24±4 30 13±1
20 7±2 15±4 20 13±1
20
10 7±2 20
10
100 100
0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(24) 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(19)
Sqrt (Hours) (24) Sqrt (Hours) (19)
Sqrt (Hours) Sqrt (Hours)
(e)
(e) (f)
(f)
100 90 100
100 Form. Brine - Alkali-Polymer 90 100 Form. Brine - Alkali-Polymer
90 Form. Brine - Alkali-Polymer 90 Form. Brine - Alkali-Polymer
90
80 70 90
80 69 70 70 70 70 70 70 70
65 68
80
70 70 80
70 61 68 69 70 70 70 70 70 70 70
59 65
%%

%%
70 53 59 70 61
60 48 60
Recovery,

Recovery,
60 53 60
42 48
Recovery,

Recovery,
50 36 50 36
50 42 50
40 29 36 40 36
40
30 29 40
30
19
30
20 19 30
20
7
20
10 7 20
10
100 100
0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(24) 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(13)
Sqrt (Hours) (24) Sqrt (Hours) (13)
Sqrt (Hours) Sqrt (Hours)
(g)
(g) (h)
(h)
Figure
Figure 17. Percentage
Figure 17. Percentage
Percentage of of production
of production versus
production versus the
versus the square
the square root
square root of
root of the
of the time
the time plot
time plot for non-aged
plot for non-aged Nordhorn
non-aged Nordhorn
Nordhorn
core
core plugs
core plugs (water
plugs (water composition
(water composition comparison)
composition comparison)
comparison) for for high
for high TAN
high TAN
TAN oiloil (a)
oil (a) and
(a) and low
and low TAN
low TAN oil
TAN oil (b)
oil (b) at
(b) at 60
at 60 °C (alkali:
◦ C(alkali:
60 °C (alkali:
7 g/L
77 g/L Na
g/L Na 2CO3; polymer: 2000 ppm FLOPAAM 3630S). High TAN oil data (a,c,e and g) are presented
Na22COCO33; ;polymer:
polymer:2000 2000ppmppmFLOPAAM
FLOPAAM3630S). 3630S).High
HighTAN TANoil oildata
data(a,c,e
(a,c,e,g)
and are presented
g) are presented on
on
on the
thethe left
leftleft
sideside whereas
whereas
side whereas lowlow
TAN
low TAN
TAN oil
oiloil data
data
data (b,d,f
(b,d,f,h) and
(b,d,f and h)
on the on
h) on the
right right
the side. side. Black-colored
Black-colored
right side. data
data data
Black-colored refer
referrefer to
to Test
to
Test
water
Test water
water (saturated
(saturated
(saturated core)
core)core) imbibed
imbibed by
by test
imbibed test
bywater, water, red-colored
red-colored
test water, data
data data
red-colored refer
refer refer to formation
to formation brine
brinebrine
to formation (saturated
(saturated core)
(saturated
core) imbibed
imbibed
core) bywater,
by testby
imbibed test water,
test water, green-colored
green-colored datatorefer
data refer
green-colored data refer to test
test(saturated
test water
to water (saturated
water (saturated core) imbibed
core) imbibed
core) imbibed by alkali-
alkali-
by alkali-polymer,
by
polymer, and blue-colored
and blue-colored
polymer, and blue-colored data
data referdata refer to
to formation
refer to formation
formation brine (saturated
brine (saturated
brine (saturated
core) imbibedcore) by
core) imbibed by alkali-polymer.
alkali-polymer.
alkali-polymer.
imbibed by Ultimate
Ultimate
recovery recovery
(UR) (UR)
refers to refers
recoveredto recovered
oil divided oil divided
bv
Ultimate recovery (UR) refers to recovered oil divided bv Soi. Soi. bv Soi.

The comparison
The comparison
The comparison of of aged
aged and
aged and non-aged
and non-aged Nordhorn
non-aged Nordhorn core
Nordhorn core plugs
core plugs is
plugs is shown
is shown
shown in in Figure
in Figure 18
Figure 18 for
18 for high
for high TAN
high TAN
TAN
oil and in Figure 19 for low TAN oil.
oil and in Figure 19 for low TAN oil. For
oil For the
For the observations
the observations obtained
observations obtained
obtained inin this
in this work,
this work, when
work, when thethe core plug
the core plug
was placed into the test water after saturation, the composition of the formation
was placed into the test water after saturation, the composition of the formation brine did not brine did not play
play
play aaa
large
large role. As
As can
can be
be seen
seen from
from Figure
Figure 18a,
18a, the
the oil
oil production
production profile
profile followed the same
same
large role. As can be seen from Figure 18a, the oil production profile followed the same path for both path
path for
for both
both
the formation brine and test water’s
the formation brine and test water’s
the initial
water’s initial saturation
initial saturation in the case of aged and non-aged
saturation in the case of aged and non-aged cores. cores.

High TAN Oil Non-Aged Nordhorn Cores High TAN Oil Aged Nordhorn Cores
100 High TAN Oil Non-Aged Nordhorn Cores 100 High TAN Oil Aged Nordhorn Cores
100 Test Water - Test Water 100
90 Test Water - Test Water
90 Test Water - Test Water 90 Test Water - Test Water
90
80 80 68±3
62±1 63±1 63±5 64±1 64±1 65±1
Recovery,%%

80
Recovery,%%

80
70 62±6 70 58±4 62±2 62±1 63±1 63±5 64±1 64±1 65±1 68±3
70 57±2
53±1 54±0 55±1 56±2 57±2 62±6 70 58±4 62±2
60 49±4 51±3 53±1 54±0 55±1 56±2 60 46±12
43±2 49±4 51±3 53±1 53±1
Recovery,

