IPTC-19605-MS

Adsorption / Desorption Phenomenon of Crude Oil to Rock Surface in Low

Salinity Waterflooding

Mai Shimokawara, Japan Oil, Gas & Metals National Corporation; Miku Takeya, Hokkaido University; Chiaki Otomo
and Yasuyuki Mino, Japan Oil, Gas & Metals National Corporation; Elakneswaran Yogarajah and Toyoharu Nawa,
Hokkaido University

Copyright 2020, International Petroleum Technology Conference

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Abstract
Wettability of reservoir rocks is important in understanding the rock properties influencing the fluid
displacement in porous media. The magnitude of wettability is provided by contact angle, Ammot, and/or
USBM methods. This however indicates the average wettability of the examined core samples, and does
not give the micro wettability of core samples.
We investigated wettability changes by the adsorption and desorption of oil on core particles after ageing
process by making measurements of composition analysis of crude oil and core samples, and zeta potential at
various conditions before and after ageing process. Carbonated core samples, which were collected from the
outcrops in Japan, were used for this study because the restoration of wettability is crucial to understand the
rock properties under the natural reservoir conditions. Experimental results showed that the core particles
were partially coated with crude oil although the zeta potential measurements were indifferent between the
crude oil and the core particles coated with crude oil. The wettability is not homogeneous although the
presence of oil on rock surface changes wettability.

Introduction
Wettability of reservoir rocks is important in understanding the rock properties influencing the fluid
displacement in porous media. The wettability is defined as water-wet, oil-wet, and intermediate-wet or
mixed-wet. Water-wet means a strong affinity toward water while oil-wet means a strong affinity toward oil.
Intermediate-wet has neither a strong affinity for water nor oil (Craig, 1971). Mixed-wet has the properties
of both water- and oil- wetness, and refer to distinct and separate water-wet and oil-wet surfaces that coexist
a porous media (Salathiel, 1973).
Core samples taken from reservoirs are used to measure the wettability. Usually, the wettability of core
samples taken changes due to changes of the conditions for storing the cores samples. Therefore ageing
process is crucial to make a measurement of the accurate and essential rock properties and employed to
restore reservoir wettability of the core samples before obtaining the rock properties such as permeability,
2 IPTC-19605-MS

capillary pressure, etc. The restoration of wettability is often performed by exposuring the similar conditions
to the reservoirs including pressure, temperature, water saturation, formation water, oil properties, etc. for
some duration.
Wettability measures with contact angle, Amott, and USBM methods. The contact angle method is a
measure of angle of the wetting phase surrounded by non-wetting phase on the solid. Near zero of the contact
angle indicates water-wet, whereas near 180°indicates oil-wet. Roughly from 45°to 135°of the contact angle
is intermediate-wet (Craig, 1971). The Amott index is given by the ratio (Iw) of the volume of spontaneously
displaced water in total displaced water, which is the sum of volume of imbibed and forced displacement
of water, and the ratio (Io) of the volume of spontaneously displaced oil in total displaced oil, which is
the sum of the volume of imbibed and forced displacement of oil. The Amott-Hervey index defined by Iw
minus Io is often used. Cuiec (1984) described water-wet indicating between 0.3 and 1, intermediate-wet
indicating between -0.3 and 0.3, and oil-wet indicating between -1 and -0.3 in Amott-Hervey index. The
index of USBM is similar to the Amott index and was proposed by Donaldson, et.al. (1969). This method is
more sensitive to intermediate-wet than the Amott index (Anderson, 1986). The above methods described
represent the average wettability of the examined core sample which is typically a few cm order in size. In
other words, they do not indicate micro wettability of the core sample.
Wettability is strongly dependent on the surface electrical charge of the particle surrounded by the fluid.
The same surface charges generate a highly repulsive force, while oppositely charged surfaces attract each
other. The surface charges of the interfaces are closely related to the zeta potential, which is the electrical
potential at the slipping plane of the electrical double layer (EDL). The ionic strength and types of ions in
the solution affect the zeta potential, and subsequently affecting the thickness of the EDL and the surface
charge, which alter the wettability of the crude oil-brine-rock system. Several studies have investigated the
impacts of pH, ionic strength, and cation type on the zeta potential of the crude oil and rock surface and
have related the potential to the adsorption and desorption of crude oil on the rock surface.
The objective of this study is to investigate the adsorption and desorption of oil on the carbonate rock
surface at ageing process as well as water displacement. We conducted the ageing using crude oil and
carbonate rock at reservoir conditions and then dispersed the carbonate rock in various components of brine.
Subsequently, zeta potential was measured. This paper describes the results of zeta potential measurements
and discusses the distribution of adsorption and desorption of oil on the particle at various ageing and
immersion conditions.

