pubs.acs.

org/EF Article

Water- and Surfactant-Based Huff-n-Puff Injection into

Unconventional Liquid Hydrocarbon Reservoirs: Experimental and
Modeling Study
Alexandra Scerbacova,* Elena Mukhina, Denis Bakulin, Alexander Burukhin, Anastasia Ivanova,
Alexander Cheremisin, Margarita Spivakova, Alexandra Ushakova, and Alexey Cheremisin

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ABSTRACT: The combination of horizontal well drilling and multistage hydraulic

fracturing is currently the leading method for developing shale reservoirs. However, oil
recovery from these techniques does not exceed 10%, and supporting technologies are being
sought. The injection of water or surfactant solutions in huff-n-puff mode is often considered
an enhanced oil recovery option for shales, which can be used alone or in combination with
other technologies, such as CO2 injection. This study presents experimental and numerical
investigations into the huff-n-puff treatment of low-permeability shale cores using water-
based compositions. Additionally, an attempt was made to displace oil by applying a
nanofluid booster. Computational tomography was used as one of the methods to determine
the oil recovery factor. Two core flooding tests with different designs and injection fluids
were conducted. The first experiment involved brine filtration in one direction, followed by
nanofluid injection. Second core flooding/huff-n-puff test implied injection of a 0.5 wt %
surfactant solution. The results showed that the oil recovery factor achieved using brine was approximately 50% and decreased after
nanofluid injection until 31%. Besides that, there was no significant effect from the use of the surfactant. At the same time, critical
issues were observed regarding a decrease in core permeability. A numerical simulation of the second experiment was performed to
restore the relative phase permeability (RPP) in the surfactant−oil system and to study the dependency of the capillary number
logarithm on the miscibility coefficient. The simulation showed a good convergence in terms of the recovery factor values, with an
error of ∼1.5%.

1. INTRODUCTION tigated and applied in unconventional reservoirs. Such high-

Developing unconventional liquid hydrocarbon reservoirs pressure gases as carbon dioxide (CO2), nitrogen (N2),
(ULRs), such as tight and shale formations, is one of the methane (CH4), and rich and lean natural gases are applied.
petroleum industry’s priorities today.1,2 Oil shales are The injection mode of fluids into the ULR can be continuous,
characterized by extremely low porosity and permeability multiple-well cyclic, and huff-n-puff.1,5 The continuous flood-
values, low pore connectivity, and no hydrocarbon migration in ing mode implies fluid injection into one well, fluid flow, and
the reservoir. Thus, the typical permeability of shale reservoirs production from another nearby well. It is worth noting that
is below 0.001 mD, which is between 100 and 10,000 times the matrix must have sufficient permeability and connectivity.
less than that in conventional layers.3 The porosity varies from During multiple-well cyclic injection, the fluid injected into a
5 to 15% in contrast with 20−30%, which is expected for well is left to soak by the diffusion mechanism and then
conventional reservoirs.4 The pore radii in shales lie at the recovered from another well. The third technique is a modified
nanoscale, whereas in conventional deposits, at the micro- cyclic injection, which includes fluid injection, soaking, and
scale.1,3,5,6 All these factors cause high capillary pressure in the production from the same well and is known as huff-n-
reservoir and thus obstruct water injection, making the puff.12−15 During the first stage (injection), the fluid is
production extremely challenging.7
Hydraulic fracturing and horizontal drilling currently applied
for the ULR extract only 10% of the original oil in place Received: April 24, 2023
(OOIP) and are associated with economic and environmental Revised: June 27, 2023
risks. Such a low recovery is related to a sharp decline in good Published: July 12, 2023
productivity (about 20% of the initial yield) during the first
year of operation.8−11 As follows, different gas- and water-
based enhanced oil recovery (EOR) techniques are inves-

