SPE 142979

Investigation on Variations in Wettability of Reservoir Rock Induced by CO2-

Brine-rock Interactions
Zihan Zhu, Mingyuan Li, Meiqin Lin, Bo Peng, Liang Sun and Long Chen, China University of Petroleum, Beijing

Copyright 2011, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE EUROPEC/EAGE Annual Conference and Exhibition held in Vienna, Austria, 23–26 May 2011.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Originally, the reservoir rock surface is hydrophilic at atmosphere pressure, because they are generally consisted of
hydrophilic minerals, such as quartz, feldspar, calcite, dolomite and clay minerals. According to different hydrophilic
magnitudes of different minerals and Cassie's law, the heterogeneous reservoir rock surface shows different hydrophilic
magnitudes with different mineral compositions. Therefore, after CO2-brine-rock interactions, minerals dissolution and
precipitation will change the mineral composition and the hydrophilic magnitude of the reservoir rock surface at the same
time.
The present study implemented a CO2-brine-rock system in laboratory with elevated CO2 partial pressures at 323K and
343K. Surface properties of the reservoir rock (such as wettability, surface mineral composition, surface topography and
surface element composition) were respectively determined by Wilhelmy plate, XRD, SEM and EDS method before and after
CO2-brine-rock interactions. The contact angle results show with the increasing CO2 partial pressure, the contact angle of
water on the reservoir rock surface increases at 323K, and decreases at 343K. SEM results show minerals dissolution and
precipitation were both taken placed on the reservoir rock surface after CO2-brine-rock interactions. EDS results indicate
carbonate minerals dissolution plays a dominate role at 343K, and secondary carbonate minerals precipitation mainly occur at
323K. There is a close relation between the contact angle variation of water and the element mole percentage variation on the
reservoir rock surface. With the increasing O, Si, Al, Na or K mole percentage, the decreasing C or Fe mole percentage, the
rock surface becomes more hydrophilic.

Introduction
CO2 enhanced oil recovery (EOR) is a proven and increasingly cost-attractive technology for boosting oil production in low
permeability reservoirs. At the same time, the oil recovery helps to pay for the cost of capturing and building the transportation
infrastructure to sequester more CO2, making the process more economical.
In the process of CO2 EOR projects, wettability of the reservoir is really important and must be addressed, because it plays
an important role on the petrophysical properties of the reservoir, including relative permeability, the capillary pressure curves,
waterflood behavior, electrical properties, and EOR. Especially, for CO2 EOR projects, the selected reservoir rock with low or
even ultra-low permeability always have a great quantity of capillary number and narrow pore size distributions. It means even
if the capillary pressure of the reservoir changed a little induced by wettability variations, the petrophysical properties change a
lot.
Several research groups have reported and investigated wettability alteration of the reservoir in the present of oil induced by
CO2-oil-rock interactions1, 2. However, variations in wettability of the reservoir in absence of oil induced by CO2-brine-rock
interactions have been less studied. This research is really important and also should be addressed. Because there is amount of
formation brine, which originally exist or be provided by water flooding, located in some oil reservoir formations, and
variations in wettability of the reservoir induced by CO2-brine-rock interactions will also change the petrophysical properties
of the whole reservoir a lot. In addition, this research is also useful for studies of the liquid-solid adhesion during CO2-water
flowing in the pore of the reservoir, and will contribute a new kind of reference database for modeling works in the future.
Wettability3 is defined as the tendency of one fluid to spread on or adhere to a solid surface in the presence of other
immiscible fluids. When displaced, the wetting fluid will occupy the small pores and will be present in the largest pores as a
film on the rock surface. The factors that affect the wettability of the reservoir are many-sided, complex, mainly including
temperature, pressure, gas properties, liquid properties and the rock surface properties.
In the present study, we were just focusing on variations in wettability of the reservoir induced by the changes in surface
2 SPE 142979