Materials and Methods

Carbonate rocks collected from the outcrops in Japan were used for this study. Figure 1 and Table 1 shows
the results of X-ray diffraction (XRD) spectrum and component analysis with X- ray Fluorescence (XRF),
respectively. They are composed mainly of calcite and are under the digenesis phase similar to those of
carbonate reservoirs in the Middle East. The carbonated rocks were then crushed no larger than 200μm in
diameter for the preparation, as shown in Figure 2. The different salinity concentrations of water (brine)
were prepared. Table 2 shows the ion concentration and pH of the brine used in this study. The stock tank
oil (STO) taken from Azerbaijan was used for this study. The API gravity is 23° and the density is 910 kg/
m3 at 25°C. Tables 3 and 4 show the results of SARA analysis and composition of crude oil, respectively.
IPTC-19605-MS 3

Figure 1—X-ray diffraction spectrum of carbonate rock (Limestone).

Table 1—Compositions of the carbonate rocks analysed with X-ray Fluorescence.

Components Cncetration, %

SiO2 0.21

Al2O3 0.05

K2O 0.06

Fe2O3 0.13

CaO 74.49

MgO 0.23

Na2O 0.02

Others 24.81

Total 100

Figure 2—Distribution of particle diameter of crushed core sample.

4 IPTC-19605-MS

Table 2—Compositions and pH of various brine. FW, SW and LSW denote formation water, sea water and
low salinity water, respectively. The compositions of formation water in South East Asia reservoir are used.

Na+, ppm Mg2+, ppm Ca2+, ppm Cl-, ppm SO42-, ppm pH

FW 62798 1233 23165 140689 231 7.51

SW 13945 1550 565 24272 3346 7.8

LSW 658 13 246 1467 2 7.02

Table 3—Results of SARA analysis. Each component unit is in%.

Saturates Aromatics Resins Asphaltenes

40.7 47.7 10.1 1.5

Table 4—Component analysis of crude oil analyzed with ICP-MS.

Concentration, ppm

Na 46.6

Mg 14.3

S 2831

Ca 53.6

Fe 20.1

Zn 97.3

Figure 3 shows the schematic of the experimental procedure. The crushed core samples were immersed
at 50°C and atmospheric pressure in the STO for 20, 40, and 60 days. Subsequently, they were filtered and
flashed with brine to extract the particles, i.e. crushed core samples, coated with oil. The particles coated with
oil were dissolved with acid for preparation of the measurement of the particle components with inductively
coupled plasma mass spectrometer (ICP-MS).

Figure 3—Experimental procesures.

In addition, the crushed core samples were immersed in the various concentrations of brine to measure
zeta potential. The zeta potential of the particle of crushed core samples in the brine was measured using
Zeta-potential & Particle size analyser ELSZ-1000, manufactured by Otsuka Electronics. All zeta potential
measurements were conducted at 50 °C. The crude oil to solution ratio was constant for each measurement:
0.1 mL (0.5%) of crude oil in 20 mL of solution. The crude oil and solution were emulsified by mixing the
sample with a vortex mixer for one minute and then an ultrasonic cleaner for two minutes. The emulsion
IPTC-19605-MS 5

was extracted with a syringe and injected into a standard cell for measurement. The pH of each sample was
measured before and after the addition of crude oil to the solution using a pH meter.

