Journal of Dispersion Science and Technology

ISSN: 0193-2691 (Print) 1532-2351 (Online) Journal homepage: http://www.tandfonline.com/loi/ldis20

The Wettability Alteration and the Effect of Initial

Rock Wettability on Oil Recovery in Surfactantbased Enhanced Oil Recovery Processes
Wan-Fen Pu, Cheng-Dong Yuan, Xiao-chao Wang, Lin Sun, Ruo-kun Zhao,
Wen-jing Song & Xiao-feng Li
To cite this article: Wan-Fen Pu, Cheng-Dong Yuan, Xiao-chao Wang, Lin Sun, Ruo-kun Zhao,
Wen-jing Song & Xiao-feng Li (2016) The Wettability Alteration and the Effect of Initial Rock
Wettability on Oil Recovery in Surfactant-based Enhanced Oil Recovery Processes, Journal of
Dispersion Science and Technology, 37:4, 602-611, DOI: 10.1080/01932691.2015.1053144
To link to this article: http://dx.doi.org/10.1080/01932691.2015.1053144

Accepted author version posted online: 29

Jul 2015.

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Date: 16 April 2016, At: 07:31

Journal of Dispersion Science and Technology, 37:602611, 2016

Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932691.2015.1053144

The Wettability Alteration and the Effect of Initial Rock

Wettability on Oil Recovery in Surfactant-based
Enhanced Oil Recovery Processes
Wan-Fen Pu,1,2 Cheng-Dong Yuan,1,2 Xiao-chao Wang,3 Lin Sun,1,2
Ruo-kun Zhao,4 Wen-jing Song,4 and Xiao-feng Li5
1

State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Chengdu, China
School of Petroleum and Natural Gas Engineering, Southwest Petroleum University, Chengdu, China
3
CNOOC EnerTech-Drilling & Production Co., Tianjin, China
4
Gas Production Engineering Research Institute of PetroChina Southwest Oil-Gas Field Company,
Guanghan, China
5
China Petroleum & Chemical Corporation Sichuan Petroleum Branch, Chengdu, China

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GRAPHICAL ABSTRACT

Wettablity alteration of rock surface is an important mechanism for surfactant-based enhanced

oil recovery (EOR) processes. Two salt and temperature-tolerant surfactant formulations
were developed based on the conditions of high temperature (97120 C) and high salinity
(20  104 mg/L) reservoirs where a surfactant-based EOR process is attempted. Both the two
sufactant formulations can achieve ultralow interfacial tension level (103 mN/m) with crude
oil after aging for 125 days at reservoir conditions. Wettability alteration of core slices induced
by the two surfactant formulations was evalutated by measuring contact angles. Core ooding
Received 7 May 2015; accepted 17 May 2015.
Address correspondence to Cheng-Dong Yuan, School of Petroleum and Natural Gas Engineering, Southwest Petroleum
University, Chengdu, China. E-mail: megycd@163.com
Color versions of one or more of the gures in the article can be found online at www.tandfonline.com/ldis.

602

WETTABILITY ALTERATION AND INITIAL ROCK WETTABILITY

603

experiments were carried out to study the inuence of initial rock wettabilities on oil recovery
in the crude oil/surfactant/formation water/rock system. The results indicated that the two
formulations could turn oil-wet core slices into water-wet at 90120 C and 20  104 mg/L
salinity, while the water-wet core slices retained their hydrophilic nature. The core ooding experiments showed that the water-wet cores could yield higher oil recovery compared with the oil-wet
cores in water ooding, surfactant, and subsequent water ooding process. The two surfactant
formulations could successfully yield additional oil recovery in both oil-wet and water-wet cores.

