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Alkaline Surfactant Polymer Flooding What Happens
Alkaline Surfactant Polymer Flooding What Happens
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6 authors, including:
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Multiscale modelling of Low Salinity Waterflooding in Enhanced oil Recovery View project
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Yara Alzahid, Peyman Mostaghimi, Majid Ebrahimi Warkiani, and Ryan T. Armstrong, The University of New South
Wales; Vahid Joekar-Niasar and Nikolaos Karadimitriou, The University of Manchester
This paper was prepared for presentation at the SPE Europec featured at 79th EAGE Conference and Exhibition held in Paris, France, 12–15 June 2017.
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Abstract
Alkaline-surfactant-polymer (ASP) flooding is a Chemical Enhanced Oil Recovery (CEOR) method
whereby alkali, surfactant and polymer are injected as the same slug. It is one of the most promising world-
wide focus of CEOR research and field trials, due to the unique synergy of the three chemical components.
Polymers increase the viscosity of injected water, which improves macroscopic sweep efficiency by
stabilizing the displacing front and counteracting heterogeneity effects. Surfactants, on the other hand,
decrease the interfacial tension between the injected water and crude oil, which improves microscopic
displacement efficiency by mobilizing trapped oil. Alkaline chemicals generate soap when reacting with
crude oil, which reduces surfactant adsorption to grain surfaces. To fully understand the flow mechanisms
in oil reservoirs and develop efficient recovery methods, it is essential to recognize the physics at the pore
scale since this is the length scale at which capillary-trapped oil is mobilized. We develop an experimental
micro-scale approach in which oil recovery is analyzed using microfluidics. The micromodels are fabricated
based on: (1) a pore network generated via a Delaunay triangulation with an average pore size of 60µm,
(2) X-ray micro-Computed Tomography images of Bentheimer sandstone with resolution of 4.95µm, and
(3) a fractured network with a porosity of 10%. The networks are etched into silicon wafers and used to
fabricate poly dimethyl siloxane (PDMS) microfluidic devices. We compare not only oil recovery with ASP
flooding between different porous networks but we also study displacement mechanisms and pore scale
emulsion formation for ASP formulations that exhibit Winsor Type II+, II- and III behaviour. Our studies
elucidate micro-scale oil recovery mechanisms for different ASP flooding scenarios. Our results provide
direct visualization of the micro-scale phenomena occurring during ASP flooding and will guide further
studies to target effective ASP flooding scenarios.
Introduction
Chemical enhanced oil recovery (CEOR) uses three main chemical compounds to recover additional oil,
which are alkaline, surfactants and polymer. Alkaline and surfactant contribute to lowering the interfacial
tension (IFT) between water and oil, which helps mobilize trapped oil in the pores. Alkaline however also
generates soap in-situ when reacting with crude oil and helps in the reduction of surfactants adsorption
on grain surfaces, both alkaline and surfactant aid in improving the microscopic displacement efficiency.
2 SPE-185832-MS
Polymers contribute to CEOR by stabilizing the displacing front by modulating the viscosity of injected
water, thereby improving the macroscopic sweep efficiency. Alkaline-surfactant-polymer (ASP) flooding
utilizes the aforementioned chemicals, and by combining the injected surfactant and in-situ surfactant
generation with controlled mobility of oil from the polymer, gives ASP flooding a potential advantage over
other CEOR methods. It is one of the most promising world-wide focus of CEOR research and field trial,
due to the synergy of these three chemical components (Olajire 2014). An average of 22% incremental oil
recovery (IOR) has been reported when evaluating 21 fields trails that implemented ASP flooding (Sheng
2013). ASP flooding aims to enhance both the microscopic displacing efficiency by increasing capillary
number (Nc) and decreasing IFT and the macroscopic displacing efficiency by improving the mobility
number (Nm).
Analysing the displacement patterns in multiphase flow is crucial for understanding transport properties.
Lenormand (1990) reported that there are three main displacement patterns that are achieved in multiphase
flow: (1) viscous fingering, (2) capillary fingering and (3) stable displacement. These patterns are
characterized by capillary number (Nc) and mobility number (Nm). Nc shows the effect of viscous to
interfacial tension forces, which is represented as
(1)
where μ is dynamic viscosity (Pa·s), u is brine velocity (m/s), and σ is the interfacial tension (N/m) between
oil and brine.
