Fuel 268 (2020) 117018

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Fuel
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Full Length Article

Pore-scale X-ray imaging with measurement of relative permeability, T

capillary pressure and oil recovery in a mixed-wet micro-porous carbonate
reservoir rock
Amer M. Alhammadi⁎, Ying Gao, Takashi Akai, Martin J. Blunt, Branko Bijeljic
Department of Earth Science and Engineering, Imperial College London, SW7 2AZ, United Kingdom

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: Differential imaging X-ray microtomography combined with a steady-state flow apparatus was used to elucidate
Relative permeability the displacement processes during waterflooding. We simultaneously measured relative permeability and ca-
Capillary pressure pillary pressure on a carbonate rock sample extracted from a giant producing oil field. We used the pore-scale
Oil recovery images of crude oil and brine to measure the interfacial curvature from which the local capillary pressure was
Micro-porosity
calculated; the relative permeability was found from the imposed fractional flow, the image-measured satura-
Mixed wettability
tion, and the pressure differential across the sample.
X-ray microtomography
The relative permeabilities indicated favourable oil recovery for the mixed-wettability conditions. The pore-
scale images showed that brine started to flow through pinned wetting layers, micro-porosity and water-wet
pores, and then filled the centre of the larger oil-wet pores. Oil was drained to low saturation through connected
oil layers. The brine relative permeability remained low until brine invaded a connected pathway of smaller
throats at a high brine saturation. The interface between the oil and brine had a small average curvature,
indicating a low capillary pressure, but we observed remarkable saddle-shaped interfaces with nearly equal but
opposite curvatures in orthogonal directions. This implies good oil phase connectivity, consistent with the fa-
vourable recovery and low residual oil saturation attained in the experiments.
This work illuminated displacement processes from both macro-pores and micro-pores which have important
implications for improved oil recovery and, potentially, on carbon storage. In future, the measured relative
permeability, capillary pressure and pore-scale fluid distribution could be used to benchmark and validate pore-
scale models.

⁎
Corresponding author.
E-mail address: a.alhammadi15@imperial.ac.uk (A.M. Alhammadi).