60
Recovery,

60
50 50 46±12
50 43±2 50
40
40
40 24±4 40
30 22±10
30 24±4 22±10
30 30
20
20
20 20
10
10
100 100
0 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(16)
(18) Sqrt (Hours)
Sqrt (Hours) (18) Sqrt (Hours) (16)
Sqrt (Hours)
(a) (b)
(b)
(a)
100 Form. Brine - Test Water Non-Aged 100 Form. Brine - Test Water Aged
100
90 Form. Brine - Test Water Non-Aged 100
90 Form. Brine - Test Water Aged
90
80 90
80
80 80 62 63 63 64 64 65 65 66
70 58 58 59 70 59 64 65 65 66
%%

58
%%

70 54 55 56 56 57 58 70 62 63 63 64
60 55 56 56 57 58 58 59 60 50 59
Recovery,

Recovery,

60 45 54 60 50
Recovery,

Recovery,

50 45 50
50
40 50
40
40 24 40
30 24 30 17
30
20 30
20 17
20
10 20
10
100 100
0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(17) 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(13)
Sqrt (Hours) (17) Sqrt (Hours) (13)
Sqrt (Hours) Sqrt (Hours)
(c)
(c) (d)
(d)
Figure 18. Cont.
Polymers 2020, 12, 2241 20 of 28
Polymers 2020, 12, x FOR PEER REVIEW 20 of 28

100 88±8 100 93

Test Water - Alkali-Polymer Non-Aged Test Water - Alkali-Polymer Aged
90 90
80 67±4 69±3 80 69
64
Recovery, %

Recovery, %
70 62±2 70
55±3 55
60 48±3 60 46
50 41±4 50 38
40 33±5 40 29
24±4 22
30 30
15±4 15
20 7±2 20 9
4
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (24) Sqrt (Hours) (25)

(e) (f)
100 90 100 98
Form. Brine - Alkali-Polymer Non-Aged Form. Brine - Alkali-Polymer Aged
90 90 80
80 70 80 74
65 66
70 59 70 59
Recovery, %

Recovery, %
60 53 60 51
48 44
50 42 50
36 33
40 29 40
30 19 30 22
20 20 12
7 6
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (24) Sqrt (Hours) (18)

(g) (h)
Figure
Figure 18.18. Percentage
Percentage of of production
production versus
versus the
the square
square root
root ofof the
the time
time plot
plot for
for non-aged
non-aged and
and aged
aged
Nordhorn core plugs saturated with high TAN oil (water composition comparison)
Nordhorn core plugs saturated with high TAN oil (water composition comparison) at 60 C (alkali: at 60 °C◦ (alkali: 7
g/L Na CO ; polymer: 2000 ppm FLOPAAM 3630S). Data of non-aged
7 g/L Na2 CO3 ; polymer: 2000 ppm FLOPAAM 3630S). Data of non-aged cores (a,c,e,g)
2 3 cores (a,c,e and g) are presented
presented
on
on the
theleft
leftside
sidewhereas
whereasagedagedcore
coredata (b,d,f
data and h)
(b,d,f,h) onon the
the rightside.
right side.Black-colored
Black-colored data
data refer to test
test
water (saturated
(saturated core)
core) imbibed
imbibed byby test
test water,
water, red-colored
red-colored data
data refer
refer to
toformation
formationbrine
brine(saturated
(saturatedcore)
core)
imbibed
imbibed by by test
testwater,
water,green-colored
green-colored data
data referrefer to water
to test test water (saturated
(saturated core) imbibed
core) imbibed by alkali-
by alkali-polymer,
polymer, and blue-colored
and blue-colored data referdata refer to formation
to formation brine (saturated
brine (saturated core) imbibedcore) by
imbibed by alkali-polymer.
alkali-polymer. Ultimate
Ultimate
recovery recovery
(UR) refers (UR) refers to recovered
to recovered oil dividedoilbv
divided
Soi. bv Soi.

Differences could
Differences couldbe bedetected
detectedwhen whenthe thealkali–polymer
alkali–polymer solution
solution was
was used
used as as displacing
displacing fluid.
fluid. A
A higher
higher production
production raterate
waswas visible
visible when when formation
formation water water
was wasusedused for primary
for primary saturation.
saturation. The
The observed
observed behavior
behavior was inwas in good
good agreement
agreement with the with thereported
data data reported
by Haaghby Haagh et al.
et al. [48], [48], can
which which be
can be explained
explained by surfactant–divalent
by surfactant–divalent ion–rockion–rock surface interactions.
surface interactions. Divalent ions Divalent ions can
can promote promote
wettability
wettabilitywhen
alteration alteration
used when used with
with anionic anionic surfactants.
surfactants. When the alkali When the alkali
reacts reacts oil
with crude with crude
acids, anoil acids,
anionic
an anionicwith
surfactant surfactant with a charged
a negatively negatively headcharged head The
is formed. is formed.
negativelyThe negatively
charged end charged
of this end of this
surfactant
surfactant
can create acan create
bridge a bridge
with with the
the mineral mineral
surface. surface.
This This effect
effect yields fasteryields faster wettability
wettability alteration,
alteration, leading to
leading to a water-wet state and higher oil production rate. This statement is
a water-wet state and higher oil production rate. This statement is supported by the results of similar supported by the results
of similar experiments
experiments performedperformed
with low TAN with oil.
low TAN oil.
Comparing the
Comparing the obtained
obtainedresults
resultsofofalkali-polymer
alkali-polymer imbibition
imbibition for for
highhigh
and and
low TAN
low TANoil, oneoil,could
one
notice that the production rate with high TAN oil is slower, which indicates
could notice that the production rate with high TAN oil is slower, which indicates that smaller that smaller capillary forces
could be acting
capillary forcesin the porous
could media.
be acting in theSmaller
porouscapillary forces occur
media. Smaller due toforces
capillary smaller IFT thanks
occur to the larger
due to smaller IFT
amount of anionic surfactants (soaps) created while reacting with high TAN
thanks to the larger amount of anionic surfactants (soaps) created while reacting with high TAN oil. oil. Ultimate oil recovery is
also slightly
Ultimate higher in is
oil recovery the case
also of highhigher
slightly TAN oil compared
in the case of to lowTAN
high TAN. oilThese observations
compared to low TAN.support the
These
affirmation that
observations application
support of alkali–polymer
the affirmation in high TAN
that application oil leads to a higher
of alkali–polymer in highdegree
TAN oil of wettability
leads to a
alteration.
higher degreeTheofoil production
wettability profiles The
alteration. for low TAN oil areprofiles
oil production presented in Figure
for low TAN oil 19.areAspresented
can be seen, in
the production
Figure 19. As can behavior
be seen,wasthesimilar for allbehavior
production cases, except for the non-aged
was similar alkali–polymer
for all cases, except for theexperiment.
non-aged
Notably, the same
alkali–polymer production
experiment. profilesthe
Notably, were observed
same among
production the aged
profiles werecores with implementation
observed among the aged of
the alkali–polymer solution. In this case, the process of wettability alteration
cores with implementation of the alkali–polymer solution. In this case, the process of wettability due to anionic surfactant
creation did
alteration due nottooccur. As asurfactant
anionic result, there are nodid
creation observable
not occur.differences between
As a result, therethearesaturation of core
no observable
plugs with brine of high or low divalent ion concentration.
differences between the saturation of core plugs with brine of high or low divalent ion concentration.
Polymers 2020, 12, 2241 21 of 28
Polymers 2020, 12, x FOR PEER REVIEW 21 of 28

