See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/229125389

Analysis of oil recovery rates for spontaneous

imbibition of aqueous surfactant solutions into
preferential oil-wet...

Article in Colloids and Surfaces A Physicochemical and Engineering Aspects December 2004
DOI: 10.1016/j.colsurfa.2004.09.013

CITATIONS READS

9 35

1 author:

Dag Chun Standnes

Statoil ASA/University of Stavanger (UiS)
41 PUBLICATIONS 936 CITATIONS

SEE PROFILE

All content following this page was uploaded by Dag Chun Standnes on 18 June 2016.

The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original document
and are linked to publications on ResearchGate, letting you access and read them immediately.
 Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 93101

Analysis of oil recovery rates for spontaneous imbibition of aqueous

surfactant solutions into preferential oil-wet carbonates
by estimation of capillary diffusivity coefficients
Dag Chun Standnes
Centre for Integrated Petroleum Research (CIPR), University of Bergen, Allegaten 41, N-5007 Bergen, Norway

Received 26 February 2004; accepted 7 September 2004

Abstract

Spontaneous imbibition (SI) is a very important oil recovery mechanism from low-permeability fractured reservoirs. However, this process
will not take place if the reservoir rock is preferential oil-wet. Recently, it was discovered that SI into preferential oil-wet carbonate is
possible if the porous medium is exposed to a water-phase containing cationic surfactants of the type Cn TAB. Estimation of SI rates for
aqueous surfactant solutions into preferential oil-wet carbonates based on the diffusion equation approach have been performed in this work.
Capillary diffusivity coefficients (CDCs) were calculated for SI tests into preferential oil-wet carbonates and compared to corresponding data
for imbibition of water into strongly water-wet chalk (reference wettability state). The diffusion approach is especially suitable for SI driven
by a foregoing wettability alteration process induced by surfactants due to problems to measure dynamic flow parameters accurately during
the wettability alteration process. The solution to the three-dimensional diffusivity equation describing oil recovery as a function of time is
expressed by an infinite series. Approximating the solution using only one term in each spatial direction makes it possible to calculate CDCs
after performing a least square fit on experimental data. The results show that CDCs for SI into preferential oil-wet carbonates are in the range
(1.714) 1011 m2 /s, which are approximately three orders of magnitude lower than for SI of water into strongly water-wet chalk. However,
CDCs for imbibition into preferential oil-wet carbonates are still larger than what is observed for cores having mixed-wettability of which
have the exponential decay parameter reduced up to four orders of magnitude compared to imbibition into strongly water-wet core material
[N.R. Morrow, G. Mason, Curr. Opin. Colloid Interf. Sci. 6 (2001) 321337]. The calculated CDC for imbibition into strongly water-wet
chalk shows good agreement with other values published in the literature.
2004 Elsevier B.V. All rights reserved.

Keywords: Spontaneous imbibition; Capillary diffusivity coefficient; Surfactant solutions

1. Introduction describing different approaches to model the SI process

analytically (see for example the paper by Reis and Cil
The process when water is sucked into a porous medium [2]). These models can be divided into four main groups
by the action of capillary forces is referred to as sponta- [3]:
neous imbibition (SI). This process is regarded as a very
important driving mechanism for oil recovery in fractured (a) diffusivity functions [48],
water-wet reservoirs which are often characterized by high- (b) scaling relations [912],
permeability fractures and low-permeability matrix. There (c) empirical functions [1315],
exist a comprehensive amount of papers in the literature (d) material balance functions [16].
Recently, Barenblatt et al. [17] have presented a non-
Tel.: +47 55 58 33 74; fax: +47 55 58 82 65. equilibrium theory to model SI based on redistribution time
E-mail address: dag.standnes@cipr.uib.no. of the flow network for water and oil. However, modeling the

0927-7757/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2004.09.013
94 D.C. Standnes / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 93101