https://doi.org/10.1016/j.fuel.2020.117018
Received 8 June 2019; Received in revised form 20 December 2019; Accepted 2 January 2020
0016-2361/ © 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
A.M. Alhammadi, et al.
1. Introduction
An understanding of multiphase fluid flow in natural porous media
is important for the management and design of engineered subsurface
processes such as hydrocarbon recovery, geological carbon dioxide se-
questration and contaminant transport [1–4]. Multiphase flow in re-
servoirs is described mathematically through two macroscopic flow
properties, relative permeability and capillary pressure [1,5–7].
Capillary pressure is measured traditionally by one of three main
special core analysis (SCAL) methods. These are centrifugation, the
porous plate technique and mercury intrusion capillary pressure, MICP
[6,8–10]. Each one of these techniques has its advantages and limita-
tions. The centrifuge method is difficult to apply at reservoir conditions
and the measured data is affected by the boundary conditions [9]. The
porous plate technique has the advantage of applying a homogeneous
saturation profile and using reservoir fluids, and can be used reliably for
both drainage and waterflooding [9,11]. Nevertheless, the porous plate
method takes a long time since capillary equilibrium has to be estab-
lished at every point in the measurement [12]. On the other hand, MICP
is cheap and can be performed relatively fast. However, the sample can
be used only once because this method is destructive while using
mercury that has a different wettability than reservoir rocks. Further-
more, MICP can only be performed on a small rock sample of volume
around 1 cm3 to study a drainage process only.
The most accurate manner to measure relative permeability is
widely considered to be the steady-state method [13]. Here a sequence
of fractional flows, fw , are applied: the pressure differential due to flow
is recorded and the saturation measured from either mass balance or
imaging. Typically, the relative permeability is measured on a different
sample from which capillary pressure is found and, in any event, the
two experiments are separate and employ different displacement pro-
tocols.
Recent advances in non-invasive three-dimensional imaging using
X-ray microtomography (micro-CT) [14], combined with the use of
high pressure high temperature apparatus [15], have facilitated mul-
tiphase pore-scale studies of flow in permeable media [16–22]. This has
enabled relative permeability to be determined in combination with
pore-scale imaging through the accurate measurement of the pressure
differential across a small rock sample during a steady-state displace-
ment. This methodology was applied to measure steady-state relative
permeability in a water-wet Bentheimer sandstone by Gao et al. [23].
Interfacial curvature can also be estimated from pore-scale images that
capture the fluid–fluid interface [17,24]. Capillary pressure can then be
found using the Young–Laplace equation and the interfacial tension. Lin
et al. [25] combined measurements of interfacial curvature and pres-
sure differential to measure both capillary pressure and relative per-
meability simultaneously on the same water-wet Bentheimer sample
during a steady-state experiment: the results agreed well with in-
dependent large-scale measurements in the literature.
It is well known that hydrocarbon reservoirs are rarely water-wet,
but instead undergo a wettability alteration on contact with crude oil
resulting in mixed-wetting conditions [26–28]. In a mixed-wet rock,
parts of the pore space remain water-wet while others, through direct
contact with the polar components of the crude oil, become oil-wet
[29]. The wettability affects the relative permeability, capillary pres-
sure and oil recovery [2,30–34]. Relative permeability has been mea-
sured using X-ray images on two Bentheimer sandstone samples, a
water-wet sample and a sample treated to become oil-wet, for oil in-
jection [35]. Lin et al. [36] measured relative permeability in combi-
nation with pore-scale imaging during a steady-state waterflood in a
mixed-wet sample of Bentheimer sandstone. These previous studies that
combined pore-scale imaging with the measurement of relative per-
meability were performed on quarry sandstones and saturated with
refined oil at room temperature. To properly assess and understand
multiphase flow properties in a reservoir setting, it is necessary to
perform experiments at the high temperatures and pressures
2
Fuel 268 (2020) 117018
encountered deep underground on hydrocarbon-bearing rocks that are
saturated with crude oil and formation brine.
An additional challenge is associated with the complexity of the
pore space in carbonates which are known to be micro-porous [37,38].
Ignoring micro-porosity can lead to very poor estimates of pore volume
and saturation. To resolve this issue, different types of differential X-ray
imaging have been employed [39–41]. A quantitative characterisation
of connected micro-porosity was recently provided using differential X-
ray imaging in single-phase flow [41,42], multiphase flow in a lami-
nated sandstone [43] and a micro-porous carbonate [44]. Gao et al.
[44] measured relative permeability in a water-wet Estaillades lime-
stone quantifying oil recovery from both macro-pores and micro-por-
osity. We will perform these measurements on a reservoir micro-porous
carbonate under mixed-wet conditions. We will use this approach in
this work to quantify the saturation in both macro-pores (resolved in
the images) and unresolved micro-porosity.
In this paper we study a carbonate sample from a giant producing
oil field which has a complex pore space that is saturated with crude oil
and prepared formation brine from the same reservoir at elevated
pressure and temperature. We measured the relative permeability using
X-ray microtomography to obtain high resolution images from which
brine and oil saturation were calculated, taking into account fluid oc-
cupancy in sub-resolution micro-porosity obtained using differential
imaging, while measuring the pressure drop across the sample. These
images were then used to characterize mixed-wettability by measuring
the in situ contact angle distribution in the pore space [28,45,46]. In
addition, the interfacial curvature was estimated on the same images to
determine the local capillary pressure [25]. Furthermore, we used the
quantified fluid distributions on the images to understand and interpret
the macroscopic flow behaviour. Specifically, we show how wettability
and pore structure combine to provide a favourable oil recovery, with
significant implications for production from giant carbonate oil fields in
the Middle East and elsewhere.
2. Materials and methods
2.1. Materials
Two cylindrical carbonate reservoir samples, mini-cores, 6.2 mm in
diameter, were drilled and assembled together to form a longer sample
with a total length of 50.1 mm, Table 1. The chemical composition of
the rock determined by X-ray diffraction analysis showed 99.8 ± 0.5
weight% calcite and traces of quartz (0.2 ± 0.1 weight%). The analysis
was performed at the Natural History Museum, London, UK.
Crude oil from the same reservoir as the rock was used as the oil
phase. The crude oil was filtered using a hydrophobic filter paper with a
pore size of 10 µ m to remove any particles larger than this size. The
crude oil density and viscosity measured at 60 °C were 812 kg/m3 and
1.94 mPa·s respectively. The composition of the crude oil was 55.23%
saturates, 38.07% aromatics, 6.22% resins and 0.46% asphaltenes,
measured by Weatherford Laboratories, Norway.
Table 1
Rock properties. The core plug refers to the larger, 38 mm diameter cy-
lindrical rock sample, from which the smaller samples (mini-cores) used
in this study were drilled.
Reservoir rock properties value
Mini-core length (mm) 50.1
Mini-core diameter (mm) 6.2
Mini-core brine permeability (mD) 291.8
Mini-core X-ray image porosity (%) 27.4
Mini-core X-ray image micro-porosity (pore volume %) 34.2
Core plug (38 mm) helium porosity (%) 27.8
Core plug trim MICP porosity (%) 27.0
A.M. Alhammadi, et al.
The prepared formation brine was doped with 30 weight%
Potassium Iodide (KI) as a high contrast dopant to resolve fluids in the
sub-resolution pore space [41]. The doped formation brine contained
104,500 mg/L, 44,300 mg/L, 11,700 mg/L, 328 mg/L, 186 mg/L and
497,600 mg/L of NaCl, CaCl2 , MgCl 2 , Na2SO4 , NaHCO3 and KI respec-
tively, and at 60 °C had a density and viscosity of 1344 kg/m3 and
0.83 mPa·s respectively. The interfacial tension between crude oil and
doped formation brine was measured to be 27.9 ± 0.6 mN/m at 60 °C
using a Rame-Hart apparatus, measured by Weatherford Laboratories,
Norway.
2.2. Methods
The steady-state flow experiment was performed at low capillary
number. The capillary number defined as µq/ , where q is the total
Darcy velocity of the injected fluids, µ is the brine viscosity and is the
interfacial tension between oil and brine, was estimated to be 3.3 × 10 7.
X-ray images were acquired at the end of each brine (water) fractional
flow at a stabilized pressure drop.
2.2.1. Flow apparatus and procedure
A high-pressure high-temperature flow apparatus was used to apply
controlled flow rates at subsurface conditions while measuring the
pressure differential across the sample, Fig. 1. The pumps were con-
nected to a carbon fibre core holder assembly which had a co-injection
end-piece at the base to introduce both crude oil and formation brine
simultaneously into the sample. The effluent of crude oil and brine was
collected after passing through the back pressure regulator. The core
holder was also connected to a proportional-integral-derivative (PID)
controller to apply constant elevated temperature through a heating
jacket, wrapped around the carbon fibre sleeve, inside the X-ray en-
closure. The PID controller had an accuracy of ±1 ° C. A 300 kPa pres-
sure transducer was connected to the inlet and outlet of the core holder
to measure the pressure differential across the sample with an accuracy
of 0.1% over the whole range.
Fig. 1. The flow apparatus is made up of five main components. 1. Core holder
assembly. 2. Four high pressure syringe pumps to apply constant flow rates,
confining pressure and back pressure. 3. Back pressure regulator. 4. PID con-
troller to apply constant elevated temperature on the sample inside the X-ray
enclosure. 5. Pressure transducer to measure the pressure drop.
3
Fuel 268 (2020) 117018
1. The confining deionized, DI, water was injected into the empty
annulus space between the Viton sleeve and the carbon fibre sleeve.
Once filled, a confining pressure of 2 MPa was applied to squeeze
the Viton sleeve onto the sample to avoid any side flow during the
co-injection of crude oil and formation brine. A reference scan of
the dry rock was acquired.
2. Carbon dioxide was injected into the sample for an hour to displace
air from the pore space. This was followed by approximately 200
pore volumes brine injection to displace CO2 out of the pore space
and fully saturate the pores.
3. The pressure differential for single phase brine injection was mea-
sured over five flow rates to calculate the absolute permeability of
the assembled mini-core and found to be 2.88 ± 0.02 × 10 13 m2 . A
reference scan of the rock fully saturated with brine was acquired.
4. After completing image acquisition, the whole core holder as-
sembly was disconnected, while keeping all valves in the closed
position, and moved carefully into the oven. The pore pressure and
confining pressure were increased to 10 MPa and 12 MPa, respec-
tively. The oven temperature was set at 80 ± 1°C.
5. The reservoir rock was maintained at these conditions for three
days to allow for ion equilibration to occur between the brine and
the rock. At this stage we assumed that the core was at conditions
representative of the reservoir rock before oil migration [29].
6. Crude oil was injected into the sample over a period of two weeks.
This process is called ageing and established the mixed-wettability
conditions known to exist in hydrocarbon reservoirs [26–28]. The
injection flow rate was increased (from 0.02 mL/min to 2 mL/min
stepwise) during this period and the flow direction was reversed to
apply a uniform initial brine saturation resulting in a homogeneous
wettability alteration.
7. The core holder assembly was then isolated and disconnected while
keeping all three-way valves in the closed position and moved back
carefully into the micro-CT scanner (with all safety precautions in
place). The pumps were then connected again and air was flushed
out of the lines through the three-way valves to avoid introducing
air into the pore space.
8. The PID controller was connected to the core holder assembly and a
target temperature of 60 ± 1 °C was applied during all fractional
flows. The back pressure regulator was set to maintain a pore
pressure of 1 MPa and a confining pressure of 3 MPa.
9. A total of eight brine (water) fractional flows were imposed in se-
quence to measure the relative permeability ( fw = 0, 0.15, 0.3, 0.5,
0.7, 0.85, 0.95 and 1) with a total co-injection flow rate of 0.02 mL/
min. The fractional flow is defined as the injected volumetric flow
rate of brine divided by the total flow rate of brine and oil. At the
beginning only oil was injected at 0.02 mL/min at a water frac-
tional flow of zero. The next step was increasing the water frac-
tional flow to 0.15 with brine and oil flow rates of 0.003 mL/min
and 0.017 mL/min respectively. The water fractional flow was in-
creased in steps until it reached 100%.
At the last fractional flow point, the brine flow rate was increased
(by 100 times, from 0.02 mL/min to 2 mL/min at which 20 pore
volumes were injected) to reach residual oil saturation and then
reduced back to 0.02 mL/min to measure the pressure drop of the
last point.
10. The pressure differential across the sample was measured using the
300 kPa pressure transducer. The co-injection of crude oil and
formation brine at each fractional flow continued for at least 20 h.
Two overlapping X-ray scans were acquired (each scan took one
hour) after reaching a stabilized pressure drop at the end of the
flow period. The pore-scale X-ray images were used to capture the
brine saturation and fluid configuration at the micro-scale.
11. All of the eight fractional flows were repeated but without the
sample to measure the pressure differential in the flow lines.
A.M. Alhammadi, et al. Fuel 268 (2020) 117018