Low TAN Oil Non-Aged Nordhorn Cores 100 Low TAN Oil Aged Nordhorn Cores
100
90 Test Water - Test Water 90 Test Water - Test Water
80 80
65±1

Recovery, %
61±2 62±1 63±1 63±1
Recovery, %

70 60±3 70 57±4 59±2 60±2

56±8 56±7 57±7 57±7 57±6 57±6
60 51±9 55±8 60 49±9
50 44±13 50
40 40 30±22
27±12
30 30 16±15
20 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(16) (13)
Sqrt (Hours) Sqrt (Hours)

(a) (b)
100 Form. Brine - Test Water Non-Aged 100 Form. Brine - Test Water Aged
90 90
80 80 71
63 65 66 66
70 53 53 54 54 54 57 70 59 60 62
54
Recovery, %

Recovery, %
53 55
60 49 52 60 47
50 41 50
40 40
24
30 30
20 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (20) Sqrt (Hours) (15)

(c) (d)
100 100 96±2
Test Water - Alkali-Polymer Non-Aged Test Water Alkali-Polymer Aged
90 90 94±1
62±16 93±2
80 80
62±9
Recovery, %

Recovery, %

70 58±11 59±12 60±12 70 85±6

54±8 56±10 48±13
60 48±6 51±7 60 77±9
50 41±1 50 69±13
32±9
40 29±2 40
30 30 19±5
20 13±1 20 9±1
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (19) Sqrt (Hours) (13)

(e) (f)
100 100 93
Form. Brine - Alkali-Polymer Non-Aged Form. Brine - Alkali-Polymer Aged 86
90 90 78
80 69 70 70 70 70 70 70 70 80 73
68 68 84
70 61 70 62
Recovery, %

Recovery, %

60 60 50
50 36 50
40 40 34
30 30 21
20 20 10
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (13) Sqrt (Hours) (15)

(g) (h)
Figure19.
Figure Percentage
19.Percentage of production
of production versusversus the root
the square square root
of the ofplot
time thefor
time plot for
non-aged andnon-aged and aged
aged Nordhorn core
Nordhorn corewith
plugs ◦ C (alkali:
plugs saturated lowsaturated with composition
TAN oil (water low TAN oil (water composition
comparison) comparison)
at 60 °C (alkali: 7g/L Na2COat3; 60
polymer: 2000
7 g/LFLOPAAM
ppm Na2 CO3 ; polymer: 2000
3630S). Data ppm FLOPAAM
of non-aged cores (a,c,e 3630S). Data
and g) are of non-aged
presented cores
on the left side(a,c,e,g)
whereasare presented
aged core data
on the
(b,d,f left
and h)side whereas
on the aged
right side. core data data
Black-colored (b,d,f,h) ontest
refer to thewater
right(saturated
side. Black-colored
core) imbibed data refer
by test to red-
water; test
water (saturated
colored core)
data refer to imbibed
formation by(saturated
brine test water; red-colored
core) imbibed bydata refer togreen-colored
test water; formation brine (saturated
data refer core)
to test water
imbibed by
(saturated test imbibed
core) water; green-colored data refer
by alkali-polymer, to test waterdata
and blue-colored (saturated
refer tocore) imbibed
formation by (saturated
brine alkali-polymer,
core)
and blue-colored
imbibed data refer
by alkali-polymer. to formation
Ultimate brinerefers
recovery (UR) (saturated core) oil
to recovered imbibed
dividedby
bvalkali-polymer.
Soi. Ultimate
recovery (UR) refers to recovered oil divided bv Soi.
3.3.4. Nordhorn and Keuper Core Plugs—Influence of Mineralogy
3.3.4. Nordhorn and Keuper Core Plugs—Influence of Mineralogy
For this set of experiments, core plugs were initially saturated with the formation brine
For this set of experiments, core plugs were initially saturated with the formation brine containing
containing a large number of divalent ions. After oil saturation, the cores were submerged into the
a large number of divalent ions. After oil saturation, the cores were submerged into the test water and
test water and alkali–polymer solution. The observed oil production behavior is presented in Figure
alkali–polymer solution. The observed oil production behavior is presented in Figure 20. The results
20. The results indicate wettability alteration, even when the core was not aged. Therefore, the
indicate wettability alteration, even when the core was not aged. Therefore, the influence of TAN is
influence of TAN is clearly indicated. For high TAN oil (16 TH), the Keuper core plugs showed a
clearly indicated. For high TAN oil (16 TH), the Keuper core plugs showed a significant decrease in both
significant decrease in both the production rate and ultimate oil recovery when test water was used
the production rate and ultimate oil recovery when test water was used as a displacing fluid. At the
as a displacing fluid. At the same time, oil production was similar to that of the Nordhorn core plugs
same time, oil production was similar to that of the Nordhorn core plugs in the case of alkali–polymer
in the case of alkali–polymer application. This suggests that even without the aging period, the polar
application. This suggests that even without the aging period, the polar components of the crude oil
components of the crude oil covered the clay mineral surfaces, resulting in a neutral (oil)-wet state of
covered the clay mineral surfaces, resulting in a neutral (oil)-wet state of the core. However, during
the core. However, during the application of the alkali–polymer solution, the oil-wetness returned to
a water-wet state and, as a result, greater ultimate recovery was achieved. Similarly, small capillary
Polymers 2020, 12, 2241 22 of 28