© 2023 American Chemical Society https://doi.org/10.1021/acs.energyfuels.3c01344

11067 Energy Fuels 2023, 37, 11067−11082
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introduced into the reservoir accompanied by reservoir of various surfactant formulations into low-permeable cores
pressure growth until the necessary soaking pressure is from the Middle member of a Bakken shale reservoir. The oil
reached. The second stage (soaking) implies the shut-in of recovery value achieved 40% in the result of a spontaneous
the well for a period of time to let the pressure stabilize and the imbibition test in Amott cells. Tu and Sheng21 conducted a
fluids interact. The third stage (puff) refers to fluid production series of spontaneous imbibition tests on Eagle Ford core plugs
assisted by reservoir pressure depletion. The cycles can be using surfactants with different abilities to decrease oil−water
repeated while the production process remains cost-effective.16 interfacial tension (IFT varied from 0.01 to 3.0 mN/m). The
Chemical EOR with water-based fluids such as fresh or low better oil recovery was achieved with a nonionic surfactant
salinity water (LSW), alkaline, surfactant solutions, or with a higher IFT value of 3.0 mN/m and a good wetting
nanofluid can also be implemented in ULRs.5,9,17 Recently, ability, thus confirming that capillary force has the main
many works studied cyclic water injection into unconventional effect.11,21 The experimental results were proved with
formations in the laboratory and during field pilot projects. Yu simulation studies. Further, the authors studied the pressure
and Sheng16 compared the performance of water and N2 gas effect on the imbibition process,31 thus comparing forced and
huff-n-puff under identical conditions, varying the injection spontaneous imbibition. It was found that high soaking
pressure and soaking time. The authors found that oil recovery pressure negatively influences imbibition and water wetness
from the water-based test was lower than that from the gas is crucial. Moreover, cluster distance and matrix permeability
one. Moreover, oil was effectively extracted in the first four are also essential factors.22
cycles only. It is known that pilot water huff-n-puff tests were According to Sheng,2 huff-n-puff surfactant technology is
conducted in the USA (Bakken), Argentina, and China.1,2,5 awaited to have a better effect on oil production than
Todd et al.18 described seven huff-n-puff pilot projects based surfactant flooding in the ULR. Cao et al.32 conducted a
on various fluids (water, natural gas, and CO2) implemented in series of surfactant huff-n-puff laboratory tests using water-wet
the Bakken formation. The injection of produced water artificial cores with extra low permeability similar to Dagang
resulted in increased oil recovery due to frac-hits. Li et al.19 Oilfield. The authors used cylindrical cores and six different
discussed a development scheme for Chang 7 Field that is plate-fractured models to study the oil-increasing effect in
suitable for water flooding. Depletion production employing micro-, meso-, and macropores. In the result, the oil recovery
volumetric fracturing of horizontal wells was suggested as a increased, but a rapid decline in oil production was observed
development strategy, followed by water huff-n-puff. As a after each cycle. According to the literature, surfactant-based
result, the daily production rate of the single well increased by huff-n-puff pilots were carried out in USA and China.2,5
∼78% after the first cycle. Han et al.20 reviewed water huff-n- Kazempour et al.33 described a selection and application of
puff tests in five wells in the Huanjiang oilfield. The technique wettability-altering agents that resulted in increased oil
implementation allows improving the reservoir pressure, and production from Middle Bakken and Niobrara formations
water displacement has a positive effect on adjacent wells. The under harsh conditions (110 °C, salinity of 220 g/L). A field
average oil production rate raised from 0.97 to 1.04 m3/day. trial test was conducted in a horizontal 30-stage hydraulically
Generally, the results showed that huff-n-puff water injection fractured well that had been in production for ∼2.5 years
worked.2 already. The injection of wettability modifiers caused the oil
The performance of water-based compositions could be recovery to increase by 25%. Besides that, projects that used
increased by adding surfactants.5,21,22 Primarily, surfactants systems of nonionic surfactants dissolved in CO2 as wettability
were applied as components of fracture fluids capable of alteration agents in unconventional reservoirs are known.34,35
reducing the capillary pressure, removing the water blockage, Such solutions modify the rock surface from oil-wet to water-
and consequently increasing the flow back.9,23,24 The main wet. The gas chromatography analysis conducted after soaking
functions of surfactants are capillary force reduction, interfacial experiments showed that surfactant promoted extraction of
tension (IFT) reduction, and hydrophilization of the rock heavier oil components.
surface, followed by promotion of oil filtration.25,26 In ULRs, A number of research papers that describe water- and
surfactants can facilitate water imbibition into the matrix of surfactant-based huff-n-puff projects held in the laboratory
shales due to the more water-wet surface.10,27−29 However, the were published recently. An overview of thermal, gas, and
screening criteria of surfactants for ULRs is still a subject of chemical EOR for shale formation was discussed by Ushakova
debate.5,30 Sheng11 discussed the types of surfactants which et al.36 The current project is focused on the investigation of
should be selected for ULRs and compared the importance of the water and surfactant huff-n-puff process in a shale reservoir
the two primary surfactants’ functions: interfacial tension by experimental work and simulation studies. The permeability
decrease and wettability alteration toward more water-wet of the cores used was less than 1 μD, the reservoir temperature
surface. The author analyzed the spontaneous imbibition was 110 °C, and the pressure was 23.4 MPa. The main purpose
process using simulation studies, theoretical analysis, and of this work was to investigate the water-based composition
published experimental data. It was concluded that the water- injectivity into shale plays and evaluate the effectiveness of this
wet state of rock and high IFT values (∼20 mN/m) are crucial technology. The recovery factor was determined after each
for effective spontaneous imbibition. In such cases, oil recovery stage of the experiment. The tests were designed for the
is comparable to conventional reservoirs.11 evaluation of huff-n-puff water injection. The surfactant and
The ability of surfactants to promote fluid penetration nanofluid screening is described in our previous work.37
process due to wettability alteration toward water wet was
proved by numerous researchers. A considerable number of 2. EXPERIMENTAL STUDY
experiments were carried out to study the spontaneous 2.1. Materials. 2.1.1. Oil. Oil from one field with shale plays was
imbibition of water and surfactant solutions into unconven- collected for the research, degassed, and dehydrated first until the
tional rocks, as a huff-n-puff-treated well is comparable with a water content was less than 0.01%. Oil density was measured with
huge Amott cell.27 Shuler et al.28 tested the penetration ability Anton Paar DMA 4200 M under reservoir temperature and at

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ambient and reservoir pressures, Table 1. The viscosity of oil was

evaluated with a rheometer Anton Paar MCR 302. The composition

Table 1. Oil Density at Different Pressures and

Temperatures
pressure, MPa temp, °C density, g/mL
Degassed Oil
atmospheric 90 0.7708
reservoir, 23.4 110 0.7757
Oil Modified with 15 wt % 1-Iodooctane
atmospheric 90 0.8226
reservoir, 23.4 110 0.8264

was determined through chromatographic analysis with Agilent 7890B

SimDis. Oil with the original composition was used in the first core
flooding test. In the second test, 15 wt % of 1-iodooctane (IC8) was
added to the oil as a contrast for the X-ray computed tomography
(CT) scan. A comparison of the chromatograms is shown in Figure 1.
Figure 2. Structure of the surfactant used in the study.

mN/m, the static adsorption onto crushed rock is 0.43 mg/g-rock,

and the contact angle on the rock surface is 17.38°37 (Table 3).

Table 3. Properties of Fluids Used in This Study

density, g/cm3
fluid (23.4 MPa, 110 °C) IFT, mN/ma CA, dega
brine 14.01 101.39
brine + KI 1.0844 10.70 83.05
brine + NP 27.26
brine + surfactant 0.9750 1.41 17.38
brine + surfactant + 0.54 7.4
nanoparticles
a
Ambient pressure.

2.1.4. Nanoparticles (NP). As it was shown in our previous work,37

the dispersion with 0.005 wt % colloidal SiO2 nanoparticles (Table 4)

Table 4. Properties of Tested Nanoparticles

Figure 1. Chromatographic analysis of the oil sample. type formula appearance manufacturer