Fig. 2. On the left, stitched dry rock three-dimensional X-ray image (6 × 6 × 9

mm3 ), with a total size of 7.1 billion voxels. On the right, the highlighted
smaller volume (2 × 2 × 2 mm3 ), where dark is pore space and grey is rock.

2.2.2. X-ray image acquisition and processing

A Zeiss Xradia 510 Versa X-ray microtomography scanner was used
to acquire the high resolution three-dimensional X-ray images. All scans
were taken at an energy and power of 75 keV and 6.5 W respectively. A
flat panel detector was used to obtain a large field of view with a voxel
size of 3.567 µ m. The total number of projections was at least 3200 to
obtain good quality images. All tomograms were reconstructed using
the Zeiss Reconstructor Software and the most appropriate centre shift
correction value was applied.
The two overlapping images were all normalized to the brine re-
ference scan and stitched together to form a larger image with a total
size of 6 × 6 × 9 mm3, with 7.1 billion voxels, Fig. 2. The stitched
images were then registered to the stitched dry reference image to have
the same spatial orientation that facilitates an accurate fluid quantifi-
cation at the same location by differential imaging. The grey-scale
images were filtered using the non-local means filter [47,48].
To quantify oil and brine saturation accurately, the differential
imaging technique was used [23,41,44] to segment the 6 × 6 × 9 mm3
images. This method allows us to quantify oil and brine volumes in
small pores that cannot be explicitly resolved in the image. The pore
space and rock phases were segmented at the beginning from the dif-
ference between the two reference scans (dry and high contrast brine
scans). The brine had an even higher grey-scale value than the solid
grains. The difference images help to identify low density minerals or
isolated micro-pores. Two step watershed segmentation [49] was used
to segment solid, micro-porous grains and macro-pores, Fig. 3. The next
step was to segment the oil phase in the macro-pores (pores that could
be resolved in the image) and in the micro-pores (pore space below the
image resolution) by applying the image difference between the mul-
tiphase scans and the high contrast brine scan, Fig. 3. These difference
images were filtered using the non-local means filter and segmented
using the interactive threshold based on the grey-scale value.
To quantify pore-scale properties in macro-pores such as interfacial
curvature, interfacial area and contact angle, a 2 × 2 × 2 mm3 image
size was used, Fig. 2. To capture the shape of oil and brine phases ac-
curately in macro-pores, differential imaging between multiphase scans
and the dry reference scan was applied to distinguish the brine phase
which was segmented using grey-scale thresholding of the difference
image. The segmented brine phase was masked by the rock phase and
the remaining phase was oil, Fig. 4. The flat panel detector had a low
signal to noise ratio allowing for the lowest possible value of similarity
to be applied as part of the non-local means filter [47,48], which
avoided over averaging the grey-scale voxels while denoising the
images.
Fig. 3. Cross-sectional views of three-dimensional X-ray images used to quan-
tify brine and oil saturation at fw = 0.5 as an example. (a) Raw X-ray image of
the dry reference scan where rock is grey and pore space is black. (b) Raw X-ray
image of the brine reference scan where rock is grey and pore space filled with
brine is white. (c) Raw X-ray image at fw = 0.5 where oil, rock and brine are
shown in black, dark grey and white respectively. (d) Difference image between
brine and dry reference scans where solid, micro-porous grains and macro-pores
are shown in back, grey and white respectively. (e) The segmented difference
image shown in part (d), where solid, micro-porous grains and macro-pores are
shown in blue, orange and red respectively. (f) Difference image between brine
and fw = 0.5 scans, where brine and rock phases are shown in black and re-
maining oil is shown in white. (g) Segmented oil and brine in macro-pores
shown in red and blue respectively. (h) Micro-pores always filled with brine
(micro-pores I) shown in dark blue. (i) Micro-pores partially filled with brine
and oil (micro-pores II) shown in green. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this
article.)
3. Results and discussion
We start with the characterization of the pore space (Section 3.1)
and in situ wettability (Section 3.2). This is followed by the determi-
nation of relative permeability with associated pore-scale observations
and quantification of brine connectivity, fluid occupancy and interfacial
area in Section 3.3. Then, the calculation of local capillary pressure
from the measured interfacial mean curvature is demonstrated in Sec-
tion 3.4 followed by a discussion of the implications of these results for
oil recovery in Section 3.5.
3.1. Pore space characterization
The reservoir rock was segmented into three phases. Phase 1 re-
presents impermeable rock grains, phase 2 represents porosity below
the image resolution, mainly contained within porous grains while