Nomenclature
Greek letters
Ai area of the ith imbibition surface (m2 ) 2 /L2 (m2 )
AN acid number (mg KOH/g oil) fit parameter describing the rate of convergence
Arquad MC-50 Arquad (min1 )
C chalk g geometrical mean of the water and the oil and
C = (g / k)(L2C /L2 ) (s/m2 ) viscosity (Pa s)
CDC capillary diffusivity coefficient (m2 /s) o oil viscosity (Pa s)
Cn TAB surfactants of the type alkyltrimethylammoni- w water viscosity (Pa s)
umbromide oilwater interfacial tension (N/m)
C12TAB (C) dodecyltrimethylammoniumbromide fractional porosity (m3 /m3 )
(chloride)
d diameter (m)
D capillary diffusivity coefficient (m2 /s) SI process using the diffusivity approach in (a) is the subject
DAV average capillary diffusivity coefficient (m2 /s) in this paper.
Do dolomite When the reservoir rock is preferential oil-wet which is
Dodigen 5462 Dodigen very often the case for carbonate formations, SI will not take
IFT interfacial tension (N/m) place due to negative capillary pressure and the result is low
IOR improved oil recovery sweep efficiency and low oil recovery. There is a great po-
k absolute permeability (m2 ) tential for improved oil recovery (IOR) from preferential oil-
kro relative permeability to oil () wet carbonate fields due to the large amount of oil residing in
krw relative permeability to water () such reservoirs. It has recently been documented in a series
li length from the ith imbibition surface to the of papers that SI of water into preferential oil-wet carbon-
no-flow boundary (m) ate is possible if the injection water contains surface-active
L length of the sides of the cube or height of cores agents of the type alkyltrimethylammonium bromide (chlo-
(m) ride) Cn TAB (C) [1824]. The process was described as a
LC characteristic length (m) wettability alteration process where the cationic surfactant
Pc capillary pressure (Pa) desorbed acidic components adsorbed to the carbonate sur-
PV pore volume (cm3 ) face under creation of ion-pairs. In this way, the carbonate
Qo oil production at time t (m3 ) surface becomes more water-wet and the aqueous phase can
Qw water volume imbibed at time t (m3 ) imbibe by capillary forces. The results in the cited papers
Qomax maximum oil recovery produced after infinite [1824] showed that the imbibition process using surfactants
time (m3 ) was significantly slower than what is typical for SI rates of wa-
Qwmax water volume imbibed at infinite time (m3 ) ter into strongly water-wet rocks. It is of crucial importance
R correlation coefficient when modeling the process and for application of wettability
S average water saturation at time t (fraction, modifying agents in the field (up-scaling to real matrix block
m3 /m3 ) sizes) to get a quantitative measure of the delay in imbibition
Sw normalized water saturation (fraction, m3 /m3 ) time compared to some wettability reference state (ideally,
Swi initial water saturation (fraction, m3 /m3 ) this state should be the reservoir wettability when planning
Swf maximum water saturation at residual oil satu- an IOR-project). However, due to the lack of reservoir cores,
ration (fraction m3 /m3 ) strongly water-wet chalk will be used as a wettability refer-
SI spontaneous imbibition ence state in this work. This also allows for comparison with
t imbibition time (min) other capillary diffusivity coefficients (CDCs) data reported
tD,MZM dimensionless imbibition time in the literature.
(MaZhangMorrow) The purpose of this work is to present a simple method to
Vb bulk volume of the rock sample (m3 ) determine CDCs from SI tests performed on preferential oil-
wt.% weight percent wet carbonate cores (chalk and dolomite cores) using surfac-
x coordinate tants as a wettability modifying agent. This approach is espe-
xD dimensionless x-coordinate cially suitable when surface-active agents are involved in the
y coordinate aqueous phase, because all the dynamic parameters, which
yD dimensionless y-coordinate are extremely difficult to determine accurately for a SI caused
z coordinate by a wettability alteration process (capillary pressure and rel-
zD dimensionless z-coordinate ative permeabilities) are lumped into one single parameter,
the CDC. The method is demonstrated by using previously
published data for SI of water into strongly water-wet chalk
 D.C. Standnes / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 93101 95

and for SI of aqueous surfactant solutions into preferential where

oil-wet carbonates (chalk and dolomite cores essentially not
imbibing any pure brine at all).
2. Theoretical model
Consider a cubic matrix block with side lengths L initially
at initial water saturation Swi . If the porous medium is water-
wet and the block is totally immersed in water at time t = 0,
the water saturation Sw at any point (x, y, z) in the block
at time t 0 will be described by the following hyperbolic
partial differential equation:
2
= (5)
L2
Qo is the oil production at time t (m3 ); Qomax the maximum oil
recovery level at infinite time (m3 ); DAV the average capillary
diffusivity coefficient (m2 /s); L the length of the sides of the
cube (m); N the normalization parameter (-).
The infinite series in Eq. (4) will be approximated using
only one term in each spatial direction (n = m = p = 0). Nor-
malizing so Qo becomes equal to unity for t requires
that N 6 /512 when t . Thus
Qo
1 e3DAV t = 1 e(3 DAV t/L )
2 2