2.1.2. Brine. Artificial brine (a model reservoir water from a real silicon SiO2 30.4 wt % colloidal suspension Chimunivers,
dioxide (7−8 nm) Russia
target field) was prepared by dissolving a specified amount of salts
with a magnetic stirrer in a flask. Mineralization was 13.5 g/L, and its
composition is given in Table 2. The first core flooding test used a and 0.05 wt % surfactant illustrated the highest stability at reservoir
temperature (90 °C) and salinity (13.5 g/L). Moreover, this
Table 2. Initial Brine Composition dispersion illustrated the lowest IFT values (0.54 ± 0.01 mN/m)
compared to that of 0.05 wt % surfactant without nanoparticles (1.41
salt mass, g/L ± 0.08 mN/m). Furthermore, the contact angle of the rock sample
NaCl 12.740 after treatment with this dispersion equaled 7.4°, corresponding to a
strong hydrophilic preference. Therefore, this dispersion was used in
KCl 0.095
further filtration experiments presented in this work.
CaCl2 0.486
The dispersion of the surfactant and nanoparticles was prepared as
MgCl2 0.179 follows: at the beginning, the nanoparticles were dispersed in distilled
TDS 13.5 water for 3 min using a Bandelin Sonopuls homogenizer to reduce the
polydispersity of the particles. After that, the surfactant was added to
such dispersions so the surfactant concentration equaled 0.05 wt %.
modified brine with additional 15 wt % KI as a contrast for the CT Further, the prepared solution was again dispersed for 3 min using a
scan. Salts NaCl, KCl, CaCl2·2H2O, MgCl2·6H2O, and KI were of homogenizer. Then, different salts were added to the prepared
chemical grade and used as received. dispersion so that the concentrations were consistent with previous
2.1.3. Surfactant. In the result of the screening described in ref 37, experiments (Table 2) with a total sum of 13 g/L. Finally, the
one surfactant was selected for the huff-n-puff test, sodium fatty acid dispersion was again dispersed for 3 min with a homogenizer. The
methyl ester sulfonate. The structure is shown in Figure 2. The properties of all fluids used in the core flooding tests are shown in
surfactant appears as yellowish granules and dissolves in water when Table 3.
heated to 60 °C. The critical micelle concentration (CMC) of the 2.1.5. Core Samples. Two cylindrical core samples with identical
surfactant is 0.025 wt %, and the operating concentration was chosen properties (one cylinder was divided into two parts to obtain
as 0.05 wt %. At this point, the IFT on the boundary with oil is 1.41 doublets) were selected from a batch of samples cut from the reservoir

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Table 5. Characteristics of Core Samples

test length, cm diameter, cm porosity, % permeability, mD volume, cm3 pore volume, cm3
water/nanofluid flooding 2.975 2.958 12.110 0.003177 20.44 2.48
surfactant huff-n-puff 3.139 2.947 11.354 0.004200 21.41 2.43

material. The core was not extracted and held to a constant mass by particles from a solution of 0.005% nanoparticles and 0.05% surfactant
vacuuming. The cylinders were examined to determine the porosity in 13.5 g/L on a TF series filter with a dense matrix with a pore size of
and permeability values and the presence of cracks. The porosity was 0.5 μm. The studies were carried out using a high-pressure pump, a
measured with an automated gas permeameter-porosimeter “PIK-PP” differential pressure sensor, L-series fine adjustment valves, a control
using helium as a probe gas as it does not cause a washout of salts and computer, and the necessary signal converters. A measuring cylinder
hydrocarbons from the pore space. The permeability was measured was used to measure the volume of liquid fluids at the outlet.
with a Cydarex Darcypress instrument.38 Microstructure imaging was Weighing of the TF series filter was carried out on an analytical
performed with a GE phoenix v|tome|x L240 X-ray computed balance.
tomography scan; no cracks or defects were observed in the selected After being brought to a constant mass in 24 h in a vacuum cabinet
samples. The characteristics and dimensions of the samples are given at a temperature of 80 °C, the TF series filter was connected to the
in Table 5. The mineral composition was determined with an X-ray differential unit. In the beginning, an 18.17 cm3 volume of solution
powder diffractometer Huber G670, and organic matter content was was pumped through the TF series filter at a flow rate of 0.5 cm3/min
obtained through Rock-Eval pyrolysis analysis with a HAWK in order to accumulate statistics. The stationary mode of filtration at a
Resource Workstation. The results are shown in Table 6. flow rate of 0.5 cm3/min was observed starting from 26 min from the
beginning of the experiment. The next step was to pump 731.83 cm3
Table 6. Mineral Composition of Rock Samples Used in the of solution through the TF series filter. First, 101.84 cm3 was pumped
Study with a flow rate of 3 cm3/min, then 283.99 cm3 with a flow rate of 6
cm3/min, and 346 cm3 with a flow rate of 9 cm3/min.
component content, % 2.2.3. Core Flooding Experimental Setup. The laboratory setup
total organic carbon (TOC) 3.39 for core flooding tests is a modernized PIK-OFP/EP apparatus from
quartz 92.2 Geologika.41,42 The central units are three high-pressure pumps,
illite 6.0 pressure and differential pressure sensors, pressure gauges, a
albite 1.1
backpressure regulator (to maintain reservoir pressure at the outlet),
valves, and a controlling computer with signal transducers. A
pyrite 0.7
graduated (0.2 mL) vial and scales are used to measure the volume
and mass of liquid fluids at the backpressure regulator (BPR) outlet.
2.2. Methodology. 2.2.1. Size Determination of Nanoparticle- The gas is diverted to a gas chromatograph to determine the gas
Augmented Surfactant Solutions. For a preliminary assessment of composition and a gas meter to measure the volume. Continuous
the possibility of filtration of nanoparticles through low-permeability supply of fluids is ensured by a system of pneumatic valves and
core samples, a comprehensive study of the size of nanoparticles was pressure sensors under computer control. The scheme is shown in
carried out using Malvern Zetasizer Nano ZS. Different solutions with Figure 3.
and without nanoparticles were tested in order to estimate the size of 2.2.4. Experimental Design. Two core flooding tests were
aggregates upon the addition of nanoparticles. The U-shaped capillary conducted in this study. The first test combined brine injection
cell was filled with 1 mL of the suspension and equilibrated for 3 min (recovery factor-1 (RF-1) was obtained) followed by a nanofluid
at 25 °C. Each measurement was performed with 3 runs and 100 sub- booster (RF-2 was determined), and all fluids were injected through
runs.39,40 one end in the same direction. The experiment consisted of five
2.2.2. Experimental Setup for the Test with a Mechanical Filter. stages, Figure 4. (1) The core holder with a core sample was placed in
This part of the study aimed to identify the retention of colloidal the heating chamber of the filtration unit and connected to the

Figure 3. Scheme of experimental setup, where 1 − heat chamber, 2 − three groups of two-piston pumps, 3 − piston column with water, 4 − piston
column with oil, 5 − pressure sensor and manometer at the core holder inlet, 6 − pressure sensor and manometer at the core holder outlet, 7 −
differential pressure sensors with a pneumatic valve system, 8 − bypass pneumatic valve, 9 − core holder, 10 − BPR, 11 − separator, and 12 −
crimp pressure maintenance pump.