Results and Discussion

Figure 4 shows the ratio of the compositions after ageing to the initial compositions of rock samples. Sulphur,
zinc and sodium, which were not included in the initial rock compositions, were detected after the ageing
process, indicating that they are originated from the oil and adsorbed on the rock particles. Significant
differences in the duration of ageing were not observed. The differences in the components of the crushed
rock samples before and after ageing indicate the rock sample coated with oil phase, suggesting changes
of wettability.

Figure 4—The ratio of compositions after ageing to the initial compositions of carbonate rock.

Figure 5 shows the ratio of the compositions after ageing to the initial compositions of crude oil. The
calcium increased significantly after the ageing process. Results show that calcium is dissolved from the
core samples and adsorbed to the oil phase possibly due to surface adsorption.

Figure 5—The ratio of compositions after ageing to the initial compositions of crude oil.

Figure 6 shows zeta potential and pH in sea water (SW), low salinity water (LSW) and 5 times diluted
formation water (5DFW) at different ageing conditions. SW and 5DFW are similar ionic strength, which
is 700mM, while LSW is 30mM of ionic strength. Carbonate represents the initial carbonate rock sample
6 IPTC-19605-MS

dispersed in brines, LN represents the crude oil dispersed in brines, and 20 days, 40 days, and 60days
represent the carbonate rock sample aged for 20 days, 40 days, and 60days dispersed in brines, respectively.
The orange and gray lines represent the pH before and after ageing, respectively.

Figure 6—Results of zeta potentian and pH in sea water (SW), low salinity water (LSW) and 5 times diluted
formation water (5DFW) at different ageing conditions: (a)SW, (b)LSW, (c)5DFW. Carbonate represents
the initial carbonate rock dispersed in brines, LN represents the oil dispersed in brines, and 20 days,
40 days, and 60days represent the carbonate rock aged for 20 days, 40 days, and 60days, respectively.

In each case the zeta potential of carbonate rock sample was positive and the pH after ageing was greater
than that before ageing. The surface of carbonate rock was positively charged and the dissolution of calcite
IPTC-19605-MS 7

increased pH. In each case the particle of crude oil had the negative zeta potential. The carboxyl groups are
the main polar components of crude oil from asphaltenes and resins and can contribute to the dissociation
and adsorption of ions (Afekare and Radonjic, 2017; Qiao et.al., 2016; Austad et.al., 2010). The carboxyl
groups can react with the cations in the brine, subsequently protons were gerenated. This led to decrease
in pH of brine after ageing.
The zeta potential of aged carbonate rock samples is negative as similar to that of crude oil, but the
absolute value is smaller than that of crude oil. This indicates that the carbonate rock particle is covered
with the crude oil and surface of calcite is covered with crude oil. However the pH of brine was greater
than that of the initial pH of brine. The dissolution of calcite can occur into brine, subsequently into crude
oil, as indicated in Figure 5. Moreover dissolition of calcite suggests that the crushed core samples contact
brine directly. This indicates that the the crushed core samples are partially covered with crude oil althogh
the zeta potential of aged core sample has similar to that of crude oil.

Conclusions
We performed the composition analysis of crude oil and core samples and zeta potential measurements
before and after ageing process to investigate the distribution of adsorption and desorption of oil on the
particle at various ageing and immersion conditions. The results element composition in brine and crude oil
show that the adsorption of crude oil on calcite surface. These results are further validated by zeta potential
measurements, which shows a negative zeta potential for aged samples. The measured absolute value of zeta
potential of aged sample is lower than that of crude oil indicating a partial compensating of crude oil surface
species with calcite surface species. Furthermore, the period of ageing did not significantly influence the
element composition in brine or crude oil and zeta potential.

Acknowledgements
This study was supported by JOGMEC and Technology Research Center of JOGMEC. We would like to
express ou sincere appreciation and gratitude to Dr. Takahashi Satoru for his help and encouragement. And
we are also thankfol to Mr. Akita Yasuyuki for his help and expertise with experiments and Ms. Shinbo
Emiko and Tsutsumi Miho for supporting with analysis.

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