Sw Sw Sw Sw Qo max
= D(Sw ) + D(Sw ) + D(Sw )
t x x y y z z = 1 et (6)
(1)
is the fit parameter expressing the rate of convergence from
where SI data (min1 ); t the imbibition time (min), and other sym-
kkro 1 dPc bols as defined above.
D(Sw ) = (2)
o 1 + (kro /krw )(w /o ) dSw The approximate solution, Eq. (6), is derived and only
valid for rock samples with cubic shape. However, Eq. (6) will
has units m2 /s and is called CDC. Sw is the normalized water also be used when analyzing tests performed on cylindrical
saturation given by: core samples. Experimental results reported in [25] indicate
that this approximation is acceptable as long as the aspect
S Swi
Sw = , 0 Sw 1 (3) ratio, i.e. the ratio between the height and the diameter of
Swf Swi the cylindrical core not deviates significantly from unity. The
where k is the absolute permeability (m2 ); kro the relative per- solution to Eq. (1) given in Eq. (6) is therefore subjected to
meability to oil (-); krw the relative permeability to water (-); the following assumptions/limitations:
o the oil viscosity (Pa s); w the water viscosity (Pa s); Pc The CDC is assumed to be constant and independent of
the capillary pressure (Pa); S the average water saturation at water saturation.
time t (fraction, m3 /m3 ); Sw the normalized water saturation The water and the oil phase flow as incompressible fluids.
(fraction, m3 /m3 ); Swi the initial water saturation (fraction, The infinite series in Eq. (4) is approximated using only one
m3 /m3 ); Swf the maximum water saturation at residual oil sat- term in each spatial direction and the fractional volume of
uration (fraction, m3 /m3 ); the fractional porosity (m3 /m3 ). oil produced is normalized allowing fractional oil recovery
The capillary diffusivity coefficient, D(Sw ), is in general to become unity at infinite time.
a function of water saturation and the equation is therefore The solution is assumed to be valid for cylindrical geome-
non-linear and has to be solved numerically. However, D will tries having aspect ratios close to unity.
be assumed to be constant in this paper and as such be referred
to as DAV (a kind of average CDC). Under this assumption Eq. (6) has the same form as the widely cited function
Eq. (1) becomes linear and the water saturation in the ma- introduced by Aronofsky et al. [13]. They arrived at this ex-
trix block Sw = Sw (x, y, z, t) can be found analytically under pression only by abstract thinking and by putting certain
boundary and initial conditions specified in Appendix A. The constraints on the function describing oil recovery by SI from
solution of Eq. (1) expressing oil recovery as a function of a single matrix block as a function of time. Chen et al. [4]
time (since oil recovered is equal to the amount of water im- showed that the Aronofsky type model is equivalent to as-
bibed (incompressible two-phase flow)) can be written as an suming that the capillary diffusivity coefficient is constant
infinite series [2]: and independent of water saturation. Likewise, Gupta and
Civan [14] also arrived at an exponential expression similar

Qo 512


to the one presented here when modeling oil recovery by SI
= 6N
Qo max using a semi-empirical method.
n=0 m=0 p=0

1 3. Experimental
(2n + 1) (2m + 1)2 (2p + 1)2
2
Details related to the experimental procedures, core han-
[1 exp(DAV ((2n + 1)2 dling, etc. are reported elsewhere [26] and only a brief de-
+ (2m + 1)2 + (2p + 1)2 )t)] (4) scription is given here.
96 D.C. Standnes / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 93101