4
A.M. Alhammadi, et al. Fuel 268 (2020) 117018

Fig. 4. Cross-sectional view of three-dimensional X-ray images of a smaller

image volume. (a) Dry rock. (b) Raw X-ray image at fw = 0.5 with oil, rock and
brine shown in black, dark grey and white respectively. (c) Brine phase from the
difference image. (d) Segmented image where oil, rock and brine are shown in
red, grey and blue respectively. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)

phase 3 represents the macro-pores, which are shown in Fig. 5 in blue,

yellow and red respectively. The macro-pores contributed 65.8% to the
total porosity with 34.2% from the micro-pores. The contribution to
porosity of the micro-porous phase 2 was determined by plotting the
histograms for the grey-scale voxels in the brine reference image to find
the peak (CT) in each phase and calculating the sub-resolution porosity
fraction ( sub ),
CTsub CTgrain
sub =
CTmacro CTgrain
The total pore volume is equivalent to the summation of macro-
pores and micro-pores,
PV = sub × Vmicro + 1 × Vmacro
The total porosity from X-ray differential imaging was 27.4%
compared to a helium porosity of 27.8% measured on the 38 mm core
plug from which the rock sample was drilled. The MICP porosity was
27.0% measured on the core plug trim. The consistency of these values
indicates that we have imaged a representative elementary volume of
this rock, at least for porosity, and that the differential imaging method
allows an accurate characterization of both macro- and micro-porosity.
Fig. 6. (a) Examples of the measured contact angles on raw X-ray images. (b)
Histogram of the measured geometric in situ contact angle distribution on the
segmented X-ray image at the three-phase contact line between oil-brine-rock at
fw = 0.5. (c) Thermodynamic contact angle measured from an energy balance,
Eq. (3).
(1)
3.2. In situ mixed-wettability characterization
It has been hypothesized that hydrocarbon reservoir rocks are
mixed-wet. Regions of the pore space become oil-wet through direct
(2) contact with the heavier fractions of the crude oil containing polar
components, while pores filled with connate water remain water-wet
[26,27,29]. In a recent study, X-ray microtomography was used to
quantify the in situ contact angle distribution in carbonate reservoir
rocks [28]. The study showed that there is a wide range of contact angle
both above and below 90° measured using an automated method [45].
Fig. 6 shows examples of measured contact angles where oil resides
at the pore corners (black) and brine at the centres (white). The mea-
sured geometric contact angle distribution on the segmented X-ray

Fig. 5. (a), (b) and (c) show the segmented impermeable solid grains, micro-porous matrix and macro-pores in blue, yellow and red respectively. (d) The histograms
of the grey-scale voxels in the brine reference image used to calculate the sub-resolution fraction in the micro-porous matrix. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article.)

5
A.M. Alhammadi, et al.
Fig. 7. Cross-sectional views of raw three-dimensional X-ray images at the eight fractional flows (perpendicular to the direction of the flow). The oil, rock and brine
are shown in black, dark grey and white respectively.
image at fw = 0.5 on the smaller sub-volume of the image presented in
Fig. 2, showed a mean contact angle of 113° ± 20° from 506,000 va-
lues. The wide range of measured contact angles is a characteristic of a
complex pore structure with rough surfaces [46]. Fig. 6(a) presents
examples of the pore-scale images showing the range of contact angles,
in this case measured manually on the raw X-ray images using the
method of Andrew et al. [50]. The geometric contact angle measure-
ments do have some uncertainty related to the quality of the images:
more details on the accuracy of the method can be found in AlRatrout
et al. [45] and Alhammadi et al. [28].
The oil-brine interfaces can hinge at the contact between the two
fluid phases and the solid. This means that the geometric contact angle
may not properly represent the contact angle during a displacement,
when water pushes oil from the pore space. An alternative approach is
the thermodynamic contact angle calculated from an energy balance
accounting for the changes in interfacial area and saturation [51]:
a ws cos t =2 Sw + aow ,
where is the porosity, a is the difference in interfacial area per unit
volume, κ is the mean interfacial curvature, and S w is the difference in
brine saturation. In this expression we only consider porosity, satura-
tion and interfacial area in the macro-pores. We find one average value
by computing the differences between an image and the image at the
next fractional flow on the sub-volume shown in Fig. 2. Details on how
saturation and interfacial area are measured are provided later in this
section. The calculated thermodynamic contact angles are shown in
Fig. 6(c): this represents the average angle for displacement. As ex-
pected the contact angle increases as displacement proceeds: initially
water preferentially fills the more water-wet regions of the pore space
followed by filling increasingly oil-wet pores.
3.3. Relative permeability
In this section, we will show the significance of the information
obtained from pore-scale images when it comes to explain the macro-
scopic behaviour of the measured relative permeability.
Fuel 268 (2020) 117018
3.3.1. Relative permeability measurement
The relative permeability of brine and oil were calculated using
Darcy’s law. The brine saturation at each fractional flow was measured
on the segmented X-ray images and the pressure differential across the
sample was measured using the pressure transducer. Cross-sectional
views of the three-dimensional raw X-ray images at the eight water
fractional flows are shown in Fig. 7. The oil, rock and brine are shown
in black, dark grey and white respectively. The brine saturation was
quantified in macro-pores and micro-pores. Micro-pores were categor-
ized into micro-pores I (filled with brine after primary drainage and
which always remained filled with brine) and micro-pores II (partially
filled with oil and brine after primary drainage), using the histograms
of grey-scale values shown in Fig. 8. A schematic diagram of the con-
tribution to the brine saturation from micro- and macro-pores which are
added to provide the total brine saturation at each fractional flow is
shown in Fig. 9.
In the micro-pores, the brine saturation was quantified in micro-
(3) pores II by
Fig. 8. Histograms of grey-scale values for solid, macro-pores, micro-pores I
and micro-pores II shown in blue, red, dark blue and green respectively. (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
6
A.M. Alhammadi, et al. Fuel 268 (2020) 117018