Nm is defined as the ratio of invading fluid viscosity to the defending fluid viscosity. Viscous fingering or
unstable displacement occurs when the pressure drop is negligible in the invading fluid (large Nm). Capillary
fingering; however, occurs when the injection rate is very low and viscous forces are negligible in both
fluids. Lastly, stable displacement occurs at high flow rate when capillary forces are low and with negligible
pressure drop in the defending phase (small Nm). Figure 1 displays a phase diagram for the three unique
displacement regimes that can occur.
Figure 1—The phase diagram showing the three displacement patterns of non-reactive flow in porous media.
Microfluidics is defined as the study of fluids at a small scale, ranging from microliters to picolitres.
These studies can be of interest to multiple fields of study within science and engineering. Applications
include drug development, biomedical analysis, genetics, proteomics, and energy conversion (Kjeang et al.
2009; Lifton 2016; Whitesides 2006). An advantage of using microfluidics is that that it allows for small
sample volumes and reagents, providing low cost, fast high-resolution analysis and a smaller footprint in
comparison to other analytical devices (Whitesides 2006; Zhao & Middelberg 2011). Most of the current
research in microfluidic systems has been carried out in poly (dimethylsiloxane), or PDMS, which is a soft
elastomer that is optically transparent,. In petroleum engineering studies, what has been extensively studied
in the past is the use of glass-etched micromodels based on network patterns (Meybodi et al. 2011), and the
SPE-185832-MS 3
results of which are often correlated and included in pore-network models to compute multiphase transport
properties (Lenormand 1990; Culligan et al. 2006). Currently, 3D representations of rock microstructure
can be generated using micro-computed tomography (micro-CT), focused ion beam-scanning electron
microscopy (FIB-SEM) and/ior nuclear magnetic resonance (NMR) imaging. These data can be used to
generate 2D relizations of the pore space that can be used for further microfluidic investigations. However,
important fluid-rock interactions, such as wetting characteristics, are difficult to recreate (Gunda et al.
2011). Therefore, there is a need for experimental studies at the micro-scale to validate and improve
these simulations to understand multi-phase flow and in particular surface properties. Gunda et al. (2011)
generated the so-called "Reservoir-On-a-Chip" (ROC) and investigated the displacement of non-wetting
fluid by wetting fluid using ROC. They generated the pore network via a Delaunay triangulation routine
in Matlab, which was then imported in AutoCAD, and lastly transferred to a glass substrate. They used
piranha solution and plasma reactive ion etching (ICPRIE) to ensure a water-wet environment. Buchgraber
et al. (2011) reported the use of a microfluidic device of a Berea sandstone pattern etched into silicon to
study polymer flood displacement efficiency of viscous oil in a water-wet environment. In addition, Nilsson
et al. (2013) developed a hydrophobic microfluidic sandstone device from micro-CT sandstone images to
investigate the effect of surfactant fluid rheology on oil recovery. Gerami et al. (2016) used PDMS chips of
a realistic coal cleat system to measure relative permeability by monitoring the liquid recovery at recorded
saturations after breakthrough. Pore network modelling was also conducted in this study to predict relative
permeability curves, which was in agreement with the experiments.
In this manuscript, we analyze the phase behaviour and IFT of three surfactants types with varying
salinities to select an optimum surfactant. We then compare oil recovery curves using surfactant floods
with different salinities in a fractured model and oil recovery curves of AS and ASP floods at optimum
salinity for a sandstone network. Lastly, we compare displacement mechanisms using two models: (1) pore-
network model generated from Delaunay tessellation and (2) a representation of sandstone rock from micro-
CT images.
in Table 2. The salinity of the solutions was varied by adding sodium chloride (NaCl). For each salinity,
a 10 mL test tube was prepared that consisted of 5 mL of surfactant with cosolvent or ASP solution with
cosolvent and 5 mL of n-decane (mixing ratio of 1:1). Test tubes were shaken and then allowed to separate
at ambient and stagnant conditions. The solubilization was analyzed by visually measuring the volumes of
the formed phases, optimum salinity was then selected based on equal oil and water solubilisation ratios
for the emulsion phase.