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Figure 5. Design of the core flooding test with surfactant (2).

moil out
K OR =
moil in (1)
Figure 4. Design of the core flooding test with brine and NP (1).
moil out − mass of the oil degassed oil displaced from the core sample
during filtration; moil in − mass of the oil remained in the core sample
after filtration, determined by the difference between the masses of
hydraulic lines and then heated to a reservoir temperature of 110 °C. oil-saturated and core after filtration.
When the temperature was reached, the core holder with the sample For better accuracy, two additional coefficients were added to the
was vacuumed. Simultaneously, all the hydraulic lines of the unit were formula:
filled with oil, and the pressure in the system is raised. (2) The system
pressure was raised to the reservoir, and when the thermobaric • ωwater, mass % − mass fraction of water in oil, determined
conditions were reached (P = 23.5 MPa and T = 110 °C), oil filtration through Karl Fischer titration;
started. When the saturation was achieved, the system was cooled, the • ωLHC, mass % − mass fraction of light hydrocarbon
pressure was reduced gradually, and the core was extracted from the components evaporated during filtration under reservoir
core holder and placed into the CT scan. (3) The core model was conditions, determined by chromatography.
weighed and placed back into the unit after scanning. After oil Thus, true moil out was calculated as:
saturation and flushing of all lines, the brine was injected into the core
model. When oil displacement with brine was accomplished with 15% moil out (true) = moil out moil out × water + moil out × LHC (2)
KI, at least 3 PV of water was injected (by pump) until pressure drop
stabilization was attained. The model was then scanned to determine 2.2.6. Additional Method for Oil Recovery Factor Determination.
the oil recovery factor RF-1. (4) Second part of the experiment started Computational tomography (CT) scanning was used as a supporting
with repeated oil saturation in the “straight” direction, followed by CT method for the determination of oil saturation at each filtration stage.
scanning as described previously for the first stage of the experiment. The standard procedure of saturation calculations based on
(5) The nanofluid was injected into the core model, similar to tomography images is described in ref 44. The current study used
artificial brine injection. After scanning, the oil recovery factor RF-2 two contrasting tomography agents to compare their efficiency: KI
was determined. No KI was added to the nanofluid to avoid the was applied for the water phase when brine was tested as an oil
agglomeration of nanoparticles. displacement fluid in the experiment (1), and IC8 was applied for oil
The design of the second experiment was developed considering in the experiment (2) with surfactant filtration.
that the huff-n-puff method is performed in one well, which is both a
producer and injector.16,43 As this test used one displacing (imbibing) 3. NUMERICAL SIMULATION
fluid, four stages were included in the experiment, Figure 5. (1) Core In this work, a simulation of the experiment of oil displacement
holder with the core sample was prepared for the experiment as in the core with a surfactant solution was performed. The main
described previously for the first test. (2) The core model was
saturated with oil (15 wt % of 1-iodooctane was added to the oil as a goal was to restore the relative phase permeability (RPP) in
contrast for the CT scan) through one end in the forward direction the surfactant−oil system and the type of dependence of the
and then scanned. (3) Surfactant composition was injected through capillary number logarithm on the miscibility coefficient in
another end backward, and at least 3 PV of surfactant (by pump) was adapting the model to experimental data. The simulations were
injected until the pressure drop stabilized; the pressure drop should performed using Rock Flow Dynamics tNavigator simulation
not exceed 9 MPa. Then, the model was scanned, and the recovery software. The target objects were two shale core cylinders
factor RF-S1 was determined. (4) The second cycle of the huff-n-puff characterized by low permeability. The size of initial oil
test started with repeated oil injection through the first core sample reserves was considered as 194 cm3. The main parameters of
end, analogous to stage (2), followed by a second injection of the core material in the model are given in Table 7.
surfactant composition, analogous to stage (3). After that step, RF-S2
was calculated. As input data for the surfactant properties, interfacial tension
2.2.5. Oil Recovery Factor Determination. The main method used and static adsorption dependencies on surfactant concen-
for oil recovery factor determination was based on mass balance, tration were experimentally derived. The graphs of IFT and
working well with degassed oil. The oil recovery coefficient (KOR, %) static adsorption plotted versus surfactant concentration were
was calculated after the formula: reported in ref 37. When adapting the model to the
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Table 7. Main Parameters of Cores Used in Simulations model in the puff stage. The scheme of development indicator
adaptation is shown in Figure 6.
parameter value
grid dimension 15 × 15 × 60 4. RESULTS AND DISCUSSION
number of active cells 10,620
4.1. Filtration Experiment with Nanoparticle-Aug-
length, cm 3.079
mented Surfactant Solutions. Before the core flood test, it
diameter, cm 2.941
is important to investigate the sizes of the formed aggregates
porosity, % 11.8
between nanoparticles and surfactant molecules in order to
permeability, mD 0.003
compare them with core permeability and porosity. The size
rock density, kg/m3 2650
distributions were obtained for the series of dispersions−0.05%
pore volume, cm3 346
surfactant in 13.5 g/L, 0.005% SiO2 and 0.05% surfactant in
initial oil saturation, % 98
13.5 g/L, and 0.01% SiO2 in 13.5 g/L. The results are
initial reservoir pressure, bar 233.85
presented in Table 8. As can be seen from Table 8, the number
saturation pressure, bar 169