regions to the total pore volume. CT refers to the peak grey-scale value
found for each phase in the histogram of the raw multiphase image.
The initial irreducible brine saturation was 18.1%. The brine sa-
turation increased with fractional flow until a high final value (82.2%)
was reached, with a residual oil saturation of 17.8%. We can see al-
ready that waterflooding could, potentially, lead to favourable re-
coveries with the majority of the oil displaced. The brine saturation
profiles (total, in macro-pores and in micro-pores) over the length of the
image for all fractional flows are shown in Fig. 10.
The measured brine saturation indicates that there is no capillary or
saturation gradient across the sample – the capillary end effect. This is
to be expected for a mixed-wet rock with a low capillary pressure (see
Fig. 9. Schematic illustration of the contributions to the total brine saturation
Section 3.4). Were such a gradient observed, the effect can be ac-
from both macro- and micro-pores.
counted for analytically in the calculation of relative permeability [25].
The largest recovery from micro-pores is observed when the frac-
CTPFmicropores CToil tional flow is increased from fw = 0 to fw = 0.3, while the largest
SwPFmicroporeII = PFmicroporeII
CTbrine CToil (4) recovery from macro-pores is observed when fractional flow is in-
creased from fw = 0.3 to fw = 0.5.
where PFmicroporeII represents the fraction of the partially filled micro-
The pressure differential across the sample for all eight fractional
pore space. CT refers to the peak grey-scale value found for each phase
flows was measured. Table 2 presents the measured stabilized pressure
in the histogram of the raw multiphase image.
differential across the sample and the pressure drop measured sepa-
We have identified three phases in the macro-pores: brine, oil and
rately in the lines, which was taken away from the total to determine
an intermittent region. An intermittent region is where during the time
the pressure change across the rock itself.
of the scan, the void space was alternately filled with both oil and brine.
The relative permeability was calculated using Darcy’s law:
The saturation of the brine in the intermittent region was found using
the differential imaging method, [44]: qw µ w L
krw =
CTintermittent CToil pK (6)
Sw (intermittent ) = intermittent
CTbrine CToil (5)

where Sw (intermittent ) is the contribution of the intermittent regions to the qo µo L

kro =
brine saturation, and intermittent is the fraction of the intermittent pK (7)

Fig. 10. Brine saturation profiles averaged in slices perpendicular to the flow direction for all of the eight fractional flows ( fw = 0, 0.15, 0.3, 0.5, 0.7, 0.85, 0.95 and
1) over the length of the image. Total brine saturation is shown on the top, brine saturation in macro-pores is shown in the middle and brine saturation in the micro-
pores is shown at the bottom. The lowest profile is for f w = 0 and the top is f w = 1. Note that the saturation profiles are approximately constant with distance
indicating that there is no noticeable capillary end effect in this experiment.

7
A.M. Alhammadi, et al. Fuel 268 (2020) 117018

Table 2
Pressure differential across the sample at the eight fractional flows. SD indicates
standard deviation and represents the fluctuations observed in the pressure
recordings.

fw 0 0.15 0.3 0.5 0.7 0.85 0.95 1

Ptotal (kPa) 6.61 10.30 18.04 42.61 40.88 36.04 25.74 5.81
Pline (kPa) 2.18 2.16 6.11 10.28 13.11 9.91 5.68 2.36
Psample (kPa) 4.43 8.14 11.93 31.33 27.77 26.13 20.06 3.45
Psample SD (kPa) 0.13 0.22 1.89 0.36 0.32 0.29 0.25 0.13

Fig. 11. Relative permeability measured for a steady state oil-brine waterflood
in the mixed-wet sample. The error bars account for the pump accuracy that
controls the flow rates and uncertainties in the pressure measurement across the
sample, and the uncertainty in the measurement of saturation from the images.

where krw is the water (brine) relative permeability, kro is the oil re-
lative permeability, q is the Darcy velocity (flow per unit area) (m/s), µ
is the viscosity (Pa·s), L is the length of the sample (m). p is the
pressure drop across the core (Pa) and K is the absolute permeability
(m2 ).
The calculated relative permeability is shown in Fig. 11. It can be
seen that the water relative permeability is low and the cross-over sa-
turation is above 0.6 which suggests a favourable waterflood recovery
[1]. Similar behaviour has been reported using traditional core-flood
measurements in lower permeability reservoir carbonate samples from
producing oilfields [5]. In the following sections we will explain this
behaviour in terms of pore-scale displacement phenomena and the
nature of the oil/brine menisci.
The water (brine) relative permeability is low until a high brine
saturation is reached: on the other hand, oil drained to a low residual
saturation, as shown in Fig. 11. The question is: why did the water
relative permeability stay low when we have altered the wettability to
favour water invasion in the larger pores? Surely this should allow the
water to flow readily with a sharp increase in water relative perme-
ability and poor waterflood recovery, or classic oil-wet behaviour
[1,52]? The explanation for this counter-intuitive behaviour comes
from a careful analysis of the pore-scale images.
3.3.2. Brine connectivity
Brine connectivity is the answer to the questions posed above.
Fig. 12 illustrates pore-scale brine configurations at different fractional
flows. At the beginning brine flows slowly through micro-pores and
along connected pinned wetting layers, which lie below the resolution
of the scan. We know that brine can flow, since it is injected at a fixed
fractional flow, but at the scale of a few microns it appears dis-
connected. This means that the brine has no well-connected high-con-
ductivity pathways through the macro-pores. Brine can fill some water-
wet regions of the pore space, but these remain poorly connected. Since
the surfaces initially contacted by oil have become largely oil-wet, see
Fig. 6, brine can only advance across these surfaces, coming from cor-
ners and micro-porosity, at a negative capillary pressure (the brine has
to be forced into the pore space). This is a forced snap-off process [1],
Fig. 12. The brine phase in macro-pores at different fractional flows illustrating
the development of the brine phase connectivity and the displacement process
in macro-pores. The colours indicate discrete clusters of the brine phase, ob-
servable at the resolution of the image. Starting from top left to bottom right are
fw of 0.15, 0.3, 0.5, 0.7, 0.85 and 1. (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this
article.)
which is illustrated in Fig. 13.
Brine, when it is the non-wetting phase, preferentially fills the larger
pores first. The image for f w = 0.15 in Fig. 12 shows that indeed the
brine is disconnected in separate ganglia filling some of the larger
pores. These pores are filled throughout the rock – the brine being
supplied by slow flow through layers and micro-porosity – and the brine
is not connected from one pore to the next through the centre of the
void space, especially as filling of the restrictions, throats, between
pores is not favoured in oil-wet regions. As the fractional flow increases
to f w = 0.3 and 0.5, the volume of brine increases, but it remains
largely disconnected, filling some water-wet regions and larger oil-wet
pores. The poor connectivity of the brine phase is the reason for the low
water relative permeability. As shown in Fig. 11, the relative perme-
ability is approximately constant, since it is governed by a largely fixed
configuration in micro-porosity. In Fig. 10, there is an increase in the
brine saturation in micro-porosity when fw increases to 0.15, corre-
sponding to a small rise in the water relative permeability. Then, for
fw = 0.3 and 0.5, the brine saturation in micro-porosity changes only
rather modestly. This is the only brine that is interconnected and hence
the water relative permeability stays low.
The water relative permeability starts to increase at f w = 0.7 as the
brine finally spans the sample, indicated by the blue cluster, shown in
Fig. 12. At f w = 0.85, the brine connectivity is enhanced even more
through the invasion of throats (restrictions in the pore space). When