Pore Morphologies
A benchtop helical micro-CT scanner at the Australian National University was used to image a Bentheimer
sandstone sample (4.5 mm diameter and 10 mm long). The resolution of this image was 4.95µm, with an
image size of 891 × 891 ×1440 voxels. The core was imaged at 65 amp and 100 meV. The second network
pattern was a pore network generated via a Delaunay triangulation routine in Matlab, as previously described
in Gunda et al. (2011), with an average pore size of 60µm. The third pattern was generated by micro-CT
images of fractures that were overlayed using an image quilting technique to make a fracture network.
Figure 2 shows the patterns used for this project.
Figure 2—Patterns of different chips used. (a and b) shows the patterns used for IOR and micro-
scale imaging of sandstone and fracture models, respectively. (c and d) show the models used
for displacement studies of sandstone and the Delaunay tessellation pore networks, respectively.
SPE-185832-MS 5
Experimental System
New PDMS microfluidics chips were generated for each experimental study to ensure no contamination
occurred between sequential experiments. The chips were first injected with their respective water salinity
meaning that the salinity matched the salinity at which the subsequent EOR treatment would be conducted.
Then decane (Sigma Aldrich, USA) is injected to achieve a 90-80% oil saturation. Surfactant at different
salinity was mixed with 1.0 wt.% food coloring the color of which depends on the experiment conducted
and is explained in the results section (AmeriColor, Placentia, CA, USA) and was then injected at a capillary
number of 10−7. A high-precision infusion syringe pump (Fusion 100 Infusion, Chemyx, Australia) is used
to monitor and control the flow rate. Images are taken using a CCD digital camera (Zeiss, Axiocam 506
color) coupled with a stereo zoom microscope (Zeiss, Axio Zoom V16) with frame resolution of 2752 ×
2208 pixels. Figure 3 (a) shows the experimental setup used.
Figure 3—(a) Experimental set-up for IOR and visualization experiments and (b) displacement experiments set-up
For the IOR tests, oil recovery is measured via image processing of the captured images. We used
ImageJ with the assumption of a 2-dimensional fluid system meaning that only a single phase can occupy a
given pixel. For displacements experiments, images were collected using a digital camera (GH4, LUMIX)
6 SPE-185832-MS
and these images were then analyzed using ImageJ. A high-precision infusion syringe pump (Fusion 100
Infusion, Chemyx, Australia) was also used to inject the different fluids. Figure 3 (b) shows the set up for
the displacement experiments.
From Table 3, 0.5% (w/v) of ENORDET J13131showed the lowest IFT and thus was chosen for phase
behavior tests with varying NaCl content. Figure 4 shows the phase behavior tests and Table 4 reports the
volume of emulsion formed at under-optimum, optimum and over-optimum salinities.
Figure 4—Phase behaviour of 0.5% ENORDENT J13131 and 2% Butanol at varying NaCl content (3.6 - 4.5 % w/v). The
red boxes indicate the middle phase, decane is on top of the middle phase and brine is shown as the clear solution.
SPE-185832-MS 7
Surfactant-oil-water system Salinity (NaCl% w/v) Volume of Emulsion (%) Vw (%) Vo (%)
3.7 29 25 4
3.8 27 22 5
Optimum 3.9 26 16 10
Over optimum 4 19 10 9
4.1 16 6 10
4.2 31 11 20
4.3 30 5 25
4.4 35 5 30
4.5 35 3 32
Solubility Measurements
Water and oil solubility ratios, γw and γo, which are defined as the amount of oil or water that is soluble in the
microemulsion phase, were determined by visually inspecting the phase behaviour tubes shown in Figure
4. Vw is the volume of emulsion below the middle line (at 5ml) and Vo is the volume of emulsion above
the middle line. Under optimum salinity is when Vw > Vo, which displays Winsor Type II- phase behaviour.
Conversely, over-optimum salinity occurs when Vw < Vo, which displays Winsor Type II+ behaviour. The
optimal salinity is when Vw is equal to Vo, which was found at 3.9% salinity. The solubility coefficients
are reported in Figure 5.