Table 1 50 (referred to as Arquad) from Akzo Chemicals Ltd.,

Composition of the brines UK, and Dodigen 5462 (referred to as Dodigen) from
Ion Brine A (g/l) Brine B (g/l) Hoechst AG, Germany, were used as surfactants in Tests 35
Na+ 2.36 12.14 (1.0 wt.% calculated as active matter). Arquad MC-50 con-
K+ 0.25 tained 50 wt.% of the cationic surfactants C12-N(CH3 )3 Cl
Ca2+ 0.80 3.43 and C14-N(CH3 )3 Cl mixed with 3540 wt.% isopropanol
Mg2+ 0.24 0.93
Sr2+ 0.02
and 13 wt.% water. Dodigen 5462 contained approximately
Cl 5.67 26.54 50% C12-N(CH3 )3 Cl, 24% C14-N(CH3 )3 Cl, 11% C16-
SO4 2 0.16 1.56 N(CH3 )3 Cl and 13% C18-N(CH3 )3 Cl.
HCO3 0.09
Total dissolved solid 9.25 44.94

4. Results and discussion

3.1. Oil phase
A crude oil diluted in the ratio of 40/60 heptane/crude by
volume was used as the oil phase in Tests 15. The diluted oil
had an acid number (AN) of about 1.04 mg KOH/g, which
rendered the carbonate cores preferential oil-wet. No precip-
itation of asphaltenes was observed after diluting with hep-
tane. The properties of the oil: density at 20 C 0.816 g/cm3 ;
viscosity at 20 C 2.5 cP; asphaltenes 0.23 wt.%. n-Decane
with grade > 95% from RiedeldeHaen was used as oil phase
in Test 6. Density and viscosity at 20 C were 0.731 g/cm3
and 0.95 cP, respectively.
3.2. Aqueous phases
Two brines termed A and B were used in Tests 15. A was
used in the tests related to the dolomite cores and B related
to the chalk cores. The composition of the brines is given in
Table 1. Distilled water was used as aqueous phase in Test 6.
3.3. Porous media
Outcrop chalk cores from Denmark and two dolomite
reservoir cores from a field in West Texas were used as porous
media. The dolomite cores were homogeneous with a sugary
texture. Relevant data regarding porosity, permeability, core
size, etc. for all tests are presented in Tables 2 and 3.
3.4. Surfactants
Pure dodecyltrimethylammonium bromide, C12TAB,
with grade > 99% from Sigma was used as surfactant in
Tests 1 and 2. Commercial products termed Arquad MC-
4.1. Calculation of diffusivity constants from imbibition
curves
The best estimate for the constant in Eq. (6) can be
found by plotting imbibition time versus ln(1 Qo /Qomax ),
which should give a straight line if the average oil saturation
follows the exponential decay curve shape. A least square
analysis can be performed and 1/ should then be equal to
the slope of the straight line fitting the experimental data
in the best way. Fig. 1 shows the result of such an analy-
sis for Tests 1, 2 and 5. It is important to point out that the
cores in Tests 1 and 5 did not imbibe pure brine at all during
40 and 5 days respectively, whereas the core in Test 2 im-
bibed a small amount of water when exposed to pure brine
at 70 C for a extended period of time (see original data in
Ref. [19] and [21]). All these tests can roughly be consid-
ered to have a DAV 0 with respect to pure brine imbibi-
tion. The time period when the core material was exposed to
pure brine (no oil production) has therefore been subtracted
in this work for the sake of clarity (total imbibition history
for each test is provided in the original experimental data
(references given in Table 2)). Consequently, all imbibition
times reported here are times where the cores were exposed
to surfactant solutions (except Test 6). The results from the
least square analysis show that the exponential function fits
the experimental data quite well, which is reflected in the R-
values. Approximating the solution of Eq. (1) valid for cubic
shapes to cylindrical cores therefore seems to work reason-
ably well. Knowing the -values from the slope of the linear
functions, the CDCs can be calculated directly from the fol-
lowing equation (using L equal to the height of the cylindrical
cores):