the application
Polymers 2020, 12, x of
FORthe alkali–polymer
PEER REVIEW solution, the oil-wetness returned to a water-wet state and, as28a
22 of
result, greater ultimate recovery was achieved. Similarly, small capillary forces led to slow production.
The large
forces difference
led to in the case
slow production. of large
The test water application
difference could
in the case alsowater
of test be related to the high
application couldvalue
also beof
heterogeneity
related in the
to the high Keuper
value outcrop core. in the Keuper outcrop core.
of heterogeneity

100 High TAN Oil 100 Low TAN Oil

90 Form. Brine - Test Water Non-Aged Nordhorn Cores 90 Form. Brine - Test Water Non-Aged Nordhorn Cores
80 80
70 58 58 59 70 53 53 54 54 54 54 57
Recovery, %

58

Recovery, %
54 55 56 56 57 53
60 60 49 52
45 41
50 50
40 40
24
30 30
20 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (17) Sqrt (Hours) (20)

(a) (b)
100 90 100
Form. Brine - Alkali-Polymer Non-Aged Nordhorn Cores Form. Brine - Alkali-Polymer Non-Aged Nordhorn Cores
90 90
80 70 80 68 69 70 70 70 70 70 70 70
65 61
70 59 70
Recovery, %

Recovery, %
60 53 60
48
50 42 50
36 36
40 29 40
30 19 30
20 7 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (24) Sqrt (Hours) (13)

(c) (d)
100 Form. Brine - Test Water Non-Aged Keuper Cores 100 Form. Brine - Test Water Non-Aged Keuper Cores
90 90
80 80
65
70 70
Recovery, %

Recovery, %

51 52 52 53 54 55
60 60 50
46
50 50
35
40 40
30 16 19 30
13 15 15 15 15 15 16 15
20 10 20
5
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (21) Sqrt (Hours) (21)

(e) (f)
100 Form. Brine - Alkali-Polymer Non-Aged Keuper Cores 100 Form. Brine - Alkali-Polymer Non-Aged Keuper Cores
90 99 90
72 77
80 80 69 71
64 67
70 59 70 59 62
Recovery, %

Recovery, %

52 56
60 49 60 49
42 45
50 38 50
40 32 40 32
30 22 30
15
20 10 20
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (19) Sqrt (Hours) (14)

(g) (h)
Figure
Figure 20.
20. Percent
Percent ofof production
production versus
versus square
square root
root of
of time
time plot
plot for
for non-aged
non-aged Nordhorn
Nordhorn andand Keuper
Keuper
core
core plugs
plugs for high TAN oil (a)
TAN oil (a) and
and low
low TAN
TANoiloil(b)
(b)at 60◦°C
at60 C (alkali: g/L Na22CO33;; polymer:
(alkali: 77g/L polymer: 2000
2000 ppm
ppm
FLOPAAM 3630S). High TAN oil data (a,c,e and g) are presented on the left
FLOPAAM 3630S). High TAN oil data (a,c,e,g) are presented on the left side whereas low TAN oil side whereas low TAN
oil
datadata (b,d,f and
(b,d,f,h) h) right
on the on theside.
rightNordhorn
side. Nordhorn cases
cases are are presented
presented from (a) from (a) to
to (d), (d), whereas
whereas Keuper Keuper
cases
cases are presented
are presented fromfrom
(e) to(e)(h).
to (h). Red-colored
Red-colored data
data refer
refer totoformation
formationbrine brine(saturated
(saturated core) imbibed
imbibed
by test
by test water;
water; blue-colored
blue-colored datadata refer
refer to
to formation
formation brine
brine (saturated
(saturated core)
core) imbibed
imbibed by by alkali-polymer;
alkali-polymer;
orange-colored data
orange-colored datarefer
refertotoformation
formation brine (saturated
brine core)
(saturated imbibed
core) imbibedby test
bywater, and mustard-colored
test water, and mustard-
data refer
colored to formation
data brine (saturated
refer to formation core) imbibed
brine (saturated core)by alkali–polymer.
imbibed Ultimate recovery
by alkali–polymer. Ultimate(UR) refers
recovery
to recovered
(UR) refers tooil divided oil
recovered bv divided
Soi. bv Soi.

Wettability alteration was also indicated for the low TAN oil (St. Ulrich), with a slower
production rate observed for the Keuper core plug. This demonstrates the neutral (oil)-wet state of
the core after aging. The lower ultimate oil recovery for the Nordhorn core plugs can be explained by
the “snap-off” effect in the water-wet system that leads to higher residual oil saturation. Another
remarkable point is the minor improvement in oil recovery with the alkali–polymer solution. As
demonstrated by IFT measurements, the low TAN oil failed to reduce the interfacial tension to low
values. Vijapurapu and Rao [49] reported a critical value of IFT, above which wettability alteration
Polymers 2020, 12, 2241 23 of 28