Table 8. Size Distributions of Different Dispersions with

Nanoparticles and Surfactants (Acceptable Particle Sizes
experimental results, these properties did not change. The
Are in Bold)
injection process was divided into several stages. The first one
was an injection of the surfactant (huff) when the injector INJ1 dispersion
was turned on with a limitation of 1 m3/day and surfactant 0.005% 0.05%
concentration of 5 kg/m3. The production restriction for SiO2 and surfactant in 0.01% SiO2 0.005% SiO2 and 0.05%
producer PROD1 was set as 1 m3/day. At the huff stage’s end, 0.05% 13.5 g/L in 13.5 g/L surfactant in 13.5 g/L
peak surfactant (without (without (after filtration through
wells PROD1 and INJ1 were shut down. The second stage was no. in 13.5 g/L nanoparticles) surfactant) a mechanical filter)
puff: switching injection well INJ1 to production PROD_OIL 1 12.36 nm 12.72 nm 8.21 nm
and production PROD1 to injection INJ_OIL and reverse oil 2 61.97 nm 50.60 nm 32.67 nm 46.32 nm
saturation with the same production and injection limitations. 3 335.6 nm 122.4 nm 277.3 nm
At the end of the oil saturation stage, both PROD_OIL and 4 5560 nm 5560 nm
INJ_OIL wells were shut down. Third, switching the injection
well INJ_OIL to the production well PROD2 and the
production well PROD_OIL to the injection well INJ2 was
performed, followed by re-injection of the surfactant with the of peaks corresponded to a polydispersed system, which
same restrictions on the production and injection of the illustrates complex behavior between nanoparticles and
surfactant. At the end of the oil saturation stage, both PROD2 surfactant molecules. Moreover, it can be seen that the sizes
and INJ2 wells were shut down. For all stages, the actual of the formed aggregates range from nm to μm in the presence
regimes for bottom-hole pressures were additionally estab- of nanoparticles. Regarding core flooding experiment, agglom-
lished for both injection and production wells over time. erates’ sizes higher than 300 nm are unsuitable and can lead to
During the simulation, a list of parameters was tuned, such pore blockage. Therefore, such dispersions are not recom-
as cumulative water injection, model inlet, and outlet pressure mended for core flooding unless filtered. As such, the
(set as producer and injector), and RF for the huff and puff dispersion of 0.005% SiO2 and 0.05% surfactant in 13.5 g/L
stages. It was impossible to estimate the injectivity in dynamics has been filtered using a mechanical filter. The results are
since the measurements were performed on the pump, so it presented in Table 8, and the comparison of results before and
was decided to compare only the accumulated injection after filtration is illustrated in Figure 7.
indicators and besides that, RF of the huff stage and surfactant As can be seen in Figure 7, the sizes of agglomerates have
re-injection, residual oil saturation, and residual water been reduced, and the biggest agglomerates of 5560 nm have
saturation in the mode of reverse oil pumping into the core been removed after filtration with a TF filter. According to size

Figure 6. Scheme of development indicator adaptation.

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Figure 7. Comparison of size distributions of 0.005% SiO2 and 0.05% surfactant in 13.5 g/L before and after filtration through a mechanical filter.

distribution, no more than 5% was removed with filters, and 4.2.1. Brine and Nanofluid Flooding. The core sample was
thus, nearly 95% was retained. saturated with degassed oil before the brine injection. Figure 9
Moreover, as can be seen in Figure 8, the TF series filter
retains colloidal particles, which is indicated by the nature of

Figure 9. Pressure drop and permeability profiles during preliminary

and first (additional saturation) stages of oil injection in the core
flooding test (1) with brine and nanofluid. The injection rate was a
constant of 0.0025 mL/min.
Figure 8. Dependence of the pressure drop (PD) across the TF series
filter when pumping the solution. shows the results of oil injection before and after core CT
scanning to obtain an oil-saturated core reference. In both
cases, the oil filtration rate was 0.0025 mL/min (i.e., 0.15 mL/
the change in pressure drop during the pumping of the h). The oil filtration patterns before and after CT scanning
solution of 0.005% nanoparticles and 0.05% of surfactant in coincide. At the chosen rate of 0.15 mL/h, the pressure drop
13.5 g/L. It can be concluded that some agglomerates could
(PD) between core ends stabilized at around 2.4 MPa when
not pass through the filter since the pore size of the filter was
the oil permeability was 0.0008 mD. The pressure drop profile
smaller than their sizes.
The difference between the weight of the filter after the is a characteristic of the fluid flow in the core model.45 The
reverse pumping with distilled water and its initial weight permeability decrease and PD growth indicate the formation
allows us to conclude that the settled particles were washed out damage caused by channel blockage resulting from clay
from the filter. swelling45,46 or adsorption of molecules from oil/water-based
4.2. Core Flooding Tests. This study describes two core chemical composition on the rock surface. The filtration
flooding tests conducted with (1) brine and nanofluid and (2) process was confirmed by releasing oil from the core during the
a surfactant solution. The main aim of the experiments was to entire injection time. The initial oil saturation of the samples
assess the feasibility of injecting water, surfactant solution, and referenced to the original pore space was 96.15%.
nanofluid into unconventional reservoir rock samples and The stage of oil displacement with brine completed with 15
determine the recovery factor (RF) on each cycle of the huff-n- wt % KI was conducted with a minimum filtration rate of 0.15
puff process. mL/h. The maximum pressure Pmax on the core holder inlet
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was set at 33.5 MPa. A general picture of the filtration through CT core analysis was 43.40% (Figure 11). To illustrate
parameter trend of the brine modified with KI is shown in the size distribution of pores in the core, NMR analysis of dry
Figure 10. The produced fluid consisted mainly of brine with a and water-saturated samples was performed. The result is given
in Figure 12 and shows that the majority of pores are
mesopores.