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Keywords

Enhanced oil recovery, rock wettabiltiy, surfactant, wettability alteration

1. INTRODUCTION
An important aspect of any enhanced oil recovery (EOR)
process is the effectiveness of process uids in removing oil
from the rock pores at the microscopic scale. This is about
microscopic displacement efciency which largely determines the success or failure of a process.[1] Microscopic displacement efciency is mainly affected by wettability,
capillary force, distributions of oil and water in pore spaces,
and relative permeability, etc.[2] These factors are also
related to each other. The relationships among these factors
are very complex in the crude oil=formation water=rock=
displacing uid system. It is very important to quantify
the effect of each factor on oil recovery.
For rock wettability, Jamaloei et al.[3] investigated the
inuence of pore wettability on the microstructure of residual
oil in surfactant-enhanced water ooding in heavy oil reservoirs. Humphry et al.[4] reported the impact of wettability
on residual oil saturation and capillary desaturation curves.
Owens et al.[5] presented the effect of rock wettability on
oilwater relative permeability relationships. Grattoni et al.[6]
studied the effects of wettability on gas and oil production
from water ood residual oil. However, rock wettability not
only affects relative permeability characteristics and the nature of uid saturations of a uid=rock system, but also determines the value of capillary force which affects microscopic
displacement efciency. Therefore, it is necessary to determine reservoir wettability and its effect on oil recovery.
As early as 1958, Bobek et al.[7] emphasized the signicance of reservoir rock wettability and investigated the factors which may alter rock wettability. In the past few
decades, a great deal of the research efforts have focused
on the rock wettability. The related studies of rock wettability have been carried out in water ooding[810] and many
EOR processes: such as, wettability alteration induced by
nanoparticles uid for EOR processes.[1115]
Wettability alteration as an important mechanism for
surfactant-based chemical ooding EOR process has also
attracted extensive attention. Ravi et al.[16] investigated the
effects of a new plant surfactant (extracted from mulberry
tree leaves) on wettability alteration. Dehghan et al.[17]
reported the interfacial tension and wettability change
phenomena during alkalisurfactant interactions with acidic
heavy crude oil. Zhang et al.[18] studied wettability alteration
by trimeric cationic surfactant at water-wet=oil-wet mica
mineral surfaces. Jarrahian et al.[19] did a mechanistic study

on wettability alteration of carbonate rocks by surfactants.

Rostami Ravari et al.[20] investigated the wettability
alteration of carbonates in combined surfactant-enhanced
gravity drainage. Bera et al.[21] carried out the mechanistic
study of wettability alteration of quartz surface induced by
nonionic surfactants. Mohan et al.[22] studied wettability
altering by many surfactants in carbonate rocks. Salehi
et al.[23] conducted mechanistic study of wettability alteration
using surfactants with applications in naturally fractured
reservoirs. Goudarzi et al.[24] indicated anionic the mixture
of surfactant and alkali can alter wettability from oil-wet to
strongly water-wet conditions for carbonates. However, most
of the scientic literatures have focused on mechanistic studies on wettability alteration by surfactants and paid less
attention to the effect of initial rock wettability on oil recovery in surfactant ooding process. And these previous studies
mainly aimed at medium-low temperature and salinity reservoirs. Reviewing the literatures in this eld, there is little
research conducted on surfactant ooding EOR techniques
for high temperature and high salinity reservoirs (e.g.,
90120 C and 20  104 mg=L salinity). Such high temperature and salinity put forward higher requirements for surfactant achieving steady ultralow interfacial tension (IFT).
In this study, we attempt to improve the recovery by
surfactant-based EOR processes from water ooded reservoirs with temperatures ranging from 97 C to 120 C and a
salinity of 20  104 mg=L. Two low concentration and
highly effective surfactant formulations that could obtain
ultralow IFT at reservoir conditions were developed. This
study focuses on a systematic investigation of the wettability alteration induced by surfactants and the effect of initial
rock wettability on oil recovery. The effects of surfactant
concentration and temperature on wettability alteration
were evaluated by measuring contact angles. Initial waterwet and oil-wet cores were employed to carry out core
ooding experiments to investigate the effect of initial rock
wettability on oil recovery in the crude oil=surfactant=
formation water=rock system.
2. EXPERIMENTAL SECTION
2.1. Materials
Sodium alpha-olene sulfonates (AOS, RCH(OH)
(CH2)n-SO3Na n C1416) and amphocaroxymethyl
imidazoline (AI) were obtained from Jinan Bao Li Yuan

604

W.-F. PU ET AL.