Wettability alteration was also indicated for the low TAN oil (St. Ulrich), with a slower production
rate observed for the Keuper core plug. This demonstrates the neutral (oil)-wet state of the core after
aging. The lower ultimate oil recovery for the Nordhorn core plugs can be explained by the “snap-off”
effect in the water-wet system that leads to higher residual oil saturation. Another remarkable point is
the minor improvement in oil recovery with the alkali–polymer solution. As demonstrated by IFT
Polymers 2020, 12, x FOR
measurements, the PEER REVIEW
low TAN oil failed to reduce the interfacial tension to low values. Vijapurapu 23 of 28
and Rao [49] reported a critical value of IFT, above which wettability alteration does not occur [48].
does
Whennot occur
this [48].IFT
critical When thisiscritical
value IFT value
not reached, oilisdroplet
not reached, oil droplet
detachment does detachment
not occur. does not occur.
Consequently,
Consequently, lower ultimate
lower ultimate production is obtained. production is obtained.
Data
Data ofofthe
theexperiments
experimentsshown showninin Figures
Figures 21–24
21–24were
wereusedused to assess the the
to assess influence
influencethatthat
aging can
aging
have on the
can have on theKeuper
Keuperoutcrop
outcrop during
during thethespontaneous
spontaneousimbibition
imbibitionprocess.
process.Figure
Figure21 21 depicts
depicts the
the
behavior
behavior of oil production from aged and non-aged Keuper samples and compares it to that
of oil production from aged and non-aged Keuper samples and compares it to that of
of the
the
Nordhorn
Nordhorn samples
samples (results
(results previously
previously discussed).
discussed). Data Data obtained
obtained from from the
the aged
aged core
core plugs
plugs confirmed
confirmed
the
the wettability changes, and minimal oil production was observed for the aged Keuper core plugsplugs
wettability changes, and minimal oil production was observed for the aged Keuper core using
using test water
test water as a displacing
as a displacing fluid.fluid.
This This represents
represents a significant
a significant wettability
wettability changechange towards
towards an oil-
an oil-wet
wet
state.state. Similarly,
Similarly, using
using the the alkali–polymer
alkali–polymer solution,solution, the oil production
the oil production rate also
rate also dropped dropped
significantly,
significantly, suggesting oil-wet behavior, but the ultimate oil recovery was
suggesting oil-wet behavior, but the ultimate oil recovery was the largest. This can be explained, the largest. This can be
explained, as previously described, by the principle of the anionic surfactant–mineral
as previously described, by the principle of the anionic surfactant–mineral surface reactions. Note that surface
reactions. Note that similar
similar observations observations
were obtained whenwere obtained
evaluating thewhen
low TANevaluating
oil (seethe low TAN
Figure oil (see
22). One Figure
important
22). One important overall observation is that a significant shift in core wettability
overall observation is that a significant shift in core wettability was observed for the Keuper outcrop. was observed for
the Keuper outcrop. The observations were based mainly on the profile
The observations were based mainly on the profile of the oil production plot. Both the aged Keuperof the oil production plot.
Both the aged
core plugs showedKeupermuchcore plugsproduction
slower showed much ratesslower production
and ultimate rates and
oil recovery, ultimate
which oil recovery,
are indicators of a
which are indicators of a strongly oil-wet system. The alkali–polymer
strongly oil-wet system. The alkali–polymer application again failed to improve the oil recovery application again failed for
to
improve
low TANthe oil.oil recovery for low TAN oil.
100 Form. Brine - Test Water Aged Nordhorn Cores
100 High TAN Oil 90
90 Form. Brine - Test Water Non-Aged Nordhorn Cores 80
80 62 63 63 64 64 65 65 66
70 59
Recovery, %

70 58 58 59
Recovery, %

54 55 56 56 57 58 60 50
60
45 50
50
40
40
24 30 17
30
20
20
10
10
0
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(17) Sqrt (Hours) (13)
Sqrt (Hours)
(b)
(a)
100 90 100 98
Form. Brine - Alkali-Polymer Non-Aged Nordhorn Cores Form. Brine - Alkali-Polymer Aged Nordhorn Cores
90 90
80 70 80 74
65 66
70 59 70 59 80
Recovery, %

Recovery, %

60 53 60 51
48
50 42 50 44
36 33
40 29 40
30 19 30 22
20 20 12
7 6
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (24) Sqrt (Hours) (18)

(c) (d)
Figure21.
Figure Percentageofof
21.Percentage production
production versus
versus thethe square
square rootroot of time
of the the time
plot plot for Nordhorn
for Nordhorn core plugs
core plugs (non-
(non-aged
aged and aged),
and aged), saturated
saturated with
with high high
TAN oilTAN
at 60 oil
°C.at 60 ◦ C.7 g/L
Alkali: Alkali: 7 g/L
Na2CO Na2 CO32000
3, Polymer: , Polymer: 2000 ppm
ppm FLOPAAM
FLOPAAM
3630Ss. Data 3630Ss. Datacores
of non-aged of non-aged cores
data (a and data
c) are (a and c)onare
presented thepresented on the left
left side, whereas agedside, whereas
cores data (baged
and
cores
d) dataright
on the (b and on the right data
d)Red-colored
side. side.refer
Red-colored databrine
to formation refer (saturated
to formation brine
core) (saturated
imbibed core)
by test imbibed
water; blue-
by test water;
colored blue-colored
data refer data
to formation refer
brine to formation
(saturated core) brine (saturated
imbibed core) imbibed
by alkali–polymer. by alkali–polymer.
Ultimate recovery (UR)
Ultimate
refers recoveryoil
to recovered (UR) refersbv
divided toSoi.
recovered oil divided bv Soi.

100 Form. Brine - Test Water Aged Keuper Cores

100 High TAN Oil 90
90
80
Form. Brine - Test Water Non-Aged Keuper Cores 80
70
Recovery, %

70
Recovery, %

60
60
50
50
40
40
30
30 16 19
13 15 15 15 15 15 16 20
20 10 2 2 2 2 3 3 3 6
5 10 0 1 1
10
0
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (18)
Sqrt (Hours) (21)

(b)
(a)
 Figure 21. Percentage of production versus the square root of the time plot for Nordhorn core plugs (non-
aged and aged), saturated with high TAN oil at 60 °C. Alkali: 7 g/L Na2CO3, Polymer: 2000 ppm FLOPAAM
3630Ss. Data of non-aged cores data (a and c) are presented on the left side, whereas aged cores data (b and
d) on the right side. Red-colored data refer to formation brine (saturated core) imbibed by test water; blue-
colored
Polymers 2020, data refer to formation brine (saturated core) imbibed by alkali–polymer. Ultimate recovery (UR)
12, 2241 24 of 28
refers to recovered oil divided bv Soi.