Table 2
Core data for spontaneous imbibition tests
Test no. Rock k L (cm) d (cm) (%) Swi (%) PV (cm3 ) Temperature Surfactant Reference
type (mD) ( C)
1 C 2 4.6 3.48 44.8 0 19.6 40 C12TAB, 1.0 wt.% Standnes and Austad, Test 1 [19]
2 C 2 5.03 3.61 45.4 0 23.37 70 C12TAB, 1.0 wt.% Standnes and Austad, Test 26 [19]
3 Do 352 5.86 3.75 26.2 46.8 16.91 40 Arquad, 1.0 wt.% active Standnes and Austad, Test 5 [21]
4 Do 101 5.64 3.80 23.2 49.5 14.84 40 Arquad, 1.0 wt.% active Standnes and Austad, Test 6 [21]
5 Do 352 5.86 3.75 25.5 42.4 16.49 40 Dodigen, 1.0 wt.% active Standnes and Austad, Test 7 [21]
6 C 2 3.8 3.8 42.3 0 22.97 20 No surfactant Standnes, Test 7 [25]
 D.C. Standnes / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 93101
Table 3
Rock-fluid systems used in the SI tests
Test no. Rock type Aqueous phase
1 C Brine B with C12TAB
2 C Brine B with C12TAB
3 Do Brine A with Arquad
4 Do Brine A with Arquad
5 Do Brine A with Dodigen
6 C Distilled water
L2
DAV =
32
Equations for the linearization, corresponding R-values and
the calculated CDCs for all tests are given in Table 4.
The results show that DAV -values for different tests per-
formed on preferential oil-wet carbonates are in the range
(1.714) 1011 m2 /s. The slowest imbibition rate was ob-
tained for C12TAB imbibition into preferential oil-wet chalk
cores at 40 C (DAV = 1.7 1011 m2 /s). It is interesting to
note that the CDC increases to 7 1011 m2 /s when the tem-
perature is raised to 70 C. This shows that the SI rate into
preferential oil-wet carbonates is very sensitive to temper-
ature a feature typical for any process modeled as a dif-
fusion process. This is especially true for processes where
surfactants are involved because an increase in temperature
will increase the diffusion rate of surfactant molecules to
the water imbibition front and thereby increase the speed
of wettability modification towards more water-wet condi-
tions. Varying the temperature will also influence the im-
bibition rate through changes in fluid viscosities, oilwater
interfacial tension (IFT) and shifts in the oil and the wa-
ter relative permeability curves. Increased temperature will
lower the fluid viscosities and enhance imbibition of the
aqueous phase into the oil containing matrix blocks. Ele-
vated temperature will also enhance water imbibition due to
an increase in the oilwater IFT with increasing tempera-
Fig. 1. Determination of optimal s from spontaneous imbibition data by least square method.
97
Oil phase Oilwater interfacial tension (mN/m) Wetting state of core material
Crude oil 0.81 Preferential oil-wet
Crude oil Not available Preferential oil-wet
Crude oil 1.0 Preferential oil-wet
Crude oil 1.0 Preferential oil-wet
Crude oil 0.3 Preferential oil-wet
n-Decane 46 Very strongly water-wet
ture for the cationic surfactant systems applied in this study.
(7) All these effects (increased diffusion rate, lower fluid vis-
cosities and increased oilwater IFT) will contribute to the
faster water imbibition observed at 70 C compared to the
tests performed at 40 C (the impact of varying the temper-
ature on the relative permeability curves is as yet undeter-
mined).
The highest CDC (14 1011 m2 /s) was obtained for
the imbibition of the surfactant Arquad into the high-
permeability dolomite core (352 mD). The corresponding
coefficient for Arquad into the 101 mD dolomite core was
6.0 1011 m2 /s.
These results can be compared to DAV determined for im-
bibition of pure water into strongly water-wet chalk (the ref-
erence wettability state, Test 6). Figs. 2 and 3 show the lin-
earization process, the imbibition curve and the model curve,
respectively, for Test 6. Oil production as a function of time
fits the exponential function very well. The CDC was deter-
mined to 6400 1011 m2 /s in this case and it should be no-
ticed that this value was obtained under 20 C test condition.
It is therefore not unreasonable to believe that the difference
in DAV -values for imbibition of surfactant solutions into pref-
erential oil-wet chalk is approximately three orders of mag-
nitude lower compared to imbibition into strongly water-wet
chalk material. Whether this decrease is too large for field
application or not is an open question, but Morrow and Ma-
son [1] report imbibition data for mixed-wet cores where the
98 D.C. Standnes / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 93101
Table 4
Linearization of SI data for calculated capillary diffusion constants
Test no. Equation from linearization
1 y = 32733x + 3877.9
2 y = 11959x + 232.37
3 y = 3619.7x 202.94 0.9955
4 y = 6707.6x 99.666 0.9878
5 y = 20452x 1187.2 0.9926
6 y = 5.36x 0.365 0.9992
Fig. 2. Determination of optimal from spontaneous imbibition of distilled
water into strongly water-wet chalk by least square method. Test temperature
20 C.
exponential convergence factor was four orders of mag-
nitude smaller than for imbibition onto strongly water-wet
systems (maximum oil recovery level also decreased signif-
icantly with decreasing ). However, it is important to re-
call that strongly water-wet systems only represent a conve-
nient wettability reference system which can be used as a
Fig. 3. Spontaneous imbibition and model curve for imbibition of distilled
water into strongly water-wet chalk. Test temperature 20 C.
R 105 (min1 ) DAV 1011 (m2 /s)
0.9941 3.055 1.7
0.9907 8.362 7.0
27.63 14
14.91 6.0
4.889 2.3
18657 6400
comparison for imbibition data determined for none strongly
water-wet systems. It is nowadays commonly accepted that
strongly water-wet reservoirs occur very rarely if ever. This
is particularly true for carbonate formations where as much
as 80% of the reservoirs can be characterized as neutral to
oil-wet [27]. Due to the initial distribution of connate wa-
ter and oil a mixed-wet situation is more likely to occur [1].
The systems investigated in this work therefore represent ex-
treme cases, i.e. SI of water into strongly water-wet chalk
and imbibition of aqueous surfactant solutions into prefer-
ential oil-wet chalk and dolomite not imbibing pure water
at all (DAV is approximately equal to zero with respect to
pure brine imbibition for all Tests 15). From a practical
point of view, what really matters when evaluating an IOR-
project is to assess the potential amount of extra oil that can
be recovered and to what rate? When considering applica-
tion of chemical flooding, it is therefore very important to
carefully perform SI tests with and without surfactants in
the aqueous phase on reservoir core samples having repre-
sentative wettability before drawing any conclusions about
SI time delay with and without wettability modifying agents
present.
It is also interesting to note that the CDC found here
for SI into strongly water-wet chalk corresponds reasonably
well with other values published in the literature. Table 5
lists some values of the CDCs reported by different authors
[4,6]. The table shows that most values of DAV are in the
range from 1000 to 5000 1011 m2 /s. It should be noticed
that the calculation procedure for these DAV -values may dif-
fer slightly from the ones calculated in this work. However,
the values confirm that typical values for DAV for counter-
current imbibition into strongly water-wet media lie in the
range 100010,000 1011 m2 /s.
Table 5
Capillary diffusivity coefficients from the literature
Reference D 1011 (m2 /s)
Chen et al. [4] Maximum 700 based on Kazemi et al.s
data from 1976
Maximum 7000 based on Beckner et al.s
data from 1988
Dutra and Aziz [6] Kleppe and Morse experiment: 50,000
Coats example: 3800 and 2000
Kazemis example: 4800
Thomas three-dimensional example: 3800
SPE cross-sectional problem: 1100
 D.C. Standnes / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 93101 99