Figure 12. Incremental liquid volumes for dry (Sdry) and water-
saturated (Sw) samples obtained through nuclear magnetic resonance
(NMR) analysis.
Figure 10. Pressure drop profile and fluid mass release during brine
injection (RF-1) in core flooding test (1). The next stage of the experiment was a second injection of
oil in a straight direction. To perform this, the core sample was
small volume of degassed oil further separated from the water placed back to the core holder after CT-scanning so that the
to calculate the recovery factor RF-1. Pressure drop inlet was located in the same direction as during the first oil
stabilization has not been reached, and it was decided to filtration. The main data obtained during this stage (pressure
stop fluid injection after PD reached 10 MPa since such high drop vs volume of injected oil) is shown in Figure 13. It
values are not relevant for the reservoir. As a pressure drop compares pressure drop profiles during oil filtration before
limitation of 10 MPa was set on the pump, fluctuations in (orange line) and after (lilac line) brine flooding. One can see
indicators of the injection rate were detected as a consequence that the PD was continuously growing at a constant injection
(Figure 10). The mass of displaced oil was found to be 1.04 g, rate of 0.15 mL/h and could not reach a plateau. Thus, it was
equivalent to 1.26 mL. RF-1 was calculated through a mass decided to reduce the flow rate from 0.15 to 0.06 mL/h, and a
balance method and was 53.1%, while the residual oil pressure drop stabilization was then achieved at ∼8.6 MPa.
saturation was 45.09%, Table 9. The RF-1 value obtained The permeability was determined as 0.000073 mD, which is
lower than before brine injection by an order of magnitude
Table 9. Results of Core Flooding Test with Water and (0.00088 mD). Presumably, this can be attributed to a water
Nanofluid (1) blockage in the core sample porous media that caused low oil
saturation equal to 62% after the second oil filtration. Oil
outcome
procedure % oil saturation % water saturation parameter saturation was determined through mass balance and density
oil saturation of the 96.13
difference.
sample After the second stage of core saturation with oil, a nanofluid
brine injection 45.4 (residual) 53.1 brine RF injection was performed. This stage aimed to test the
through the oil- (RF-1) nanofluid’s ability to filter through the shale core sample or
saturated core
even efficiently displace oil due to positive wettability changing
oil saturation of 62.38 33.76 (residual)
sample 2 (CT = 75.14%) characteristics. No contrasting agent was used for the fluid to
nanofluid injection 42.54 (residual) 31.8/34.4 (no nanofluid avoid undesired particle agglomeration. The comparison of the
through the oil- match with the RF pressure drop profiles during brine injection and nanofluid
saturated core mass method) (RF-2) injection is shown in Figure 14. The process of the pulsed
filtration mode is depicted by oscillations of the filtration rate
from “0” to 0.15 mL/h. It should be noted that PD

Figure 11. Tomographic section images of the core sample, XZ plane: (a) oil saturated, (b) after displacement with an aqueous KI solution, (c)
differential image.

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Figure 13. Comparison of pressure drop profiles with (a) injection rate and (b) permeabilities during first and second oil injection (before and
after brine injection) in core flooding test (1).

nature of which could not be established. The CT analysis

(Figure 15) showed the uneven distribution of the fluids
within the core sample, which points to a gradual colmatation
of the smaller channels in the core sample by nanoparticles.
The attempts to clean the sample with an alcohol-benzene
mixture, even with the opposite direction of filtration, did not
lead to success. Even though the size of nanoparticles is 7−8
nm, the addition of surfactants or salts leads to the formation
of agglomerates larger than the pore size (estimated pore size
for samples is 13−30 nm).
Consuming the results, water injection into productive
reservoirs of unconventional formations was recognized as an
inefficient recovery technique due to two main causes. First, it
is impossible to achieve high recovery factor values under
reservoir conditions (high-pressure drops). Second, the water
blockage creation caused a critical permeability decrease.
4.2.2. Surfactant Huff-n-Puff. The second core flooding test
Figure 14. Comparison of oil displacement by nanofluid (RF-2) with was designed to simulate the huff-n-puff mode with a
oil displacement by brine (RF-1). The arrow indicates the PD surfactant solution as an injecting fluid, and it included five
stabilization achieved after the injection rate decrease; the circle steps. The fluids were injected and produced through one end,
highlights oscillations of the injection rate. Figure 5. In this experiment, 15 wt % of 1-iodooctan was
introduced into oil as a contrast for a CT scan. The pressure
stabilization did not occur (the limitation was set as 10 MPa). drop profile obtained during the core saturation process is
The mass of oil that emerged from the core sample was 0.35 g shown in Figure 16. A constant PD growth was observed at an
(the mass of light oil components evaporated during the injection rate of 3.006 mL/h, and it was decided to reduce it to
experiment was calculated using chromatographic analysis, and 0.15 mL/h. The pressure drop decreased and stabilized at ∼3
water content was determined through Karl Fischer titration). MPa after 2.7 PV of oil was injected. The oil permeability value
Thus, the recovery factor RF-2 was 33%, considering the initial of the sample was 0.00018 mD. The mass of oil injected into
oil saturation of 62% after the oil filtration-2 stage, Table 9. the core sample was 2.07 g (2.39 mL), and the whole sample
It should be noted that the water phase released from the pore volume corresponds to 2.43 mL. Thus, the initial oil
core after the nanofluid injection contained white particles, the saturation was 98%.

Figure 15. Tomographic section images of the core sample, XZ plane: (a) after secondary oil saturation, (b) after nanofluid filtration, and (c)
differential image.

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Figure 16. Pressure drop profile with stabilization during oil injection before a surfactant solution huff-n-puff test (2).