properties of the reservoir rock after CO2-brine-rock interactions. Therefore, a CO2-brine-rock system was previously
implemented in the present study using pure CO2, reservoir rock slices obtained from block Hei 47, Daqingzi region of
southern Songliao basin and the model Daqingzi formation brine. The determination of wettability of the reservoir was
measuring the contact angle of de-ionized water on the reservoir rock surface at 20 and under atmosphere pressure. It means
other factors including temperature, pressure, gas properties and liquid properties remain the same, but the rock surface
properties change induced by CO2-brine-rock interactions. The surface topography and element composition of the reservoir
rock surface were determined by SEM and EDS, respectively.
‘’
Experiments
Material. Rock slices (20×20×2 mm) are made of reservoir rocks obtained from block Hei 47, Daqingzi region of southern
Songliao basin. The XRD pattern and mineral composition of the reservoir rock surface have been determined by XRD, and
shown in Fig.1 and Table 1. According to ions composition in Daqingzi region, standard laboratory-grade salts (including
NaHCO3, >99.5%, NaCl, >99.5%, CaCl2, >96% and MgCl2·6H2O, >99%), which are provided by Beijing Modern East Fine
Chemical Co., were used to synthesize the model formation brine (Table 2). CO2 (≥99.95%) was provided by BJJGGAS Ltd.
and double-distilled water was self-made in our laboratory.

[zzh1103.ASC] <2T(0)=0.05>
d=3.3471

10.0

8.0
Intensity(CPS)

6.0
d=3.1930

4.0
d=1.8192
d=4.2610

d=1.5422
d=3.6717
d=4.0351

d=3.1609

d=2.9089
d=3.7731

d=2.2828
d=3.0285

d=2.4590

d=2.1296

d=1.3748
d=1.3821
d=2.2382

2.0
d=1.9812
d=6.3888

d=1.8021
d=1.7837

d=1.6727
d=3.4889

d=2.5552

d=2.0906

d=1.9069
d =2.2031
d=2.4106

d=1.4591
d=2.0257

x10^3
10 20 30 40 50 60 70
2-Theta(°

Fig.1. XRD pattern of the reservoir rock obtained from block Hei 47, Daqingzi region of southern Songliao basin.

Table 1 Mineral composition of the reservoir rock obtained from block Hei 47, Daqingzi region of southern
Songliao basin.
Mineral Composition Content (%)
Quartz SiO2 38.7
K-feldspar KAlSi3O8 1.4
plagioclase NaAlSi3O8-CaAl2Si2O8 34.4
Calcite CaCO3 10.4
Dolomite MgCa(CO3)2 11.2
Clay minerals - 3.9

Table 2 Content of compounds in the model formation brine of Daqingzi region of southern Songliao
basin.
Composition NaHCO3 NaCl CaCl2 MgCl2 salinity
content/mg•L-1 3734.5 1381.6 66.4 82.7 5265.2

Mineral grains, including quartz (≥98.3%, BJYL), kaolin (≥99.1%, BJYL), illite (≥99%, BJYL), outcrop calcite (≥97.8%,
888Quartz Co. Ltd), outcrop feldspar (≥96.5%, 888Quartz Co. Ltd) and outcrop dolomite (99.2%, 888Quartz Co. Ltd) were
prepared. These six minerals are mostly common and high content in reservoir rock (sandstone and carbonate rock). All
mineral grains were prepared by grinding with an agate mortar into 74~150μm size particles. Mixed mineral grains, such as
quartz-calcite, quartz-dolomite and quartz-kaolinte grain samples, were prepared by mixing different kinds of mineral grains
uniformly with different mass ration.

CO2-brine-rock interaction experiments. CO2-brine-rock system was consisted of pure CO2, a reservoir rock slice and the
model formation brine. Eight experiments are implemented with four different partial pressures of CO2 (PCO2) and under two
SPE 142979 3

different temperatures, respectively. According to the reports4, 5, 15MPa and 20MPa of CO2 at 323K or 343K is above both the
critical pressure (7.38MPa) and temperature (31.1 ), CO2 in that reaction cell is a supercritical fluid. When the experiment
was terminated, the surface of the rock slice is analyzed. Summary of batch experiments performed in the CO2-brine-rock
system is shown in Table 3.