Fig. 4. Spontaneous imbibition curves for the tests used in the analysis on linear time-scale. The model curves are also included using optimal from least
square analysis.

Fig. 5. Spontaneous imbibition curves for the tests used in the analysis on log time-scale. The model curves are also included using optimal from least square
analysis.

4.2. Comparison between imbibition curves and curves increasing with the square root of time fits experimental data
generated by Eq. (6) with optimal better than the exponential term for early times [28,29].

Fig. 4 depicts the imbibition curves for Tests 15 together

with the curves generated from Eq. (6) using the optimal
determined from least square fitting. The model describes the
experimentally curves quite well as expected due to R val-
ues close to unity (Table 4), but there is a clear tendency for
the experimental curves to lie above the model curves at early
times (this fact is clearly shown when the curves are plotted in
a semi-log diagram, Fig. 5). This fact has been demonstrated
by several authors (see for example Reis and Cil [28]). Ap-
proximating the solution of Eq. (1) by assuming a constant
CDC implies a solution which increases exponentially as a
function of time. It is commonly accepted that an oil recovery
5. Conclusions
A simple analytical model based on the capillary diffu-
sivity approach has been used to get quantitative information
about spontaneous imbibition rates of aqueous surfactant so-
lutions into preferential oil-wet carbonates (core material es-
sentially not imbibing any pure brine at all). In the model
used, the imbibition rates are characterized by one single pa-
rameter, the CDC. This approach is particularly suitable for
quantifying imbibition rates for processes involving wettabil-
ity alterations due to problems to measure flow parameters
100 D.C. Standnes / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 93101