Next, the first cycle of oil displacement with the surfactant in filtration through the core were impossible due to the
a reverse direction was performed. A high-IFT surfactant that contamination of the solution with impurities from the core.
provides an IFT value of 100 mN/m order of magnitude was The mass of displaced oil was 1.09 g, which corresponds to
selected for the experiment. According to Tu,47 a surfactant 1.26 mL. Notably, the loss of light hydrocarbons was calculated
with high IFT and strong wetting ability can lead to effective based on chromatographic analysis, and water content was
oil displacement in a low-permeability reservoir. The determined through Karl Fischer titration. Thus, the recovery
parameters that describe the injection dynamics are shown in factor RF-S1 was 52.50%, and residual oil saturation was
Figure 17. To avoid hydraulic fracturing due to the high PD 47.38%.
After the first cycle of oil displacement with a surfactant
solution, the sample was again saturated with oil. To do that,
oil was injected through the same end as during oil filtration-1,
Figure 5. Figure 18a demonstrates the pressure drop dynamics
during the oil filtration process. Due to the increase in pressure
drop during the filtration, the rate was adjusted downward
from 0.15 to 0.06 mL/h, and PD stabilization was observed. At
a rate of 0.06 mL/h, the pressure drop was 10.5 MPa, while the
oil permeability decreased until 0.000067 mD, an order of
magnitude lower than with oil-1 filtration in this core flooding
test, where the oil permeability was 0.00064 mD. Most likely,
this is associated with the blockade of an aqueous surfactant
solution in the porous core medium and the low oil saturation,
which was 53.44% after oil-2 filtration.
Then, oil was displaced in a reverse direction for the second
time. The injection rate was decreased from 0.15 to 0.06 mL/
h, Figure 19. PD stabilization (8.6 MPa) can be observed after
4.5 pore volumes of surfactant solution were injected. It was
Figure 17. Oil displacement by a surfactant (RF-S1). The circle found that the water permeability was 0.00097 mD. The mass
indicates a sharp PD growth due to the adsorption of the surfactant or of displaced oil was 0.63 g, which corresponds to 0.715 mL.
I-C8. Consequently, the recovery factor RF-S2 calculated through
mass balance was 50.88%. The permeability dynamics are
value, the injection rate was decreased from 0.15 to 0.09 mL/h. shown in Figure 18b. The core permeability during the second
However, the PD did not reach a plateau, and the injection was stage of surfactant solution injection decreased by an order of
stopped. According to the PD profile (Figure 17), the main magnitude compared to the first stage. This can be attributed
part of oil was displaced after the injection of 0.2 PV of to several issues, such as water blockage, rock surface
surfactant solution. Afterward, there was a breakthrough of the hydrophilization, or swelling. Besides that, a certain amount
surfactant and further oil “washing” in the core. It can be of surfactant was adsorbed onto the rock, which can be
explained by the adsorption of the surfactant onto the rock concluded from the pressure drop dynamics, Figure 20. A PD
surface in nano- and micropores. To track the changes in the growth indicates pore blockage with surfactant molecules and
surfactant solution composition, specifically the surfactant agglomerates. Table 10 summarizes the main results of the
concentration, the interfacial tension on the boundary with oil second huff-n-puff experiment with surfactant composition.
(with 15 wt % IC8) was measured. The IFT after filtration An interesting phenomenon was observed during the CT-
through the core was 1.336 mN/m, which is ∼2 times higher scanning of the sample, Figure 21. According to the CT-image
than the initial IFT, which was 0.847 mN/m. These results analysis, RF-S1 calculated with this method was two times
support the idea that a significant amount of the surfactant was lower than expected, namely 21.47% with residual oil
adsorbed. The direct measurements of concentration after saturation of 65.60%, and oil saturation after oil filtration-2
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Figure 18. Comparison of pressure drop profiles with (a) injection rate and (b) permeabilities during first and second oil injection (before and
after surfactant injection) in core flooding test (2).

Figure 19. Pressure drop profile during oil displacement by surfactant (RF-S2).

Table 10. Results of the Core Flooding Test with a

Surfactant Solution (Test 2)
% oil % water outcome
procedure saturation saturation parameter
oil saturation of the sample 98.12
surfactant solution injection 45.49 52.62 RF-S1
through the oil-saturated core (residual)
(huff)
oil saturation of the sample (puff) 55.66 44.34
(residual)
surfactant solution injection 28.40 50.88 RF-S2
through the oil-saturated core (2) (residual)

contrasting agent 1-iodooctane in the core sample material.

Thus, the accumulation of IC8 in the sample leads to an
inaccurate determination of oil saturation. The most probable
Figure 20. Comparison of injection fluids filtration (Water, reason for the contrast accumulation is the absorption on the
Nanofluid, Surfactant-1,2). A sharp PD change is highlighted that organic component (kerogen) or clay minerals (a bright ring
indicates the adsorption of surfactant molecules. on Figure 20). Therefore, the obtained CT data for IC8-
experiments cannot be accepted as reliable and is not
considered in further calculations.
was 114.29%. In the second case, the value of oil saturation 4.3. Simulation Study. The main uncertainty parameters
significantly exceeds the maximum saturation determined by in evaluating the effectiveness of surfactant flooding are the
the open porosity of this sample. Oil saturation on CT images type of relative phase permeability (RPP) in the surfactant−oil
is usually calculated based on the concentration of the system and the dependence of the capillary number logarithm
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values reduce the residual oil saturation and flatten relative

permeability curves. This behavior has been experimentally
shown in the past literature.48,49
In this study, the simulation of surfactant injection (core
flooding test 2) was performed. The transition to a set of
relative phase permeabilities corresponding to surfactant
injection was carried out using the capillary number. Two
sets of RPP were established: (1) for water injection when the
surfactant concentration was zero and (2) for surfactant
injection when the surfactant concentration was maximum, as
in the core flooding experiment. The relative permeability in
the water−oil system was not modified since no oil was
Figure 21. Comparison of tomographic images of a core sample displaced by water in this experiment; they were set on the
artifact: (a) dry core, (b) after oil saturation, (c) differential image basis of a separate experiment on oil displacement by water
between oil saturated core and after surfactant solution filtration (the (the simulation of this experiment is not presented in this
bright ring points at accumulated contrast agent around the artifact).
paper).
Iteratively, the factors influencing the main tuning metrics
on the degree of emulsion formation, for which the miscibility were identified. In our case, the accumulated surfactant and oil
coefficient is responsible. The capillary number is a tool for injection rates were influenced by relative phase permeabilities
describing miscible displacement and allows switching to a new that were not determined during the experiment. The
set of RPPs that describe the behavior of oil in the presence of exceptions were residual oil saturation values during surfactant
surfactants in the reservoir. It is the parameter that ultimately injection1 − huff stage (SOWCR = 0.4549), re-injection of
affects the assessment of the surfactant injection effectiveness surfactant2 with SOWCR = 0.2840, residual water saturation
during oil displacement in the case of three-dimensional (SWL = 0.4434) during reverse oil injection − puff stage, and
modeling for a pilot project or the entire field. oil phase permeability values during initial oil saturation. The
Generally, when describing incomplete mixing, pH changes, main difficulty of this stage was the selection of a single
changes in surfactant concentrations, or a significant increase uniform RPP describing the process of injection of surfactant 1
in applied flow rates, it is not sufficient to assume that the and surfactant 2 as well as the displacement of the surfactant
properties of the reservoir fluid depend solely on its saturation by oil. The values of the relative phase permeability of oil at
in order to accurately describe the observed behavior of the minimum water saturation were set on the basis of oil
seepage flow. In such cases, it becomes necessary to have the displacement experiments. It was 0.06 in the case of water
ability to interpolate relative permeability and capillary displacement and 0.3 for surfactant displacement. The relative
pressure based on the surfactant concentration. Therefore, phase permeability value of water at residual oil saturation was
the capillary number serves as a dimensionless parameter that also set from the experiment and was equal to 0.02. RPPs were
represents the ratio of viscous forces to interfacial forces: modified during the setup for the surfactant−oil system.
V Comparison of relative phase permeability before modification
Nc = and after settings tuning in the surfactant−oil system and in
(3)
the water−oil system is shown in Figure 22.
where V − filtration rate (m/sec), μ − viscosity (cP), and σ − Atypical wettability behavior is usually not observed in
interfacial tension (mN/m). conventional reservoirs. However, in our case of unconven-
As a surfactant is added to the system, the residual oil tional shale formation, the surfactant failed to demonstrate its
saturation decreases and the relative wettability changes. effectiveness compared to waterflooding. The adaptation of
Ultimately, high concentrations of surfactants and low IFT experimental results led to the demonstrated RPPs, which

Figure 22. Relative phase permeability in the system surfactant−oil and water−oil.