100 Form. Brine - Test Water Aged Keuper Cores

100 High TAN Oil 90
90
80
Form. Brine - Test Water Non-Aged Keuper Cores 80
70

Recovery, %
70
Recovery, %

60
60
50
50
40
40
30
30 16 19
13 15 15 15 15 15 16 20
20 10 2 2 2 2 3 3 3 6
5 10 0 1 1
10
0
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (18)
Sqrt (Hours) (21)
Polymers 2020, 12, x FOR PEER REVIEW 24 of 28
Polymers 2020, 12, x FOR PEER REVIEW 24 of 28
(a) (b)
100 Form. Brine - Alkali-Polymer Non-Aged Keuper Cores 100 Form. Brine - Alkali-Polymer Aged Keuper Cores
100
90 Form. Brine - Alkali-Polymer Non-Aged Keuper Cores 99 100
90 Form. Brine - Alkali-Polymer Aged Keuper Cores 99
99 99
8090 8090
7080 59 7080 59
Recovery, %

Recovery, %
56
6070 52 59 6070 53 59
Recovery, %

Recovery, %
49 52 56 46 53
45
5060 38 42 45 49 5060 40 46
42
4050 32 38 4050 27
33
33
40
32
3040 22
22 3040 20 27
2030 10 2030 14 20
9 14
5
1020 10 1020 5
9
010 010
0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(19) 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(18)
Sqrt (Hours) (19) Sqrt (Hours) (18)
Sqrt (Hours) Sqrt (Hours)
(c)
(c) (d)
(d)
Figure
Figure 22. Percentage of production versus the square root of the time plot for Keuper core plugs
Figure 22.
22. Percentage
Percentageof of production
productionversus
versusthe
the square
square rootroot of of the
the time
time plot
plot for
for Keuper
Keuper core
core plugs
plugs
(non-aged
(non-aged and aged), saturated with high TAN oil at 60 °C.
◦ Alkali: 7 g/L Na 2CO3, Polymer: 2000 ppm
(non-aged and aged), saturated with high TAN TAN oiloil at
at 60
60 °C. Alkali: 7 g/L Na22CO33,, Polymer:
C. Alkali: Polymer: 20002000 ppm
ppm
FLOPAAM
FLOPAAM 3630Ss. Data ofofnon-aged cores data (a and c) are presented on the left side, whereas aged
FLOPAAM 3630Ss. Data Data of non-aged
non-aged cores
cores data
data (a
(a and
and c)c) are
are presented
presented on on the
the left
left side,
side, whereas
whereas aged
aged
cores
coresdata (b(band
andd) d)on the right side. The orange-colored data refer totoformation brine (saturated
cores data (b and d) onthe
on theright
right side.
side. TheThe orange-colored
orange-colored data data
referrefer formation
to formation brinebrine (saturated
(saturated core)
core)
core)imbibed
imbibed by test water and the mustard-colored data refer to formation brine (saturated core)
imbibed by testbywater
test water
and theand the mustard-colored
mustard-colored data referdata torefer to formation
formation brine (saturated
brine (saturated core)
core) imbibed
imbibed
imbibed bybyalkali–polymer.
alkali–polymer.
by alkali–polymer. Ultimate Ultimate
Ultimate
recoveryrecovery
recovery (UR)
(UR)
(UR) refers torefers
refers totorecovered
recovered recovered
oil dividedoil
oildivided
Soi. bv
divided
bv bvSoi.
Soi.
100 Form. Brine - Test Water Aged Nordhorn Cores
100 Low TAN Oil 100
100
90 Low TAN Oil 90 Form. Brine - Test Water Aged Nordhorn Cores
Form. Brine - Test Water Non-Aged Nordhorn Cores 8090 71
8090 Form. Brine - Test Water Non-Aged Nordhorn Cores 65 66 66 71
7080 59 60 62 63 66 66
7080 65
Recovery, %

53 54 54 57 55 60 62 63
53 54 54 6070
Recovery, %

53 59
Recovery, %

53 57 55
6070 52 53 54 54 54 54 47
Recovery, %

49 53
52 5060 47
5060 41 49
41 4050
4050 24
3040
3040 24
2030
2030
1020
1020
010
010 0
0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR Sqrt (Hours) (15)
Sqrt (Hours) (20) (15)
(20) Sqrt (Hours)
Sqrt (Hours)
(b)
(b)
(a)
(a)
100 100 93
100 Form. Brine - Alkali-Polymer Non-Aged Nordhorn Cores 100 Form. Brine - Alkali-Polymer Aged Nordhorn Cores 93
90 Form. Brine - Alkali-Polymer Non-Aged Nordhorn Cores 90 Form. Brine - Alkali-Polymer Aged78
Nordhorn Cores
8090 68 69 70 70 70 70 70 70 70 8090 68
73
73 78
70 70 70 70 70 70 84 86
7080 61 68 69 70 7080 62 68 84 86
Recovery, %