accurately under such circumstances. The following conclu- where tD,MZM is the dimensionless time (MaZhangMorrow
sions can be drawn from this work: [9]); the fractional porosity (m3 /m3 ); the oilwater IFT
(N/m); g the geometrical mean of oil and water viscosities
Oil recovery by spontaneous imbibition of aqueous surfac-
(Pa s); L the length of the sides in the cube (m).
tant solutions into preferential oil-wet carbonates can be
The characteristic length term in A.5 is given by:
modeled fairly well by an exponential increasing function
of the Aronofsky type (there is a tendency for the model Vb
L2C = (A.6)
to underestimate recovery at early times). 
n
Ai / li
DAV -values expressing the imbibition rates varies in the i=1
range (1.714) 1011 m2 /s for the preferential oil-wet
carbonate systems investigated (low-permeability chalk where Vb is the bulk volume of the rock sample (m3 ); Ai the
(2 mD) and dolomite with permeabilities equal to 101 area of the ith imbibition surface (m2 ); li the length from the
and 352 mD). ith imbibition surface to the no-flow boundary (m).
The value of DAV obtained in this work for SI into strongly The above substitutions transform the equation into the
water-wet chalk corresponds well with other published val- following form:
ues of CDCs.  L2 Sw 2 Sw 2 Sw
The results show that DAV -values are approximately three k = D AV + D AV
g L2C tD,MZM xD 2 yD 2
orders of magnitude smaller for imbibition into preferen-
tial oil-wet chalk than imbibition into strongly water-wet 2 Sw
chalk (reference wettability state used here). This differ- + DAV (A.7)
z2D
ence is probably artificially large when evaluating the IOR-
potential from fields due to the rare occurrence of strongly Equally:
water-wet reservoirs.  2 
Sw 2 Sw 2 Sw Sw
DAV C + + = (A.8)
x2 y2 z2 tD,MZM
Appendix A where
g L2C
Conservation of water volume in a three-dimensional cu- C= (s/m2 ) (A.9)
k L2
bic rock sample with porosity leads to the so-called diffu-
sivity equation: This equation is solved under the following boundary and
initial conditions expressing that the cube is totally immersed
Sw Sw Sw Sw
= D(Sw ) + D(Sw ) + D(Sw ) in water at t = 0:
t x x y y z z
(A.1) Sw (0, yD , zD , tD ) = Sw (1, yD , zD , tD )

where = Sw (xD , 0, zD , tD,MZM )

kkro 1 dPc = Sw (xD , 1, zD , tD,MZM )
D(Sw ) = (A.2)
o 1 + (kro /krw )(w /o ) dSw = Sw (xD , yD , 0, tD,MZM )
and = Sw (xD , yD , 1, tD,MZM ) = 1,
S Swi Sw (xD , yD , zD , 0) = Swi
Sw = , 0 Sw 1 (A.3) (A.10)
Swf Swi
Solving the equation using separation of variables and su-
D(Sw ) with unit m2 /s plays the role as the capillary diffusivity perposition gives the following expression for the volume of
coefficient in this equation and has been shown to be a bell- water, Qw , imbibed as a function of dimensionless imbibition
shaped function of the water saturation [4]. However, D(Sw ) time [2]:
is assumed to be independent of water saturation here so
the equation becomes linear and can be solved analytically. Qw 512


1
= 6
Introducing the dimensionless variables tD and xD , yD and zD Qw max (2n + 1) (2m + 1)2 (2p + 1)2
2
n=0 m=0 p=0
defined by:
x y z [1 exp(2 DAV C((2n + 1)2 + (2m + 1)2
xD = , yD = , zD = (A.4)
L L L + (2p + 1)2 )tD,MZM )] (A.11)
and where Qwmax is the volume water imbibed after infinite time

(m3 ).
k 1
tD,MZM = t (A.5) This equation requires that an infinite number of
g L2C terms should be included to approach maximum water
 D.C. Standnes / Colloids and Surfaces A: Physicochem. Eng. Aspects 251 (2004) 93101 101

imbibition level of unity after infinite time. Introduc- References

ing a normalization parameter so the fractional volume
of water imbibed is approaching unity at infinite time [1] N.R. Morrow, G. Mason, Curr. Opin. Colloid Interf. Sci. 6 (2001)
gives: 321337.
[2] J.C. Reis, M. Cil, IN SITU 24 (1) (2000) 79106.