Chemical Co., Ltd (China) and Taiyuan Finechem

Chemical Co., Ltd (China), respectively. Sodium alcohol
ether sulfate (AES, C12H25NaO3S) and ethoxylated fatty
alcohol carboxylate (AEC, R-(OCH2CH2)nOCH2COO
Na, R C16=C18, n 9) were provided by Guangzhou
Hui He Chemical Co., Ltd, China. Crude oil, reservoir
injection water, and sandstone core were obtained from a
block (Tarim Basin, China). This block is a sandstone
reservoir with a formation temperature of 97 C. The properties of reservoir injection water are shown in Table 1. The
viscosity and density of the crude oil are 2.88 mPa s and
0.814 g=cm3 at reservoir condition, respectively. The saturated hydrocarbon composition was analyzed by the HP
6890 Series gas chromatography (Agilent Technologies,
Inc., USA), and the results are presented in Figure 1.

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FIG. 1. Saturated hydrocarbon composition of crude oil.

2.2. Surfactant Formulation Preparation
Two surfactant formulations, AOS AEC and AES
AI, were prepared with reservoir injection water. The mass
concentration ratio of AOS to AEC and AES to AI are 1:3
and 1:1, respectively. Each surfactant formulation was prepared at different concentration (0.05%, 0.1%, 0.2%, 0.3%).
The determination of the two surfactant formulations was
based on a large number of evaluation experiments where
the capabilities of reducing IFT of 12 surfactants belonging
to 5 different types of surfactants and their compounded
formulations were investigated. The whole evaluation
process is not the purpose of this paper and will not be
illustrated in detail here. Two surfactant formulations
(0.05%AOS 0.15%AEC and 0.05%AES 0.05%AI)
obained stable ultra-low IFT of 5.78  103 mN=m and
7.83  103 mN=m, respectively, with crude oil after aging
for 125 days at 120 C and 20  104 mg=L salinity.
2.3. Core Slices Preparation
A series of core slices were used as the solid substrates to
determine the wettability behavior with the surfactant formulation. Thin core slices were cut from reservoir cores
and were polished smooth. Core slices were immersed in
diluted hydrochloric acid for 12 hours and then were
washed with deionized water. The wash was continued until
the pH of ushing uid was neutral, and they were dried in
an oven thermostat at 80 C for 24 hours. The contact angles
of the washed core slices obtained after all these treatments

are about 28 , which is considered as water-wet. Some core

slices were submerged in simethicone to alter wettabilities
from water-wet to oil-wet. These core slices successfully
became hydrophobic after the surface treatment aging for
5 weeks (approx.) at approx.100 C in simethicone. The
measured contact angles are about 138 .
2.4. Contact Angle Determination
Both water-wet and oil-wet core slices were loaded into
heat-resistant plastic bottles lled with surfactant formulations. These core slices were immersed in the surfactant
formulation AOS AEC or AES AI at different temperatures (60 C, 90 C, 120 C) aging for different time (3 hours
15 days). Then the core slices were taken out at the planed
time. The contact angle was measured directly on a contact
angle measuring instrument (HARKE-SPCA) at ambient
conditions (25 C and 1 atm). The formulation consisted of
a core slice as solid substrate, crude oil as oleic-phase, and
reservoir injection water as aqueous-phase. Treiber et al.[25]
dened the aqueous contact angle in a three-phase system
(water, oil, and rock surface) as shown in Table 2. The schematic diagram of contact angle measuring is shown in
Figure 2. Procedures were as follows: (1) The measuring
unit lled with injection water was placed in the middle of
objective table. The core slice was loaded into one place
where is two-thirds of the measuring unit height from the
bottom of the measuring unit. (2) Open gure analyzing

TABLE 1
Properties of reservoir injection water
Ion content (mg=L)
Salinity
(mg=L)
204672.24