Table 3 Summary of the batch experiments performed in the CO2-brine-rock system

Sample/expt PCO2 (MPa) T (℃) t (h)

1# 3.7 49.4 120

2# 6.2 49.4 120

3# 15.0 49.6 120

4# 20.0 49.0 120

5# 3.7 69.0 120

6# 6.2 68.9 120

7# 15.0 68.9 120

8# 20.0 68.9 120

High pressure reactor (Fig.2), which was designed by our laboratory, was used for CO2-brine-rock interaction experiments.
The capacity of the reactor is 100 ml, and the maximum operating pressure is up to 32MPa. The 316 Specialty steel, which is
resistance to corrosion of brine and the solution of H2S, is used for the material of the high pressure reactor.

valve 2

valve 1

Fig. 2. Schematic of experiment apparatus.

A rock slice and constant 50ml formation water were firstly placed in the high pressure reactor. CO2/N2 was injected into the
high pressure reactor from valve 1 to remove the remaining air from valve 2. Then valve 1 was closed, and CO2/N2 was
continuously injected from valve 2 to increase pressure to a constant pressure value. This pressure was approximately equal to
the CO2/N2 partial pressure in this paper, ignoring the H2O partial pressures6 which is equal to water vapor saturation pressure.
The whole system was located in the on-off thermostat. Before fluid samples were withdraw from the high pressure reactor,
the reactor should be be rapidly cooled to ambient conditions in less than a few seconds, in order to avoid retrograde reactions
with minerals that may occur during a prolonged quench process of CO2 pressure drop7.

Analysis. Mineral composition of a rock surface was determined by X-ray diffraction (XRD) method. XRD measurement at
the CuKα wavelength was carried out using a D/MAX 2500 diffract meter equipped by Rigaku Industrial Corporation. The
instrument was operated at 40kV and 100 mA. Scanning range and scanning rate of rock dried at room temperature was
2.6°~15° and 6°/min, respectively. Scanning electron microscopy (SEM) and Energy dispersive spectrometry (EDS) of
Cambridge Instruments Stereoscan S-360 was used to observe surface topographies of the reservoir rock and determine the
element composition of the reservoir rock surface, respectively. The contact angle of water on the reservoir rock surface was
determined by Wilhelmy plate method using a tensiometer (Dataphysics, Germany). The wetted length of the rock was
measured by a caliper (precision ±0.02mm mm). The slide was suspended from the electronic microbalance (precision 1μg)
and moved in and out of the test liquid at a speed of 1 mm·min-1. Test temperature was 20 . Test liquid is double-distilled
water, which density, viscosity and surface tension is 0.9982g/cm3, 1MPa·s and 72.8mN/m at 20 , respectively. The force
4 SPE 142979

acting on the balance was continuously measured. The contact angle was calculated according to Eq. 1:
(F − Fb )
cos θ = (1)
Pγ L
where θ is dynamic contact angle, F is the measured vertical force (N), Fb is the buoyancy force (N), P is the wetted length
(m), and γL is the surface tension of the test liquid (Jm−2).
The contact angle of water on mineral grains was measured by modified Washburn method. The sample holder was a glass
tube with an inner diameter of 8.90 mm (Dataphysics, Germany). A 30μm mesh membrane was placed into the sample holder
to prevent the sample powder from falling out. Five grams of dry powder were placed into the sample holder with manual
tapping (several times) to obtain uniform packing of the aggregates. After packing, the holder was placed onto the electronic
balance of the tensiometer. The weight gain of the sample holder after contact with test liquids was recorded.
In the capillary penetration (rising) method, the relationship of the rising height h of a liquid with time t in a capillary tube
of radius r can be expressed as Washburn equation8,
r γcos θ
h2 = t (2)
2η
where γ is surface tension of liquid in mN/m, and η is viscosity of the liquid in mPa·s. If γ, η and r are already known or have
been measured, the contact angle can be calculated from the above equation via a straight line fit to the h2–t diagram.
The relation between liquid mass m and height in the column is linear as given by Eq. 3:
m = πRk hρε
2
(3)
3
where ρ and ε is density of the liquid (g/cm ) and the number of capillaries, respectively, and Rk is the effective radius (m) of
the liquid in the column.
Substitution into Eq. 4 gives the modified Washburn method:

m =⎢
2 k( )
⎡ r πR 2 2 ε 2 ⎤ ρ 2 γcosθ
⎥ t (4)
⎢⎣ 2 ⎥⎦ η
which leads to
Cρ 2 γcosθ
m2 = t (5)
η
with

k ( )
⎡ r πR 2 2 ε 2 ⎤
C=⎢ ⎥ (6)
⎢⎣ 2 ⎥⎦
C is the calibration factor for the irregular orientation of capillaries in the bed. Therefore, the modified Washburn’s equation
is used as dependence between wetting liquid mass and time. For similarly packed beds, C is approximately a constant and its
value can be obtained by experiment with a liquid known to give a θ=0°. In our experiment, for each series solution, we
selected that n-Pentane which had the fastest water penetration rate in each packed bed of the Washburn tube as the standard
and assumed its θ value on the surface of the mineral sample to be zero to calculate C.
m2 η
C= （7）
t ρ γcosθ
2

Base on the result of C, the contact angle of solid samples with a liquid can be calculated by:
⎛ m2 η ⎞
θ = arccos⎜⎜ ⎟⎟ (8)
⎝ t ρ γC ⎠
2
SPE 142979 5

Results and discussion

Wettability of reservoir rocks and minerals. Generally speaking, reservoir rocks are hydrophilic. As shown in Table 7,
contact angles of water on reservoir rocks obtained from block Hei 47, Daqingzi region of southern Songliao basin are all less
than 90° at 20 . It is because they are all consisted of hydrophilic minerals, such as quartz, feldspar, calcite, dolomite and clay
minerals, as shown in Table 1. Table 4 shows contact angles of water on different minerals determined in this study and
reported in references. The results are a little different with each other because of different measurement methods of
wettability, or different sample sources. an approximate regularity can be drawn that (1) all of minerals show hydrophilic and
their contact angles of water are less than 90° at 20 , and (2) minerals can be ranked as quartz> feldspar> carbonate minerals
according to their magnitudes of hydrophily. Hydrophily of a mineral depends on interactions between the unsaturated bond
force of the mineral surface and the dipole polarization of water. Unsaturated bond was obtained from the crystalline fracture
surface, and was controlled by the crystal structures of mineral. Therefore, different minerals with different crystal structures
show different magnitudes of hydrophily.

Table 4 Contact angles of water on minerals using various determination methods

a
Mineral Contact angle (°) Contact angle (°) Method
9
0~4 Wilhelmy plate
Quartz 0.00 10
35 Wahburn
10
Dolomite 63.81 51.7 Directly contact angle measurement
11
K-feldspar 0.00 45 Thin layer wicking
11
Plagioclase - 43 Thin layer wicking
12
illite 75.12 34.2 Sessile drop method
11
Calite 81.09 55.9 Thin layer wicking
13
Kaolinite 84.13 46.1 Thin-layer wicking
a
Contact angle represents the value is determined using Washburn method in this study. Test condition is 20℃ at atmosphere pressure and
test liquid is deionized water.

According to Cassie law14, 15, surfaces having heterogeneities on a flat due to impurities or polycrystalline over small length
scales can be modeled with the Cassie equation (Eq.9).
cosθ = f1 cosθ1 + f 2 cosθ 2 + ... + f i cosθ i (9)
where f1 and f2 are the fractions of the surface occupied by surface types having contact angles θ1 and θ2.
Fig. 3, 4 and 5 show relations between the mass/area fraction of mineral and the contact angle of water. Mass fraction
values were controlled by actual measurement, and area fraction values were calculated by Cassie law. When the mass fraction
of strong hydrophilic quartz increases, and the mass fraction of relatively weak hydrophilic calcite, dolomite or kaolinite
decreases, the contact angle of water decreases and the mixed sand turns more hydrophilic. Although the actual measurement
values and the calculation values have a similar trend, there are some difference between them, because the mass fraction of
mineral is different from the area fraction of mineral.