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clearly indicated that waterflooding exhibited greater efficiency. relationship was iteratively corrected to achieve the required
This finding highlights the challenges associated with using a residual saturation value in the core.
standard surfactant as an EOR agent on such objects. The results of the model adaptation to the experiment
During the adaptation of the surfactant displacement showed a satisfactory convergence of the numerical and
coefficients in the first and second surfactant injection, the experimental recovery factors. Comparison of the accumulated
dependence of capillary number logarithm on the mixing ratio injection rates, pressures at the inlet and outlet of the core, and
with water was iteratively adjusted, please see Figure 23. displacement factors are shown in Figures 25, 26, and 27.

Figure 23. Dependence of the capillary number logarithm on the

Figure 25. Comparison of numerical and experimental recovery factor
mixing ratio.
values.

In the result, the relative phase permeabilities restored in

Capillary number logarithm values were analyzed in values adapting the model to experimental data were obtained, and
of maximum surfactant concentration in the core (Figure 24) the dependence of the capillary number logarithm on the
at each time step of surfactant injection and oil pumping. The miscibility coefficient was obtained. In the future, these

Figure 24. Capillary number logarithm for huff and puff stages.

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5. CONCLUSIONS
The study conducted two complex filtration experiments on oil
shale samples to investigate the suitability of water-based fluids,
including a nanofluid and surfactant solution as EOR agents.
The main outcomes of the study can be summarized as
follows:
1. The use of nanofluid as an EOR agent for shales is not
recommended due to the small size of rock pores and
channels which do not exceed the size of nanoparticles
or agglomerates. The filtration of nanofluids may
eventually lead to critical damage to the shale rock,
which is indicated by an increase in pressure drop and an
uneven distribution of oil saturation after the filtration of
nanoparticles. This finding suggests that alternative EOR
agents should be explored for oil recovery in shale
reservoirs.
Figure 26. Comparison of numerical and experimental accumulated 2. 1-Iodooctane is not recommended as a CT-contrasting
surfactant injection for first and second stages. agent for oil in core flooding experiments on oil shale
samples because it can be adsorbed on the core material.
To avoid absorption during CT, it is recommended to
contrast the water phase instead of the oil phase. This
finding highlights the importance of selecting appro-
priate contrasting agents for core flooding experiments.
However, it should be noted that this issue may be less
severe when utilizing alternative X-ray techniques to
estimate oil saturation, such as X-ray scanning.
3. The volume-mass method shows that water and
surfactant solution achieve an oil recovery factor of
over 50% after the first injection cycle.
4. The selected surfactant was found to be ineffective as an
EOR agent as it did not affect the course of filtration or
RF in any way compared to brine (RFsurfactant = 52.62%,
RFwater = 53.09%). Therefore, it is recommended to
continue searching for a more suitable surfactant and to
carry out additional core flooding tests.
5. Despite the relatively high recovery factors achieved, at
the moment, there is no reason to recommend the
Figure 27. Pressure comparison in the model and experiment. injection of water, brine, or water-based chemical
compositions into the productive strata of a shale
formation due to the inability to achieve high RF under
reservoir conditions (an increase in pressure drop up to
dependencies will allow evaluation of the effectiveness of 9−10 MPa per 30 mm), the critical decrease in
surfactant flooding according to the huff-n-puff technology on permeability, and the creation of water blockade.
a three-dimensional field-scale geological model of a real field 6. Thorough numerical simulation based on the exper-
object. However, it should be taken into account that the value imental data enables the determination of relative phase
of the capillary number strongly depends on the flow rate, and permeabilities even for an unsteady state filtration
therefore, it is necessary to scale the shape of the capillary process. This can subsequently be utilized for field
number curve, taking into account the real filtration rates in the scale modeling after further adjustment.
reservoir. Also, a good convergence in terms of RF values was In conclusion, the study provides valuable insights into the
obtained: an error of 1.6% for the 1st surfactant injection stage suitability of water-based agents for oil recovery in shale
and 1.4% for the 2nd stage. Accumulated injection error was reservoirs and highlights the importance of selecting
11.25 and 4.86% for the first and second stages, respectively. It appropriate contrasting agents for shale core flooding experi-
was found that the best parameters influencing the ments. Based on the results obtained, the concluding
accumulated surfactant injection are the RPP curvature and recommendation is to carry out additional research to assess
the mechanisms for reducing the permeability of oil-saturated
the endpoint of the relative phase permeability in the
reservoirs after filtration of the water phase, such as water
surfactant−oil system. At the same time, the convergence of blockade, surface hydrophilization, swelling and contraction,50
the RF during the pumping of surfactant was directly affected or the presence of two immiscible phases. Nonetheless, the
by the shape of the capillary number logarithm curve potential of using water-based fluids in EOR applications
depending on the miscibility of the surfactant with oil during should not be completely dismissed, provided the challenge of
the formation of emulsions. reducing permeability is effectively addressed.
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■ AUTHOR INFORMATION
Corresponding Author
INJ = injector
PROD = producer
Alexandra Scerbacova − Center for Petroleum Science and RPP = relative phase permeability
Engineering, Skolkovo Institute of Science and Technology, SOWCR = critical oil saturation
Moscow 121205, Russia; Western Australian School of Mines SWL = connate water saturation
(WASM): Minerals, Energy and Chemical Engineering,
Curtin University, Kensington, Western Australia 6151,
Australia; orcid.org/0000-0003-3132-7850;
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■ GLOSSARY
CT = computational tomography
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Evaluation of the Potential of Improving Oil Recovery from Shale
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