K Na

Ca2

Mg2

Cl

SO4 2

HCO3 

I

Br

pH

Density
(g=cm3)

67430.31

10279.6

1200.74

125501.51

150

88.17

60

5.4

1.144

WETTABILITY ALTERATION AND INITIAL ROCK WETTABILITY

605

TABLE 2
The evaluation index of rock wettability[25]
Wettability

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Strong oil-wet
Oil-wet
Weak oil-wet
Intermediate wet
Weak water-wet
Water-wet
Strong water-wet

Wettability index

Contact angle ( )

10.7
0.70.3
0.30.1
0.10.1
0.10.3
0.30.7
0.71

153180
117153
99117
8199
6381
2763
027

software. Adjust the height of the objective table and the

location of the measuring unit to make video image be in
a proper measuring region. (3) Oil drop was hung below
the lower surface of the core slice through a syringe needle.
The contact angle was analyzed using the gure analyzing
software when the oil drop was stable.
2.5. Core Flooding Experiment
2.5.1. Core Preparation
The initial wettability of cores was determined by both
Amott method and contact angle method at ambient conditions. The AmottHarvey wettability index (Iw) are ranging from 0.5 to 0.7, and contact angle are ranging
from 29 to 35 , which are considered as water-wet. To
alter the wettabilities, the cores were soaked in simethicone
at approx.100 C for 5 weeks (approx.). The cores wettabilities were successfully altered from water-wet to oil-wet.
The measured Iw of cores after treatment were in the range
of 0.4 to 0.3, and contact angle were ranging from 129
to 133 , which are considered as oil-wet. Core sample with
its dimensions is shown in Figure 3.
2.5.2. Experimental Procedures
Rocks with different initial wettabilities (oil-wet and
water-wet) were chosen for the ooding experiments.
Figure 4 shows the schematic diagram of the experimental
apparatus. Procedures were as follows:
1. All core samples were dried at 80 C for 12 hours and
the dry weight was measured. Each core sample was

FIG. 2.

FIG. 3. Core sample with its dimensions.

vacuumized for 12 hours and saturated with reservoir
injection water. Then the wet weight was measured.
Pore volume (PV) and porosity were calculated based
on the weight difference before and after the core was
saturated.
2. All equipments were connected as shown in Figure 4.
The single-phase liquid (formation water) water
permeability was tested.
3. The core holder was placed in an oven thermostat (set in
100 C). An annular pressure was put on to the core
holder, and crude oil was injected into the core at a
constant rate of 1.0 ml=min. The oil injection did not
stop until there was no water produced in the outlet
and the pressure difference was stable. Irreducible water
saturation and initial oil saturation were established
according to the water yield. The core holder was settled
for 3 days.
4. The reservoir injection water was injected into cores at a
constant rate of 2.0 ml=min for water ooding. The
water ooding was stopped when water cut was at

The schematic diagram of contact angle measuring.

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606

W.-F. PU ET AL.

FIG. 4. Schematic diagram of the water ooding and surfactant ooding experiments.
70%. Meanwhile, accumulative oil production was
recorded. The water ooding recovery was calculated.
5. A 0.3 PV surfactant formulation (0.05% AOS 0.15%
AEC or 0.05% AES 0.05% AI) was injected for surfactant ooding. Then, the subsequent water ooding was
conducted. The water injection was stopped when water
cut was at 98%. The accumulative oil production was
recorded. The water ooding recovery was calculated.
The surfactant and subsequent water ooding recovery
was calculated.
3. RESULTS AND DISCUSSION
3.1. Wettability Alteration of Core Slices by AOS AEC
Surfactant Formulations
3.1.1. The Effect of the Concentration of AOS AEC
Surfactant formulations with different concentrations
(0.05%, 0.1%, 0.2%, 0.3%) were evaluated at 100 C. The
results are shown in Table 3. All initial water-wet core slices
kept their hydrophilic nature after being immersed in these
different concentration AOS AEC formulations. The
hydrophilic groups in AOS AEC formulation were anion
and nonionic. There is an electrostatic repulsion between
anionic surfactant molecule and core slice surface with a
negative charge. Therefore, the anionic surfactant molecules could only absorb the quartz plate surface in small
amounts with the hydrophilic group toward the solution
through a Van der Waals force and a hydrophobic interaction force. Thus, the core slices still retain hydrophilic.
However, the contact angles of the water-wet core slices
overall increased with aging time and concentration. This