Recovery, %

61 62
6070 6070
Recovery, %

Recovery, %

50
5060 36 5060 50
4050 36 4050 34
34
3040 3040 21
21
2030 2030 10
10
1020 1020
010 010
0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(13) 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
(15)
Sqrt (Hours) (13) Sqrt (Hours) (15)
Sqrt (Hours) Sqrt (Hours)
(c)
(c) (d)
(d)
Figure
Figure23.
Figure 23.Percentage
23. Percentageofof
Percentage ofproduction
productionversus
production versus
versus thethesquare
the squareroot
square rootofof
root ofthe
thetime
the timeplot
time plotfor
plot forNordhorn
for Nordhorncore
Nordhorn coreplugs
core plugs
plugs
(non-aged
(non-aged andandaged),
aged),saturated
saturated with
with low
low TAN
TAN oil
oilat
at60
60 ◦ C.Alkali:
°C. Alkali: 77 g/L
g/LNa
Na 2COCO 3,3Polymer:
, Polymer: 2000
2000ppm
ppm
2
(non-aged and aged), saturated with low TAN oil at 60 °C. Alkali: 7 g/L Na2CO3, Polymer: 2000 ppm
FLOPAAM
FLOPAAM 3630Ss.
3630Ss.Data
Dataof non-aged
of non-aged cores data
cores data (a and
(a andc)c)are
arepresented
presented ononthethe
FLOPAAM 3630Ss. Data of non-aged cores data (a and c) are presented on the left side, whereas agedleft side,
left whereas
side, whereas aged
aged
cores
coresdata
cores data(b
data (band
(b d)d)
andd) on
on the
the
on right
right
the side.
side.
right Red-colored
Red-colored
side. Red-coloreddatadata
referrefer
data to totoformation
formation
refer brine
brine(saturated
brine (saturated
formation core)
core) imbibed
(saturated core)
by test
imbibed water;
by test blue-colored
water; data
blue-coloredrefer
datato formation
refer to brine
formation (saturated
brine core)
(saturated imbibed
core)
imbibed by test water; blue-colored data refer to formation brine (saturated core) imbibed by alkali– by alkali–polymer.
imbibed by alkali–
Ultimate recoveryrecovery
polymer. (UR) refers torefers
recovered oil divided bv Soi. bv Soi.
polymer.Ultimate
Ultimate recovery(UR) (UR) referstotorecovered
recoveredoil oildivided
divided bv Soi.
100 Form. Brine - Test Water Aged Keuper Cores
100 Low TAN Oil 100
100
90 Low TAN Oil
90 Form. Brine - Test Water Aged Keuper Cores
Form. Brine - Test Water Non-Aged Keuper Cores 8090
8090 Form. Brine - Test Water Non-Aged Keuper Cores 65 7080 59
7080
Recovery, %

65 6070 59
Recovery, %

Recovery, %

54 55
6070 52 52 53
Recovery, %

50 51 55
46 50 51 52 52 53 54 5060
5060 46
35 4050
4050 35
3040 20 21 22
3040 14 16 17 18 21 22
15 2030 12 16 17 18 20
2030 15 4
9 12 14
1020 9
1020 4
010
010 0
0 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR Sqrt (Hours) (18)
Sqrt (Hours) (21) (18)
(21) Sqrt (Hours)
Sqrt (Hours)
(b)
(b)
(a)
(a)
 Figure 23. Percentage of production versus the square root of the time plot for Nordhorn core plugs
(non-aged and aged), saturated with low TAN oil at 60 °C. Alkali: 7 g/L Na2CO3, Polymer: 2000 ppm
FLOPAAM 3630Ss. Data of non-aged cores data (a and c) are presented on the left side, whereas aged
cores data (b and d) on the right side. Red-colored data refer to formation brine (saturated core)
imbibed
Polymers 2020, by
12, test
2241water; blue-colored data refer to formation brine (saturated core) imbibed by alkali– 25 of 28
polymer. Ultimate recovery (UR) refers to recovered oil divided bv Soi.

100 Form. Brine - Test Water Aged Keuper Cores

100 Low TAN Oil 90
90
Form. Brine - Test Water Non-Aged Keuper Cores 80
80
65 70 59

Recovery, %
70
Recovery, %

51 52 52 53 54 55 60
60 50
46 50
50
35 40
40 21 22
30 17 18 20
30 12 14 16
15 20 9
20 4
10
10
0
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (18)
Sqrt (Hours) (21)
Polymers 2020, 12, x FOR PEER REVIEW 25 of 28
(a) (b)
100 Form. Brine - Alkali-Polymer Non-Aged Keuper Cores 100 Form. Brine - Alkali-Polymer Aged Keuper Cores
90 90
72 77
80 69 71 80
64 67 63
70 59 62 70
Recovery, %

Recovery, %
60 49 60
50 50
40 32 40 30
23 27
30 30 16 20
15 12
20 20 7 9
3 5
10 10
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 UR
Sqrt (Hours) (14) Sqrt (Hours) (18)

(c) (d)
Figure
Figure24.
24.Percentage
Percentage ofof
production
production versus
versusthethe
square
square root
rootofofthe
thetime
timeplot
plotforforKeuper
Keupercorecoreplugs
plugs
(non-aged
(non-agedandandaged),
aged),saturated
saturatedwith
withlow
lowTAN
TANoil oilatat60 ◦ C.Alkali:
60°C. Alkali:7 7g/L Na2CO
g/LNa 3, 3Polymer:
, Polymer:2000 ppm
2 CO 2000 ppm
FLOPAAM
FLOPAAM3630Ss.3630Ss.Data
Data ofof
non-aged
non-aged cores
coresdata
data (a(a
andandc)c)
are presented
are presented onon
the
theleft side,
left whereas
side, whereas aged
aged
cores
coresdata
data(b(band
andd)d)on
onthe
theright
right side.
side. The
Theorange-colored
orange-coloreddata datarefer
refertotoformation
formationbrinebrine(saturated
(saturatedcore)
core)
imbibed
imbibed byby test
test water
water andand
thethe mustard-colored
mustard-colored datadata
referrefer to formation
to formation brine
brine (saturated
(saturated core)core) imbibed
imbibed by
by alkali-polymer.
alkali-polymer. Ultimate
Ultimate recovery
recovery (UR)torefers
(UR) refers to recovered
recovered oil divided
oil divided bv Soi. bv Soi.