1.0 1.0
Calculation
Atual measurement
0.8 0.8
Mass fraction of calcite/%
Area fraction of calcite/%

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0

0 20 40 60 80
Contact angle/°

Fig. 3 Relations between the area/mass fraction of calcite and the contact angle of water on quartz-calcite grains.
6 SPE 142979

1.0 Calculation 1.0

Atual measurement

Mass fraction of dolomite/%

0.8 0.8

Area fraction of dolomite/%

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0

-10 0 10 20 30 40 50 60 70
Contact angle/°

Fig. 4 Relations between the area/mass fraction of dolomite and the contact angle of water on quartz-dolomite grains.

1.0 1.0
Calculation
Atual measurement
0.8 0.8

Mass fraction of kaolin/%

Area fraction of kaolin/%

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0

0 20 40 60 80 100
Contact angle/°
Fig. 5 Relations between the area/mass fraction of kaolin and the contact angle of water on quartz-kaolin grains.

Surface topography variations after CO2-brine-rock interactions. SEM method was used to observe surface micro
topographies of the reservoir rock obtained from block Hei 47 before and after CO2-brine-rock interactions. Fig.6-a shows the
initial surface micro topography of the reservoir rock before CO2-brine-rock interaction. Like most sandstone, there are good
porosity and connectivity in the consolidated rock. Detrital minerals, mainly including quartz and feldspar, are coated with
some small clay mineral grains. Cementing and filling minerals are mostly locating among detrital minerals or distributing in
the pore throat. Fig.6-b shows cementing and filling minerals in the pore throat disappear, more quartz is exposed on the
reservoir rock surface after CO2-brine-rock interactions at 3.7MPa CO2 and 323K. It is because feldspar and cementing
minerals (which mainly are carbonate minerals) dissolution occurs, and clay minerals coated on the reservoir rock surface have
splitted away after CO2-brine-rock interactions. However, minerals precipitation on the reservoir rock surface is an another
result of CO2-brine-rock interactions16, 17. Fig.6-c, Fig.6-d, Fig.6-e and Fig.6-f show there are precipitations of calcium
carbonate aggregate, albite grains, spherical nanoparticles of hematite and foliated aggregate chlorite precipitation at 15MPa
CO2 and 323K.
SPE 142979 7

Fig. 6. Scanning electron microphotographs of the reservoir rocks from block Hei 47 before and after CO2-brine-rock interactions. a)
Initial surface of the reservoir rock, b) more quartz and K-feldspar expose at 3.7MPa CO2, c) calcium carbonate aggregate
precipitation at 15MPa CO2 and 323K, d) albite grains precipitation at 15MPa CO2 and 323K, e) spherical nanoparticles of hematite
(< 2μm) precipitation at 15MPa CO2 and 323K, f) foliated aggregate chlorite precipitation at 15MPa CO2 and 323K.

Element composition variations after CO2-brine-rock interactions. Element mole percentages of the reservoir rock
surface before and after CO2-brine-rock interactions are determined by EDS method. The detection areas are approximately
6.4mm2. The element mole percentages and their variations at different CO2 partial pressures and temperatures are shown in
Table 5 and Fig. 7.