is because the anionic surfactant molecules would aggregate

in core slices surface and form hemi-micelle or micelles
adsorption with increasing aging time and concentration.[26]
This leads to the wettability alteration from strongly
water-wet to weak water-wet.
However, for the initial oil-wet core slices, wettability
reversal occurred in 1 day after being immersed in different
concentration AOS AEC formulations. The higher the concentration, the quicker the core slices changed from oil-wet to
water-wet. This is because micelles were formed in the higher
concentration AOS AEC solution. The micelles had a good
solubilization capacity to simethicone on the core slices
surface. The simethicone was washed out of core slices, which
recovers the hydrophilic nature of core slices.[27]
TABLE 3
The effect of the concentration of AOS AEC on the
wettability of core slices
Contact angle ( )
3
hours

1
day

6
days

10
days

15
days

0.05

0.10

0.20

0.30

0.05 128.9
0.10 125.3
0.20 114.5
0.30 98.8

37.7
23.4
38.2
32.8
41.6
40.7
40.9
36.7

46.6
28.0
33.5
46.3
25.9
44.3
29.3
50.4

41.9
46.2
55.0
51.5
36.5
36.4
37.2
27.2

27.9
50.6
54.9
57.3
23.6
38.8
24.9
27.8

Concentration (%)
Initial
water-wet
core slices
Initial oil-wet
core slices

607

3.1.2. The Effect of Temperature on Wettability for

AOS AEC Formulation
The initial water-wet and oil-wet core slices were treated
with 0.05%AOS 0.15%AEC formulation at different temperatures (60 C, 90 C, 120 C). The results are shown in
Table 4. For water-wet core slices, in each temperature,
the contact angles increased with aging time at rst. Compared with 60 C and 90 C, this increased trend was ahead
at 120 C where the contact angle increased to 58.3 after
the core slice was immersed for 1 day. The primary cause
is that the higher temperature (120 C) enhanced the thermal
motion of surfactant molecules, which accelerates the
adsorption of surfactant molecules on the surface of core
slices. However, the contact angles decreased with the
increasing of aging time. This can be attributed to two
aspects. On the one hand, the adsorption is an exothermic
process.[28] Long duration in high temperature is detrimental
to the adsorption process. On the other hand, the solubility
of ionic surfactant in water is increased, which causes the
decrease of adsorption capacity as the ability of surfactant
molecules to absorb on the solid surface is reduced.
For oil-wet core slices, wettability reversal occurred in
each temperature. And, it was easier for wettability reversal
at higher temperatures. After aging for 3 hours, the core
slices at 60 C and 90 C still retained oil-wet, but the core
slice at 120 C was changed to intermediate wet. At a relative
low temperature, there is a strong hydrogen bonds action
between simethicone molecules and core slices. It is more
difcult to strip simethicone molecules from the surface of
core slices. When temperature is increased to higher temperature (120 C), the hydrogen bonds are weakened even
broken. In addition, the activity of surfactant formulation
is enhanced. Consequently, it is easier to strip simethicone
molecules from core slices, and the core slices restored their
hydrophilic nature. These core slices after becoming waterwet were continued to be immersed in the surfactant
solution. The contact angle variation exhibited the same
trend with that of the initial water-wet core slices.