4.4.Summary
Summary and
and Conclusions
Conclusions
Theparameters
The parametersand andconditions
conditionsdefiningdefiningthe thewettability
wettabilityalteration
alterationand andIFT IFTreduction
reductionininthe the
alkali–polymer were identified for low and high TAN oils. The
alkali–polymer were identified for low and high TAN oils. The work showed how oil composition work showed how oil composition
(lowand
(low andhighhighTAN),
TAN),chemical
chemicaltype, type,brine
brinecomposition,
composition,core coreplug
plugcondition
condition(aged (agedand andnon-aged),
non-aged),
and reservoir mineralogy (2.5% and 10% clay content) clearly influence
and reservoir mineralogy (2.5% and 10% clay content) clearly influence fluid–fluid and rock–fluid fluid–fluid and rock–fluid
interactions. These results are used as a guidance to understand the field application envisaged ininthe
interactions. These results are used as a guidance to understand the field application envisaged the
Matzen1616TH
Matzen THreservoir.
reservoir.
The interfacial
The interfacial tension tensionbetween
betweentested testedoils oilsand
andtesttestwater
water(without
(withoutdivalent
divalentions) ions)remained
remained
constant.When
constant. When alkali
alkali waswas added,
added, thethe decrease
decrease ininIFTIFTforforhigh
highTANTANoiloilwas wasmoremoresignificant
significantand and
reached the low equilibrium value. The addition of polymer to the
reached the low equilibrium value. The addition of polymer to the alkali solution diminished the alkali solution diminished the effect
of IFT
effect of reduction
IFT reduction and increased
and increased the observed
the observed IFT peak value.
IFT peak value.
Low and high TAN oil did not lead to
Low and high TAN oil did not lead to a difference when usinga difference when usingthe thetest
testwater.
water.Regardless
Regardlessofofthe the
TAN of the oil, the imbibition rate was larger when using test water
TAN of the oil, the imbibition rate was larger when using test water as a displacing fluid. For the as a displacing fluid. For the
polymer,this
polymer, thisrate
rateslowed,
slowed,presumably
presumablydue duetotothethemolecule
moleculesize sizeandandviscosity
viscosityofofthe thesolution.
solution.For Forthe
the
alkaliand
alkali andalkali–polymer,
alkali–polymer,the theslower
slowerimbibition
imbibition cancanbebe explained
explained byby a reduction
a reduction inin capillary
capillary forces.
forces.
For the non-aged core plugs, in the case of low TAN oil, all chemical
For the non-aged core plugs, in the case of low TAN oil, all chemical solutions provided a similar solutions provided a similar
ultimaterecovery,
ultimate recovery, while
while forfor high
high TANTANoil, oil,the
theuseuseof of
alkali andand
alkali alkali–polymer
alkali–polymer solutions
solutionsled toleda larger
to a
amount of produced
larger amount of produced oil. oil.
Coreaging
Core aging(aged(agedorornon-aged)
non-aged)for forthe
thetest
testwater
waterand andpolymer
polymerasasdisplacing
displacingfluidsfluidsreflected
reflecteda a
slowerproduction
slower productionrate rateonly
onlywithin
withinthe thefirst
firsthour
hourofofthetheimbibition
imbibitionprocess.
process.Other Othercases
casesexhibited
exhibiteda a
significantly slower initial production rate. The lower ultimate
significantly slower initial production rate. The lower ultimate oil production for non-agedoil production for non-aged (water-wet)
(water-
core plugs can be explained by the oil droplet snap-off phenomenon.
wet) core plugs can be explained by the oil droplet snap-off phenomenon. By submerging more oil- By submerging more oil-wet core
plugs
wet coreinto
plugsdifferent solutions,solutions,
into different the invading fluid can enter
the invading the middle
fluid can enter the of middle
the poreofthroat,
the pore displacing
throat, a
larger amount of oil in the case of a water-wet core. Moreover, when
displacing a larger amount of oil in the case of a water-wet core. Moreover, when alkali was used alkali was used on the oil-wet
on
core samples, the fluid imbibed larger pores and displaced the oil from
the oil-wet core samples, the fluid imbibed larger pores and displaced the oil from the middle areas the middle areas of the pore
ofthroats;
the porethen, the inthen,
throats; situ-created surfactants surfactants
the in situ-created caused wettability
caused alteration.
wettabilityInvading
alteration. fluid subsequently
Invading fluid
subsequently started to spread around the inner surface of the pore throats which ledfrom
started to spread around the inner surface of the pore throats which led to oil detachment the
to oil
detachment from the mineral surfaces. The residual oil saturation decreased for all aged Nordhorn
core cases compared to non-aged samples with alkali and alkali–polymer.
The brine composition did not yield significant changes in the oil production rate or ultimate oil
recovery when the formation brine or test water was used for initial saturation in the case of non-
aged (water-wet) cores. For aged (neutral to oil wet) core plugs saturated with high TAN oil, a higher
Polymers 2020, 12, 2241 26 of 28

mineral surfaces. The residual oil saturation decreased for all aged Nordhorn core cases compared to
non-aged samples with alkali and alkali–polymer.
The brine composition did not yield significant changes in the oil production rate or ultimate oil
recovery when the formation brine or test water was used for initial saturation in the case of non-aged
(water-wet) cores. For aged (neutral to oil wet) core plugs saturated with high TAN oil, a higher
production rate was detected when the formation water was used for primary saturation and the
alkali–polymer solution was used as a displacing fluid. For the low TAN oil, the divalent ions did not
play a role in the case of aged cores with the implementation of the alkali–polymer solution.
According to the observed data, core mineralogy is linked to wettability alteration. Core samples
containing 10% clay content exhibited neutral to oil-wet behavior even when the core was not aged.
For high TAN oil, the Keuper (high clay content) core plugs showed a significant decrease in the
production rate and ultimate oil recovery, indicating a strongly oil-wet system. During the application
of the alkali–polymer solution with high TAN oil, the oil-wet sample returned to a water-wet state,
and higher ultimate recovery was achieved. In the case of the low TAN oil, a minor improvement in
oil recovery with the alkali–polymer solution was observed, meaning that no oil detachment from
the mineral surfaces occurred. Overall, core plug mineralogy tremendously affects the process of
wettability alteration due to aging and the implementation of chemical solutions; substantial wettability
change effects were observed particularly when alkali was injected.

Author Contributions: Data curation and original draft preparation, V.A. Conceptualization and validation,
R.E.H. Supervision and editing, T.C. Review and editing, format, and analysis, M.T. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: The authors thank OMV E&P GmbH for granting permission to publish this paper.
Conflicts of Interest: The authors declare no conflict of interest.

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