Qw 512


1 [3] M. Cil, J.C. Reis, M. Miller, D. Misra, SPE Paper, No. 49005, 1998.
= 6N [4] J. Chen, M. Miller, K. Sepehrnoori, SPE Paper, No. 29141, 1995.
Qwmax (2n + 1)2 (2m + 1)2 (2p + 1)2 [5] J. Cruz Hernandez, C. Perez Rosales, SPE Paper, No. 23748, 1992.
n=0 m=0 p=0
[6] T.V. Dutra, K. Aziz, SPE Paper, No. 21248, 1991.
[7] J.A. Hayashi, C. Perez Rosales, SPE Paper, No. 23745, 1992.
[1 exp(2 DAV C((2n + 1)2 + (2m + 1)2
[8] M. Pooladi-Darvish, A. Firoozabadi, SPE J. 5 (1) (2000) 311.
[9] S. Ma, N.R. Morrow, X. Zhang, J. Pet. Sci. Eng. 18 (1997) 165178.
+ (2p + 1)2 )tD,MZM )] (A.12)
[10] S. Ma, X. Zhang, N.R. Morrow, CIM Paper, No. 95-94, 1995.
The fractional amount of oil produced from the matrix block [11] C.C. Mattax, J.R. Kyte, SPE J. (1962) 177184.
[12] X. Zhang, N.R. Morrow, S. Ma, SPE Paper, No. 30762, 1995.
at time t will then be (since oil volume produced is equal to [13] J.S. Aronofsky, L. Masse, S.G. Natanson, Petroleum Trans., AIME
the influx of water): 213 (1958) 1719.
[14] A. Gupta, F. Civan, SPE Paper, No. 28929, 1994.
Qo 512


1 [15] F. Civan, SPE REE (1998) 141147.
= 6N
Qomax (2n + 1) (2m + 1)2 (2p + 1)2
2 [16] D.S. Schechter, D. Zhou, F.M. Orr Jr., J. Pet. Sci. Eng. 11 (1994)
n=0 m=0 p=0 283300.
[17] G.I. Barenblatt, T.W. Patzek, D.B. Silin, SPE Paper, No. 75169,
[1 exp(2 DAV C((2n + 1)2 + (2m + 1)2 2002.
[18] T. Austad, D.C. Standnes, J. Pet. Sci. Eng. 39 (34) (2003) 363376.
+ (2p + 1)2 )tD,MZM )] (A.13) [19] D.C. Standnes, T. Austad, J. Pet. Sci. Eng. 28 (2000) 123143.
[20] D.C. Standnes, T. Austad, Colloids Surf. A: Physicochem. Eng. As-
Qomax is the maximum oil volume produced after infinite time pects 216 (13) (2003) 243259.
(m3 ). [21] D.C. Standnes, T. Austad, Colloids Surf. A: Physicochem. Eng. As-
Written out in real imbibition time gives: pects 218 (13) (2003) 161173.
[22] D.C. Standnes, T. Austad, J. Pet. Sci. Eng. 39 (34) (2003) 431446.

Qo 512


1 [23] D.C. Standnes, L.A.D. Nogaret, H.L. Chen, T. Austad, Energy Fuels
= 6N 16 (2002) 15571564.
Qomax (2n + 1) (2m + 1)2 (2p + 1)2
2
n=0 m=0 p=0 [24] S. Strand, D.C. Standnes, T. Austad, Energy Fuels 17 (5) (2003)
11331144.
[1 exp(DAV ((2n + 1)2 + (2m + 1)2 [25] D.C. Standnes, Energy Fuels 18 (1) (2004) 271282.
[26] D.C. Standnes, T. Austad, J. Pet. Sci. Eng. 28 (2000) 111121.
+ (2p + 1)2 )t)] (A.14) [27] H.H. Downs, P.D. Hoover, In oil-field chemistry, enhanced recovery
and production stimulation, in: J.K. Borchardt, T.F. Yen (Eds.), ACS
which is equal to Eq. (4). Symposium Series, American Chemical Society, Washington, DC,
1989.
[28] J.C. Reis, M. Cil, J. Pet. Sci. Eng. 10 (1993) 97107.
[29] Y. Li, N.R. Morrow, D. Ruth, J. Pet. Sci. Eng. 39 (2003) 309326.

View publication stats