3.2. Wettability Alteration of Core Slices by AOS AEC

Surfactant Formulations
3.2.1. The Effect of the Concentration of AES AI
Surfactant formulations with different concentrations
(0.05%, 0.1%, 0.2%, 0.3%) were evaluated at 100 C. The
results are shown in Table 5. For initial water-wet core slices,
the results are consistent with AOS AEC formulation. All
core slices kept their initial water-wet state after the treatment
of different concentration AES AI formulations. Surfactant
AI is an ampholytic surfactant with cationic groups. The
hydrophilic groups of surfactant AI have both anionic and
cationic groups. The hydrophilic groups of surfactant AI
have both anionic and cationic groups, which means there
exists anion and kation in the surfactant solution. The hydrophilic groups of the surfactant AI molecules absorb on the
negatively charged core slices surfaces. However, there is
electrostatic repulsion between the anionic groups of hydrophilic groups and negative charge in the surface of core slices,
which reduces the interaction point between core slices surface and hydrophilic groups of surfactant AI molecules.
Thus, the other surfactant molecules can insert the absorbed
layer through the hydrophilic groups interaction with
absorbed surfactant AI molecules. Consequently, the analogous single absorbed layer structure with hydrophilic groups
facing outward was formed.[27] Therefore, the core slices surface still retained their hydrophilic character with only a slight
uctuation of the contact angle. For initial oil-wet core slices,
AES AI formulation could make wettability reversal occur
as AOS AEC did. Also, the higher the concentration of
AES AI formulation, the faster the core slices changed from
oil-wet to water-wet.
3.2.2. The Effect of Temperature on Wettability for
AES AI Formulation
The initial water-wet and oil-wet core slices were treated
in 0.05% AES 0.05% AI formulation at different temperatures (60 C, 90 C, 120 C). The results are shown in Table 6.
TABLE 5
The effect of the concentration of AES AI on the
wettability of core slices

TABLE 4
The effect of temperature on the wettability in AOS AEC
system
Initial water-wet

Initial oil-wet

Aging
time

60 C 90 C 120 C

60 C

3 hours
1 day
3 days
6 days
10 days
15 days

22.1
24.6
47.5
44.6
38.5

126.2 115.5
26.2 26. 8
34.1 37.7
42.6 45.1
43.2 37.0
37.7 37.1

Contact angle

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WETTABILITY ALTERATION AND INITIAL ROCK WETTABILITY

27.5
39.4
41.6
39.8
40.6

58.3
44.8
30.5
33.0
31.5

90 C

120 C
88.3
38.4
52.5
29.7
31.7
33.9

Contact angle ( )
3
hours

1
day

6
days

10
days

0.05

0.10

0.20

0.30

0.05 119.0
0.10 103.5
0.20 71.1
0.30 82.7

21.9
23.2
27.1
26.4
48.1
39.4
41.8
27.3

29.8
30.7
28.0
43.1
28.1
26.5
35.3
41.3

24.4
27.2
25.3
36.3
27.8
32.2
45.0
32.3

Concentration (%)
Initial
water-wet
core slices
Initial oil-wet
core slices

15
days
22.7
23.0
32.0
38.4
22.0
32.3
29.6
30.3

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W.-F. PU ET AL.

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TABLE 6
The effect of temperature on the wettability in AES AI
system
Initial water-wet

Initial oil-wet

60 C 90 C 120 C 60 C 90 C 120 C

3 hours
1 day
6 days
10 days
15 days

25.2
23.7
26.3
21.2

Contact
angle ()

Aging
time

27.3
25.4
34.4
22.1

24.0
37.2
44.1
41.4

115.3
28.2
32.0
30.8
27.2

95.9
24.7
23.8
32.6
20.9

83.4
47.9
52.2
44.1
36.9

For both the initial water-wet and oil-wet core slices, the
contact angles have the same change trend in AES AI
formulation with that of AOS AEC formulation.
3.3. The Effect of Initial Rock Wettability on Oil
Recovery
The core ooding experimental results from several cores
are summarized in Table 7 and Figures 57. The initial
water saturation (Swi) of oil-wet core was smaller than that
of water-wet core. These results are consistent with Craig[29]
and Hendraningrat et al.[2]. In water-wet cores, water lls
TABLE 7
Petrophysical properties of cores and the results of core
physical simulation experiment
Core no.
Diameter (cm)
Length (cm)
Wettability
Porosity (%)
Permeability
(103 mm2)
Initial oil
saturation (%)
Initial water
saturation (%)
Water ooding
recovery (%)
Surfactant
system
Surfactant and
subsequent
water ooding
recovery (%)
Total recovery
(%)
Residual oil
saturation (%)