8
A.M. Alhammadi, et al.
Fig. 13. An example of the forced snap-off process. Brine percolates from
water-wet corners and micro-porosity through connected water layers and is
then forced into the oil-wet pore-body. Brine preferentially first fills the larger
pores.
injection continued with f w = 1 most of the oil was eventually dis-
placed, since the oil is connected in layers and, as shown in Fig. 6(c),
water invades increasingly oil-wet regions. Hence, finally, the brine
does occupy most of the pore space and consequently is well connected
with a high end-point relative permeability of approximately 0.5, as
shown in Fig. 11.
An intermittent region was captured in macro-pores at the first two
water fractional flows. This represents regions of the pore space where
during the hour-long scan time, both oil and brine were present. The
intermittent region occupied up to 6% of the pore space, Fig. 14. The
maximum amount of the intermittent region was seen when the brine
saturation was low (with a poor brine connectivity in macro-pores)
which is in agreement with a mixed-wet steady-state study in Ben-
theimer sandstone [35]. However, in our study the intermittent region
was not evident at higher water fractional flows ( fw 0.5).
The physical origin of this intermittency is twofold, as illustrated in
Fig. 14. In oil-wet regions (the majority of the macro-pores) brine
bulges out into the larger pores, and this arrangement may fluctuate
before brine permanently occupies a pore. In more water-wet regions of
the pore space, in contrast, it appears that partial filling of the void
space is caused by the slow swelling of brine layers encroaching from
micro-porosity into larger pores. In both cases, the brine is supplied
through the sharp increase in saturation in micro-porosity evident for
the lowest fractional flows in Fig. 10.
3.3.3. Fluid occupancy in throats
The X-ray segmented images of a smaller selected region of the
image, see Fig. 2, (2 × 2 × 2 mm3 ) were used to quantify the throat
occupancy by oil and brine. In this work, we have used the maximal ball
method to segment the macro-pore space into large regions (pores)
separated by restrictions (throats) [53,54]. The largest spheres that
could fit into the pores and throats were generated on the segmented
pore space, Fig. 15. The pore space is partitioned into pores labelled
with different numbers, which are separated by restrictions, which are
the bounding surfaces of pores, called throats. The image volume used
in this study consisted of 5563 pores and 9207 throats. The label ana-
lysis was performed by commercial image analysis software (Avizo
9.5.0) to determine the phase occupying the throats based on the seg-
mented images for all fractional flows. Here we only consider the
macro-pore space. The mean value for all voxels in the throat was used
to define oil and brine occupancy: a voxel containing brine was given a
9
Fuel 268 (2020) 117018
Fig. 14. An illustration of the intermittent region in water-wet and oil-wet
pores. On the left, X-ray images of an oil-wet pore (brine at the centre of the
pore space) and on the right, X-ray images of a water-wet pore (oil in the centre
of the pore space). The intermittent region is highlighted by the circles. The
fraction of the pore space occupied by the intermittent region is shown in the
lower part of the figure.
value 2, and oil a value 1. If the mean value of all voxels in the throat
was between 1 and 1.5, then it was considered occupied by phase 1,
which is oil in this case. On the other hand, if the mean value of all
voxels in the throat was greater than 1.5, then it was occupied by phase
2, which is brine.
Based on the image volume analyzed, the mean pore radius was
17.5 µ m and the mean throat radius 10.4 µ m. To support our hy-
pothesis, made in the previous section, that brine initially occupies the
smaller regions of the pore space but during waterflooding pre-
ferentially fills the wider macro-porous regions, Fig. 16a shows the
mean throat radius of throats occupied by oil and brine as a function of
water (brine) saturation. At the end of drainage at f w = 0, when the
brine saturation is lowest, brine occupies throats with a mean radius of
approximately 10 µ m. Then, as brine displaces oil, it preferentially fills
wider throats, as expected since the majority of the macro-pore space is
oil-wet with contact angles above 90° , see Fig. 6. Then, brine is forced to
fill smaller oil-wet throats with an increase in brine saturation. The oil
now preferentially remains in the smaller-than-average throats as the
wetting phase, [28,55,56]. The oil is preferentially displaced from the
larger throats, corresponding to the steep decline in oil relative per-
meability shown in Fig. 11.
The fraction of throats with a radius of less that 15 µ m occupied with
A.M. Alhammadi, et al. Fuel 268 (2020) 117018

Fig. 16. (a) Mean throat radius occupied by oil and brine shown in red and blue
respectively. (b) Fraction of throats with radius less than 15 µ m filled with
brine as a function of water (brine) saturation.