Table 5 Mole percentages of elements and their variations of the reservoir rock before and after CO2-brine-
rock interactions
Sample/expt C/% ΔC/% O/% ΔO/% Na/% ΔNa/% Mg/% ΔMg/% Al/% ΔAl/%
Before 38.20 0.00 40.9 0.00 2.08 0.00 0.92 0.00 2.75 0.00
1# 50.80 12.6 42.62 1.72 1.42 -0.66 0.48 -0.44 1.42 -1.33
2# 55.14 16.94 29.87 -11.03 1.29 -0.79 0.75 -0.17 2.11 -0.64
3# 52.31 14.11 41.23 0.33 1.28 -0.80 1.05 0.13 1.34 -1.41
4# 52.13 13.93 41.47 0.57 0.49 -1.59 0.31 -0.61 1.39 -1.36
5# 23.96 -14.24 45.39 4.49 2.59 0.51 0.77 -0.15 3.42 0.67
6# 28.07 -10.13 41.21 0.31 2.78 0.70 0.81 -0.11 3.35 0.60
7# 32.85 -5.35 43.30 2.40 2.33 0.25 0.44 -0.48 3.10 0.35
8# 25.13 -13.07 46.63 5.73 2.65 0.57 0.61 -0.31 3.34 0.59
Sample/expt Si/% ΔSi/% K/% ΔK/% Ca/% ΔCa/% Fe/% ΔFe/%
Before 11.50 0.00 0.40 0.00 2.62 0.00 0.73 0.00
1# 2.23 -9.27 0.00 -0.40 0.06 -2.56 0.98 0.25
2# 8.57 -2.93 0.23 -0.17 0.90 -1.72 1.14 0.41
3# 0.46 -11.04 0.14 -0.26 0.92 -1.70 1.27 0.54
4# 3.19 -8.31 0.42 0.02 0.00 -2.62 1.17 0.44
5# 20.52 9.02 0.49 0.09 2.51 -0.11 0.34 -0.39
6# 19.57 8.07 0.62 0.22 2.86 0.24 0.72 -0.01
7# 15.69 4.19 0.54 0.14 1.51 -1.11 0.24 -0.49
8# 19.20 7.70 0.52 0.12 1.25 -1.37 0.67 -0.06
8 SPE 142979

60 60
C C
O 50 O
50
Si Si

40 40

Mole percentage/%
Mole percentage/%

30 30

20 20

10 10

0 0
0
Initial 5 10 15 20 Initial
0 5 10 15 20
P/MPa P/MPa
(A) Nonmetallic elements content at 323K (B) Nonmetallic elements content at 343K
5 5
Na Mg Al Na Mg Al
K Ca Fe K Ca Fe
4 4

Mole percentage/%
3 3
Content/%

2 2

1 1

0 0

Initial
0 5 10 15 20 Initial
0 5 10 15 20
P/MPa P/MPa

(C) Metallic element content at 323K (D) Metallic element content at 343K
Fig. 7. Mole percentages of elements including nonmetal elements (C, O and Si) and nonmetal elements (Na, Mg, Al, K, Ca and Fe) of
the reservoir rock surface at different CO2 partial pressures and temperatures. Carbon dioxide was injected into the reaction cell at
120 h (50ml CO2 plus 50ml brine) to produce a ratio of 1/1 for brine/CO2.

As shown in Fig.7, carbonate minerals dissolution plays an important role in CO2-brine-rock interactions at 343K. With the
increasing CO2 partial pressure, the mole percentages of C, Ca and Mg decreases. It indicates that the increasing CO2 partial
pressure will increase CO2 solubility in brine and the acidity of brine, and then will enhance carbonate minerals (such as
calcite, dolomite and magnesite) dissolution. However, the mole percentages of K, Na, O, Al and Si increase with the increase
in CO2 partial pressure, because quartz and silicate minerals expose on the surface of the rock after other minerals
disappearing. The mole percentages of Si, Al, Na, Ca, Mg and K on the reservoir rock surface decreases respectively with the
increasing partial pressure of CO2 at 323K, which indicates that the dissolution of silicate (plagioclase and K-feldspar) and
carbonate minerals (calcite, dolomite and magnesite) occurs induced by CO2-brine-rock interactions. However, the mole
percentages of Fe, O and C increases with the increasing partial pressure of CO2, indicating that there are secondary minerals
precipitation, such as carbonate or iron-bearing minerals, on the reservoir rock surface.