ww1

ow1

ww2

ow2

3.74
3.76
3.75
3.74
6.98
7.04
7.02
7.00
Water-wet Oil-wet Water-wet Oil-wet
32.03
35.48
32.96
35.23
38.17
38.03
39.13
36.52
72.99

78.27

74.06

81.63

27.01

21.73

25.94

18.37

36.48

31.57

35.47

30.25

0.05% AOS
0.15% AEC
24.06
19.86

0.05% AES
0.05% AI
21.42
15.25

60.54

51.43

56.89

45.50

28.80

38.01

31.93

44.49

FIG. 5. Oil recovery versus injected PV prole during WF, SF, and
SWF processes in cores with different wettabilities for AOS AEC
system.

the small pores and forms a thin water lm on rock surfaces.

Hence, water saturation is relatively high. However, in
oil-wet cores, water is found as discrete droplets in the center of larger pores, and oil is found in the small pores as thin
oil lms on rock surfaces. Water saturation will typically be
much lower than in water-wet cores. The oil recovery during
the water ooding process indicated that initial wettability
affects water ooding behavior. Water-wet cores have a
higher oil recovery than oil-wet cores. This is mainly
because capillary force is driving force in water-wet pores
during water ooding. However, capillary force is resistance
in oil-wet pores.
For the two surfactant formulations, after 0.3 PV formulation was injected, additional oil recovery was successfully
obtained in both oil-wet and water-wet cores due to the surfactant ooding and subsequent water ooding recovery
processes. Similar to the trend in the water ooding process,
for both two surfactant formulations, water-wet cores have

FIG. 6. Oil recovery versus injected PV prole during WF, SF, and
SWF processes in cores with different wettabilities for AES AI system.

609

WETTABILITY ALTERATION AND INITIAL ROCK WETTABILITY

to the other. The additional capillary force, p, can be

expressed by (assuming h1 h2)[30]:


1
1
p2  p1 p 2row cos h

r2 r1

FIG. 7.

Water ooding recovery, surfactant, and subsequent water

ooding recovery for different initial wettability.

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2

For example, r2 1 mm, row 5 mN=m, then the driving

force that pushes the oil drop through the narrower part
must exceed 104 Pa. Further, assuming the average length
of these unequal diameter pores is 50 mm, and there is one
drop in each pore. If we want to mobilize every oil drop,
the needed pressure gradient should be calculated as
follows:


p2  p1 =L 104 N=m2  50  106 m 2  108 N=m
3
Obviously, there are no such reservoirs that can give such a
high pressure gradient. That is, only reducing the required
pressure gradient could the oil drop hopefully be mobilized
again. The ultralow IFT is expected at this situation. This is
why the two ultralow IFT surfactant formulations have the
capability to greatly enhance oil recovery.
For oil-wet cores, the capillary force is always a resistance in water ooding process. The concept of capillary
number (Nca) was introduced to quantitatively analyze
how the residual oil could be remobilized again. The Nca
has been proven to be reasonably successful. The capillary
number was dened as the ratio of viscous force to capillary force as in Equation (4).[1]
Nca

FIG. 8. A oil drop is trapped in a preferentially water-wet unequal

diameter pore. Adapted from reference [30].