Fig. 15. (a) Segmented macro-pore space shown in three-dimensions. (b)

Labelled pores in different colours which are separated by restrictions (throats). Fig. 17. Oil-brine, brine-solid and oil-solid interfacial areas per unit volume,
(c) For effective visualization, the maximal balls in all pores are shown which aow , a ws and aos respectively, measured as a function of water (brine) saturation.
are connected by throats shown as cylinders.

selected regions of the pore space.

brine is plotted as a function of saturation in Fig. 16b. We suggest that The oil-brine interfacial area was found to increase, reach a max-
these throats provide the critical connections that allow the brine to imum and decrease with brine saturation, Fig. 17. The menisci con-
become well connected. The steep rise in the fraction filled with brine tributing to the area principally block pores and throats and so add to
at a saturation of approximately 0.6 mirrors the increase in water re- the resistance to flow. The maximum in the interfacial area corresponds
lative permeability shown in Fig. 11. to the lowest total mobility of the fluids, or when the sum of the relative
permeabilities is the smallest, Fig. 11.
The maximum oil-brine interfacial area is reached for brine as the
3.3.4. Interfacial area
mostly non-wetting phase for a saturation of around 60–70%. This is
The measured interfacial area per unit volume between oil-brine,
similar to what has been found by [58] for a water-wet bead pack, but
brine-solid and oil-solid is shown in Fig. 17. The extracted interfaces
the maximum was at 35% water saturation (as the wetting phase): in
were smoothed using a volume preserving Gaussian smoothing to re-
both cases the non-wetting phase saturation is approximately 65%.
move voxelization artefacts [57]. Again only the macro-pores are con-
The initial increase in interfacial area is caused by the emergence
sidered in this analysis. The interfacial area between oil and solid re-
and growth of brine ganglia in the larger pores, illustrated in Fig. 12. As
mained relatively high until a high brine saturation as a result of oil-wet
these merge near the end of the displacement, the interfacial area de-
surfaces covered by oil layers. At higher brine saturation some of the oil
creases again corresponding to an increase in water relative perme-
layers started to collapse allowing direct contact of brine with the solid.
ability thanks to better connectivity, Fig. 11. However, there is still a
The area between brine and solid increased approximately linearly with
significant remaining interfacial area in disconnected oil layers which
saturation. We have a rough complex pore space and hence, at the re-
have a larger area than the fluid arrangements at the start of water-
solution of the scan, the total solid/fluid interfacial area is much larger
flooding, before oil layers were present.
than that between oil and brine which represents only menisci in

10
A.M. Alhammadi, et al.
Fig. 18. (a) Measured oil-brine curvature distribution for 4.5 million values
shown in black. Also shown are the distribution of values where both principal
curvatures are positive, 1 > 0, 2 > 0 , both negative, 1 < 0, 2 < 0 and when
one value is positive and the other negative, 1 2 < 0 . (b) Three-dimensional
view of the measured mean curvature on the smoothed oil-brine interfaces,
where the colours indicate the negative and the small number of positive cur-
vature values in blue and red respectively. (For interpretation of the references
to colour in this figure legend, the reader is referred to the web version of this
article.)
3.4. Capillary pressure
Understanding capillary pressure, which controls how the fluids are
configured at the micro-scale, is essential to predict the performance of
hydrocarbon reservoirs at the macro-scale. Capillary pressure, Pc , is
defined as the difference in pressure between the oil and brine phases
(Pc = Po Pw ) . The segmented pore-scale images were used to capture
the oil-brine interfaces, Fig. 17, for which the mean curvature was
measured. Then, from the Young–Laplace equation, the capillary pres-
sure can be estimated. However, this imaging approach provides a
range of local estimates of curvature and not a single value. The mean
of the curvature was determined on the smoothed interfaces by the
average of the two principal curvatures obtained using commercial
image analysis software: = ( 1 + 2 )/2 [17,24,25,59]. Fig. 18 shows
the curvature distribution of 4.5 million measured values at the water
fractional flow of 0.5 when the mean value was −0.01 ± 0.04 µm 1.
The curvature measurement was performed on connected oil layers
and brine clusters of volume greater than 0.01 mm3 . Very large cur-
vature values larger than 1 µm 1 or smaller than −1 µm 1 were
considered to be outliers and were excluded. The number of excluded
values is very small compared to the total number of values. For ex-
ample, the total number of excluded values at f w = 0.5 was 15,000
points out of 4.5 million making a very small percentage of 0.33%.
We might expect the mean curvature to be similar to the inverse of a
typical pore or throat radius - from the previous section where the
11
Fuel 268 (2020) 117018
Fig. 19. The capillary pressure estimated from the average curvature of the oil-
brine interfaces plotted as a function of water (brine) saturation. No point is
shown at the end point of fw = 1, since oil appears disconnected in macro-
pores.
average throat radius is 10 µ m, we expect to see curvatures of the order
of 0.1 µ m 1 or 100 mm 1. The peak of the distribution of curvatures
shown in Fig. 18 is lower by a factor of approximately 4, while the
mean is ten times lower; however, this is not because the interfaces are
flat. Instead we see, remarkably, that most of the menisci have one
radius of curvature that is positive and one that is negative. In the mean
these values cancel out, but the Gaussian curvature 1 2 is negative: as
shown in Fig. 18 the vast majority of the interface has, locally, a ne-
gative Gaussian curvature. A similar phenomenon has been observed in
a mixed-wet Bentheimer sandstone, but in this case the system was less
oil-wet and the mean curvature was closer to zero [36,51]. A negative
Gaussian curvature implies good connectivity and points to a possible
topological origin to the favourable oil recoveries obtained in this ex-
periment [60].
The local capillary pressure was calculated from the measured
average value of the mean interfacial curvature using the
Young–Laplace law
Pc = 2 , (8)
where, is the mean curvature, and is the interfacial tension which
was measured to be 27.9 ± 0.6 mN/m at 60 °C.
The calculated capillary pressure is shown in Fig. 19. The capillary
pressure decreases with saturation as brine – the non-wetting phase –
invades progressively smaller throats, see Fig. 16. The values are always
negative indicating that displacement is forced: on average the brine
has to be at a higher pressure than oil to force movement over oil-wet
surfaces.
3.5. Oil recovery
We conclude our analysis by considering how recovery occurs in
both macro- and micro-pores. The filling sequence is controlled by both
pore size and wettability. Fig. 20 shows two distinctive oil desaturation
trends from the macro-pore space and micro-pore space. Here the re-
maining oil saturation normalised to the initial oil saturation is plotted
as a function of brine saturation. In the macro-pores, many of the large
pores are oil-wet, as quantified by the contact angle distribution shown
in Fig. 6, resulting in well-connected oil layers after brine displacement,
where the oil is retained in the corners of the pore space between brine
that remained after primary drainage and brine in the pore centres - for
examples of this arrangement see Fig. 4. An increase in brine saturation
results in a continuous decrease in oil saturation as brine displaces oil
from water-wet regions as well as the larger oil-wet pores and throats
followed by the filling of progressively smaller and more oil-wet ele-
ments, see Figs. 6 and 16.
The displacement behaviour in the micro-pores is distinct from that
seen for macro-pores. After primary drainage, some oil is present in the
micro-porosity (which we have called micro-pore region II). While we
have insufficient image resolution to measure contact angle directly,
A.M. Alhammadi, et al. Fuel 268 (2020) 117018