Wettability variations after CO2-brine-rock interactions. Wettability of the reservoir is determined by measuring the
contact angle of water on the reservoir rock surface, using Wilhelmy plate method. Table 6 shows results of contact angles
before and after CO2-water-rock interactions and their difference values (D-values). Fig.8 shows variations in D-values at
different CO2 partial pressures and temperatures. As shown in Table 6, contact angles of water change after CO2-brine-rock
interactions. At 323K, contact angles increase after CO2-brine-rock interactions, and D-value of the contact angle is positive.
In contrast, at 343K, contact angles decrease after CO2-brine-rock interactions, and D-value of the contact angle is negative. In
addition, Fig.8 shows with the increasing CO2 partial pressure from 3.7MPa to 20.0MPa at 323K, D-values increase from 9.3°
to 18.8°. And with the increasing CO2 partial pressure from 3.7MPa to 20.0MPa at 323K, D-values decrease from -7.1° to -
20.2°.
SPE 142979 9

Table 6 Contact angles of water and their D-values on the reservoir rock surface before and after CO2-
water-rock interactions
Before After D-value
Sample/expt
Contact angle(°) Contact angle(°) ΔContact angle(°)
1# 45.4 54.7 9.3
2# 36.0 43.7 7.7
3# 44.4 53.9 9.5

4# 34.8 53.6 18.8

5# 63.6 56.5 -7.1
6# 63.4 52.3 -11.1
7# 61.0 50.1 -10.9
8# 40.2 20.0 -20.2
*D-value of the contact angle means the value of the contact angle after CO2-water-rock interactions subtract that before CO2-water-rock
interactions.

20
70℃
15 50℃
10
5
ΔContact angle( °)

0
-5
-10
-15
-20
-25
-30
0
Initial 5 10 15 20
PCO2/MPa

Fig. 8. Contact angle variations at different CO2 partial pressures and temperatures.
10 SPE 142979

Relations between variations in wettability and element mole percentage. Fig.9 shows there are close relations
between contact angle variations of water and element mole percentage variations on the reservoir rock surface. As shown in
Fig.9, with the decreasing mole percentage variation of C or Fe element and the increasing mole percentage variation of Si, Al,
Na or K element, the contact angle variations of water decreases from positive value (18.8°) to negative value (-20.2°),
indicating the reservoir rock surface turns from less hydrophilic to more hydrophilic. On the contrary, with the increasing mole
percentage variation of C or Fe element and the decreasing mole percentage variation of Si, Al, Na or K element, the contact
angle variation of water increases from negative value (-20.2°) to positive value (18.8°), indicating the reservoir rock turns
from more hydrophilic to be less hydrophilic. In fact, different elements represent different minerals on the reservoir rock
surface. The mole percentage variations of C and Fe elements indicate the content variations of carbonate and iron-bearing
minerals due to minerals dissolution or precipitation on the reservoir rock surface. The mole percentage variations of Si, Al,
Na and K elements indicate the content variations of quartz, albite and K-feldspar, since these minerals turn to be exposed on
the rock surface or coated with secondary minerals precipitation. The wettability of the reservoir rock surface is controlled by
the mineral composition of the reservoir rock surface. After CO2-brine-rock interactions, because of minerals dissolution and
precipitation on the reservoir rock surface, when the content of quartz, abilite or K-feldspar increases, or the content of
carbonate or iron-bearing minerals decreases on the reservoir rock surface, the reservoir rock will turns to be more
hydrophilic. On the contrary, the reservoir rock will turns to be less hydrophilic.
30
C 1.0
O
20
Si 0.5
ΔMole percentage (%)

ΔMole percentage (%)

10 0.0

-0.5
0
-1.0

-10 -1.5
Na Al
-20 -2.0
K Fe

-2.5
-30 -20 -10 0 10 20 30 -30 -20 -10 0 10 20 30
ΔContact angle( °) ΔContact angle( °)
Fig. 9. Relations between contact angle variations and element mole percentage variations

Conclusion
According to overall results in the present study, conclusions can be drawn in the following:
1. The wettability of the reservoir rock obtained from block Hei 47 changes after CO2-brine-rock interactions.
2. There are minerals dissolution and precipitation occurring on the reservoir rock surface. It results in changing the mineral
composition and wettability of the resercoir rock surface at the same time.
3. There are close relations between contact angle variations of water and element mole percentage variations on the
reservoir rock surface. With the increasing O, Si, Al, Na or K mole percentage, the decreasing C or Fe mole percentage, the
rock surface becomes more hydrophilic.

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