1

Because r1 > r2, then p2 > p1 and a pressure drop

(additional capillary force) exists in the direction from
point 2 to 1. Hence, an extra driving force that will have
to exceed the additional pressure drop is required to force
the oil drop through the narrower part of the capillary
constriction.
If r1  r2, then Equation (1) can be written as following:
p2  p1 p 2row cos h=r2

a higher additional oil recovery than oil-wet cores as shown

in Figure 7. To water-wet cores, the additional oil recoveries
of 24.06% and 21.42% were achieved for AOS AEC and
AES AI formulation, respectively. The oil-wet cores
yielded the additional oil recovery of 19.86% and 15.25%
for AOS AEC and AES AI formulation, respectively.
This indicated that the two surfactant formulations could
greatly improve oil recovery. The improving oil recovery
mechanism of the surfactant formulations was mainly
attributed to the reducing IFT effect. Whether the residual
oil after water ooding would ow again depends on the
relative values of the driving force and the resistance. At
the initiation of a typical water ooding, the displaced
phase (oil phase) is initially at a relatively high saturation.
The phase is essentially in continuous contact throughout
the porous medium. For water-wet cores, at this situation,
the capillary force is the driving force. However, experience
indicates that once the oil phase is trapped, it is more difcult to mobilize it due to the Jamin effect where the pressure
required to force a trapped oil phase through a capillary
system, such as a porous rock, can be quite high.[1] The
phenomenon can be described most easily by analyzing a
trapped oil droplet in a preferentially water-wet unequal
diameter pores, as shown in Figure 8. Assuming the pressure within the oil drop is constant from one end of the drop

vmw
row cos h

4

where v is interstitial velocity, mw is the viscosity of displacing phase, and row is the IFT between the displaced and
displacing phases. It has been veried that the bigger the
Nca, the higher the oil recovery. Therefore, we can see that
reducing row is still the effective method which is easier to
achieve.
The initial oil-wet cores after ooding were taken out
and cut into thin core slices using the method mentioned
in Sec. 2.3. The core wettabilities were checked. Table 8

610

W.-F. PU ET AL.

TABLE 8
The contact angles of the initial oil-wet core slices before
and after surfactant ooding

ooding under the ultralow IFT is a promising EOR

technique for high temperature and high salinity oil
reservoirs.

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Contact angles ( )
Core
no.
ow1
ow2

Surfactant system

Before
ooding

After
ooding

0.05% AOS 0.15% AEC

0.05% AES 0.05% AI

129.57
132.41

37.72
34.46

shows the results of wettability check. We also observed

that both two surfactant formulations changed the wettability from oil-wet to water-wet (from 129.57 to 37.72
for AOS AEC formulation, from 132.41 to 34.46 for
AES AI formulation) during the ooding process. This
means that the two surfactant formulations have an excellent improvement effect on the oil-wet core wettability,
which facilitates for the mobilization of trapped oil.
4. CONCLUSION
1. The two ultrolow IFT surfactant formulations AOS
AEC and AES AI can make the wettability of the
initial oil-wet cores slices changed from oil-wet to
water-wet at 90120 C and 20  104 mg=L salinity.
The higher the temperature, the quicker the wettability
reversal occurred. The initial water-wet cores still retain
their hydrophilic nature.
2. Surfactant concentration has an effect on wettability
reversal of the initial oil-wet cores. The higher the
concentration, the quicker the core slices changed from
oil-wet to water-wet.
3. The Swi of oil-wet cores was smaller than in water-wet
cores due to the different existing state of water in the
porous media. The initial rock wettability affects the
water ooding process. Water-wet cores have a higher
oil recovery than oil-wet cores during the water ooding
process as the capillary force is resistance in oil-wet
pores and the driving force in water-wet pores.
4. The initial rock wettability also has an inuence on the
surfactant ooding and subsequent water ooding
recovery processes. Similar to the trend in the water
ooding process, water-wet cores have a higher
additional oil recovery than oil-wet cores. Likewise, the
ultralow IFT surfactant formulations can make the
initial oil-wet cores change their wettability to water-wet
during ooding process.
5. The two ultralow IFT surfactant formulations successfully yielded additional oil recovery in both oil-wet and
water-wet cores. The results indicated that the two surfactant formulations have a great potential for improving oil recovery, and low concentration surfactant

FUNDING
This research is partially supported by technology innovation talent project (2014-070), Sichuan province.
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