Figure 5—Solubility ratios of surfactant in aqueous and oil phases. Water (γw) and oil (γo) solubility ratios as a
function of salinity (NaCl% w/v). Increasing NaCl content, the water solubility decreases, as opposed to oil solubility.
As discussed in Unsal et al. (2016), the equilibration time for the middle phase formation is important
to note for the different salinities. Similar to their findings, under and optimum middle phase formation
occurred at a much faster rate than the over optimum tubes. Within 5-7 hours, the emulsion at under-optimum
and optimum conditions appeared and reached equilibrium. However, the over-optimum salinity took 2 days
to show the emulsion phase and reach equilibrium. Consistent with the findings from Unsal et al. (2016),
salinity plays a pivotal role in the surfactant equilibration times.
8 SPE-185832-MS
Figure 7—(a) The viscosity of (0.5% NaCO3, 0.5% ENORDET J13131 and 0.1% HPAM w/v) at 3.9 NaCl% (w/
v) in response to shear rate. (b) Viscosities of ASP formulations (0.5% NaCO3, 0.5% ENORDET J13131
and 0.1% HPAM w/v) at different salinities (3.6%-4.5% NaCl w/v) at a representative shear rate of 6.91 s−1.
Figure 9—IOR vs. PV of Surfactant flooding and ASP flooding at optimum salinity in Sandstone pattern
Figure 10—Surfactant (0.5% ENORDET J13131 w/v) oil (decane) interactions at different salinities in fractured network. (a-
d) under-optimum with 3.6% NaCl (w/v), (e-h) optimum with 3.9% NaCl (w/v) and (i-l) over-optimum with 4.5% NaCl (w/v).
We also investigated micro-scale images of the AS and ASP formulations at 3.9% NaCl (w/v) in the
sandstone network. The AS solution consisted of 0.5% ENORDET J13131 surfactant (w/v), 0.5% NaCO3
(w/v), 3.9% NaCl (w/v) and green dye (1% w/v). Figure 11 (a) shows an overview of the initial stages
of the AS flooding. Some channels in the chip (shown on the left of Figure 11 a) were difficult to access
with AS flooding and thus some oil was trapped in these channels. Figure 11 (b-c) shows the mixing of
AS with decane (shown in middle section of Figure 11 b-d). Figure 11 (a-d) images are similar to images
obtained in previous sections in terms of how the surfactant is mixing with decane. After the AS flood, an
ASP slug was injected as shown in light red in Figure 11 (e-h). The ASP slug consisted of 0.5% NaCO3
(w/v), 0.5% ENORDET J13131 (w/v), 0.1% HPAM (w/v) and 1% red dye (w/v). It can be concluded from
the images obtained that ASP successfully swept most of the trapped oil, due to altering the mobility ratio,
hence improved sweep efficiency. Figure 11 (e-h) show the ASP sweeping the AS slug (green) and some oil
trapped in the pores with the AS slug. Figure 11 (h) shows the final stage of ASP injection, and it can be seen
that all of the liquid present in the chip is the ASP with some interstitial water present in the narrow channel
at the top and bottom of the image and one section in the middle of the chip showed the AS slug left behind.
Figure 11—AS and ASP flooding in sandstone patterned PDMS chip at 3.9% NaCl content (w/v). (a-d)
Alkaline (0.5% NaCO3 w/v), surfactant (0.5% ENORDET J13131 w/v) flooding. (e-h) Alkaline (0.5% NaCO3
w/v) surfactant (0.5% ENORDET J13131 w/v) and polymer (0.1% HPAM w/v) flooding. Dark red is connate
water (4.5% NaCl w/v), decane is transparent, green is the AS solution, and light red is the ASP solution.
12 SPE-185832-MS
Figure 12—Displacement of decane oil (transparent) in a Delaunay tessellation pore network by (a-b) surfactant flooding
of 0.5% ENORDET J13131 (w/v) at a salinity of 3.9% NaCl (w/v), and (b-c) Alkaline (0.5% NaCO3 w/v) surfactant (0.5%
ENORDET J13131 w/v) and polymer (0.1% HPAM w/v) flooding at 3.9% NaCl (w/v). Injection of surfactant and ASP floods were
coloured with red dye and shown here in black, decane oil is transparent. Both a and c show the initial stage of surfactant
flooding and ASP flooding, respectively. The final stages of each flood type after breakthrough are shown in b and d.