Fig. 20. Normalized remaining oil saturation in macro- and micro-pores shown in red and black respectively as a function of brine saturation. Each point in the figure
is measured from a 6 × 6 × 9 mm3 image. The top row of raw X-ray images illustrates brine invasion into macro-pores, where at stage 1, it flows through brine layers
in water-wet pores (indicated by the red arrow) and swells in oil-wet pores; at stage 2, the brine saturation increase dramatically in larger oil-wet macro-pores; at
stage 3, the brine saturation continues to increase and brine fills smaller oil-wet macro-pores. The oil, rock and brine are shown in black, grey and white. The lower
row of X-ray images (difference between brine and multiphase scans) illustrates the percolation of brine from micro-pores I (micro-pores always filled with brine) into
micro-pores II (micro-pores containing oil and brine), indicated by the white arrow. Oil filled micro-porous grains are shown in white and the shrinkage of these
white regions indicates oil displacement by brine.

the behaviour is consistent with these oil-filled elements being a mix-
ture of water-wet and oil-wet regions. As a consequence, filling occurs
in three stages, Fig. 20.
1. In stage 1, brine percolates through micro-pores I which remained
filled with brine after primary drainage into micro-pore region II
which contains some oil, Fig. 20. The most favourable displacement
process at the beginning of waterflooding is to fill the small water-
wet micro-porous regions first. This is seen in the saturation profiles,
Fig. 10. As a consequence, a greater fraction of the oil in micro-
porosity is displaced initially, compared to the macro-pores.
2. In stage 2, after filling the water-wet micro-porous regions, most of
the micro-porosity is now water-saturated, see Fig. 10. This provides
a connected path to allow invasion of the macro-pores. Here filling
of the smaller water-wet elements and the larger oil-wet elements is
most favorable. The initial stage of this displacement is at a small
negative capillary pressure, see Fig. 19. There is, however, an in-
sufficiently large and negative capillary pressure to enter oil-wet
micro-pores and so the displacement from the micro-porosity is
small.
3. In stage 3, the capillary pressure now allows the smaller, more oil-
wet macro-pores and the oil-wet micro-porosity to be invaded at the
end of the displacement. This stage takes place after the cross-over
of the relative permeabilities, Fig. 11, and after reaching the max-
imum oil-brine interfacial area, Fig. 17, and when most of the oil
displacement happens in the smaller oil-wet pores, Fig. 16. This
stage is the target for improved oil recovery techniques.
The initial oil saturation was 81.9% and the residual oil saturation
at the end point was 17.8% resulting in a total oil recovery of 78.3%.
Fig. 21 shows the initial and residual oil saturation in macro- and
micro-pores and the total. This indicates that a significant amount of oil
was recovered from both macro- and micro-pores.
4. Conclusions and implications
We have performed a steady-state experiment on a mixed-wet car-
bonate reservoir rock saturated with crude oil using doped formation
brine from the same reservoir at subsurface conditions.
1. The relative permeability was measured from the saturation ob-
tained on X-ray segmented images and the pressure differential
measured across the sample by a pressure transducer. The mea-
sured relative permeabilities indicated favourable oil recovery with
a cross-over saturation above 60%.
2. We used differential imaging to quantify both macro-porosity,

12
A.M. Alhammadi, et al.
Fig. 21. The initial oil saturation in red and the residual oil saturation in black. The total saturation is shown as well as the contribution from macro-pores and micro-
porosity.
where the pores could be explicitly resolved at the resolution of the
image, and micro-porosity that could not. In the macro-pores we
identified oil, brine and an intermittent region where the pore
space was occupied by both oil and brine during the scan time. In
the micro-porosity we identified pores that remained brine-satu-
rated and those that contained both oil and brine.
3. The measured contact angles in the larger pores indicated oil-wet
conditions on average with a mean value of 113°.
4. The brine phase remained poorly connected in the larger macro-
pores until a high brine saturation was reached, allowing oil to
drain to low saturation by flowing through connected oil layers.
During waterflooding, water-wet regions and the larger macro-
pores and throats were preferentially filled first. Once these ele-
ments connected across the rock, the water relative permeability
rose steeply.
5. The capillary pressure was determined from the average of the local
interfacial curvature. As expected for a largely oil-wet system, the
capillary pressure was negative and decreased with increasing
water saturation.
6. The interfacial area between oil and brine increased with saturation
before reaching a maximum shortly before the residual oil satura-
tion was reached. The oil-brine menisci block the pore space: the
maximum interfacial area corresponded to the minimum total
mobility of the phases.
7. This work illustrates a procedure to perform oil and brine satura-
tion quantification in micro-porous carbonate reservoir rocks,
opening the door for further studies to investigate a wide range of
reservoir systems.
8. The brine saturation did not change with distance along the core
indicating that there was no capillary end effect which is expected
for such a low capillary pressure system.
9. The results could be used in future as a benchmark for pore-scale
modelling to improve predictions of multiphase flow in hydro-
carbon reservoirs.
10. This imaging and analysis methodology could also be used to study
a wide variety of porous medium problems, including fuel cells,
water and vapour transport in plants, catalysis, carbon dioxide
storage, and imbibition in cloths and other fibrous materials, for
instance.
Disclosure
The three-dimensional X-ray images are available from the corre-
sponding author.
Credit authorship contribution statement
Amer M. Alhammadi: Conceptualization, Investigation, Formal
analysis, Writing - original draft, Writing - review & editing. Ying Gao:
13
Fuel 268 (2020) 117018
Investigation, Writing - review & editing. Takashi Akai: Investigation,
Writing - review & editing. Martin J. Blunt: Conceptualization,
Supervision, Writing - review & editing. Branko Bijeljic:
Conceptualization, Supervision, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
We gratefully thank Abu Dhabi National Oil Company (ADNOC) and
ADNOC Onshore for funding this work.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.fuel.2020.117018.
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