SPE-185832-MS 13
Lastly, we investigated the displacement of AS and ASP in the sandstone chip. Each flood was colored
in red (shown in the results as black) and performed in a new PDMS chip that was saturated with decane oil
(transparent). During the AS flood, the start of the injection (Figure 13a) displayed a very unstable front,
and the fluid moved through fracture lines that were generated due to the mirroring of the sandstone image
to achieve the chip dimensions of 58×46 mm2. At the end of the AS displacement (Figure 13 b), it can be
seen that very little oil was recovered and a slightly unstable flood front was visible, due to the low intensity
of the dye captured in the images. When ASP was injected (Figure 13 c), the flood front apeared more stable
than the previous AS flood, and towards the end of the flooding (Figure 13 b), the dye was intense in the
image, suggesting a stable front with better sweep efficiency, as exhibited from the ASP displacement in
the previous section.
Figure 13—Displacement of decane oil (transparent) in a representative sandstone pore network by (a-
b) Alkaline surfactant flooding of 0.5% NaCO3 (w/v) and 0.5% ENORDET J13131 (w/v) at a salinity of 3.9%
NaCl (w/v), and (b-c) Alkaline (0.5% NaCO3 w/v) surfactant (0.5% ENORDET J13131 w/v) and polymer (0.1%
HPAM w/v) flooding at 3.9% NaCl (w/v). Injection of AS and ASP floods were coloured with red dye and
shown here in black, decane oil is transparent. Both a and c show the initial stage of surfactant flooding and
ASP flooding, respectively. The final stages of each flood type after breakthrough are displayed in b and d.
14 SPE-185832-MS
Conclusion
We demonstrated the phase behavior of a selected surfactant exhibiting Winsor type II+, II- and III behavior.
We characterized the solubility ratios, and determined the optimum salinity being 3.9% NaCl (w/v). We
measured viscosities of ASP formulations with varying NaCl content, which resulted in a shear thinning
behavior of the solutions and a viscosity ranging from 8-5 mPa.s at a shear rate of 6.81 s-1. We then
conducted microfluidic flow experiments to measure IOR for different flooding scenarios and studied the
micro-scale mixing of the phases and components. We analyzed IORs in two different PDMS models, a
fractured network and a sandstone network. The fracture models analyzed IORs of surfactant floods at
varying NaCl content (3.6%, 3.9% and 4.5% (w/v)), with the highest IOR achieved by the under-optimum
salinity (3.6% NaCl w/v), proving that salinity has an effect on the efficacy of the surfactant to produce
more oil. With the sandstone model, we tested the IOR achieved by surfactant flooding and AS followed
by ASP flood at optimum salinity, and as expected, the ASP flood achieved the highest IOR. ASP resulted
in an IOR increase of 72.2% when compared to AS flooding at optimum salinity. These IOR studies were
then visualized using the same two models (fracture and sandstone) at the micro-scale. The images obtained
complemented the IOR results, as we were able to visualize the interaction of the surfactant with oil at
different salinities and the interaction of AS and ASP with different network patterns saturated with decane
oil. Lastly, we demonstrated the displacement mechanisms of surfactant flooding, AS and ASP using the
Delaunay tessellation pattern and a sandstone pattern. From these displacement studies, we found that
displacement efficiency is dependent on, as expected, the viscosity of the displacing fluid. Also, the pore-
scale morphology of the porous networks tested provided significantly different displacement patterns for
the exact same capillary and mobility numbers.
Acknowledgment
The authors would like to thank EXPEC ARC at Saudi Aramco, specifically the Chemical EOR group for
allowing us to use their spinning drop and viscometer machines and obtain results that were essential to
this study. In addition, the authors would like to acknowledge the Microfluidics lab at the Mechanical and
Manufacturing engineering at UNSW for their support with the PDMS visualization studies.
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