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Colloids and Surfaces A: Physicochem. Eng. Aspects xxx (2014) xxxxxx

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Visualising surfactant enhanced oil recovery

Andrew M. Howe , Andrew Clarke, Jonathan Mitchell, John Staniland,
Laurence Hawkes, Caroline Whalan
Advanced Recovery Group, Fluid Mechanics Department, Schlumberger Gould Research, High Cross, Madingley Road, Cambridge CB3 0EL, UK

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Surfactant EOR followed in 2D and

3D porous media by microscopy and
NMR.
Adding surfactant in L1-based for-
mulations reduces  and enhances
recovery.
L3-based formulations give ultra-low
interfacial tensions and better recov-
ery.
L3-based oods show two saturation
fronts and surfactant hold-up.
L3-based oods consistent with
formation then displacement of
microemulsion phases.

a r t i c l e i n f o a b s t r a c t

Article history: Surfactant formulations that give rise to ultra-low interfacial tensions are used to enhance the recovery
Received 20 June 2014 of crude oil by eliminating the trapping effects of capillary forces. The formulations, when mixed with oil,
Received in revised form 20 August 2014 often give microemulsion-type phase behaviour. Depending on the surfactant afnity for oil and water,
Accepted 22 August 2014
the microemulsion may exist as water-in-oil (L2), oil-in-water (L1), or bi-continuous (L3). Here, an aque-
Available online xxx
ous formulation of anionic surfactants and butan-2-ol that would give rise to L1 and L3 phase behaviours
at different NaCl concentrations is injected into decane-lled porous media. The displacement processes
Keywords:
in rock cores are followed by spatially resolved NMR and in microuidic models by optical microscopy.
Surfactant applications
Chemical enhanced oil recovery
Both surfactant formulation types enhance the oil displacement from the core but the L3-forming sys-
EOR tem shows more complex behaviour, consistent with rst the formation and then the displacement of
Micromodel microemulsion phases, which leads to signicant enhancements in oil recovery.
NMR visualisation 2014 Elsevier B.V. All rights reserved.
Core oods

1. Introduction

The study of microemulsion formation and microemulsion ow

Manuscript of oral presentation Surfactant Enhanced Oil Recovery Complex
Fluids in Conned Environments. Topic: 07. Micelles, Emulsions and Microemulsions
abstract, 262. To be presented at 20th International Symposium on Surfactants in
Solution (SIS 2014), Coimbra, Portugal, June 22nd to 27th, 2014.
Corresponding author. Tel.: +44 1223325278.
E-mail address: ahowe2@slb.com (A.M. Howe).
in porous media with respect to chemical enhanced oil recovery
(cEOR) has a long history dating back to at least the 1960s. Work
on chemical EOR stalled following the 1986 collapse in oil price but
has resumed more recently as the oil price has increased signi-
cantly since 2002. The ongoing use of EOR techniques to maximise
oil recovery is supported by consistent oil prices of over $100/bbl
($630/m3 ). Traditional oil recovery is divided into two main pro-
cesses; commonly referred to as primary and secondary. Primary

http://dx.doi.org/10.1016/j.colsurfa.2014.08.032
0927-7757/ 2014 Elsevier B.V. All rights reserved.

Please cite this article in press as: A.M. Howe, et al., Visualising surfactant enhanced oil recovery, Colloids Surf. A: Physicochem. Eng.
Aspects (2014), http://dx.doi.org/10.1016/j.colsurfa.2014.08.032
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recovery is the initial expulsion of oil after drilling caused by the
inherent pressure within the reservoir. When this initial pressure
has dissipated, further oil can be recovered by applying an external
pressure (secondary recovery), generally from the injection into
or ooding of the reservoir with locally available water (e.g.,
sea-water). Enhanced oil recovery (EOR) refers to reservoir pro-
cesses that recover oil not produced by brine ooding. In 1989
Lake [1] summarised EOR methods in general, while cEOR has been
reviewed by Sheng [2].
Reservoirs of crude oil are found in porous rock formations
where oil is contained in networks of micron-scale pores with con-
necting throats. After brine ooding, oil ganglia remain trapped in
the network by capillary forces. Whether a ganglion can become
mobile is controlled by the balance between the applied pressure
gradient of the ooding uid (viscous forces) and the interfacial
tension between oil and that uid (capillary forces) [3,4]. The bal-
ance between the interfacial tension and the viscous forces of the
ood acting on a trapped ganglion within a porous network can be
expressed by the capillary number
U
Ca =

where  is the viscosity of the injected phase, U is the linear velocity
of the injected phase and  is the interfacial tension between the
crude oil and the injected phase. The value of the capillary number
can be directly correlated to the amount of residual oil trapped in
the reservoir after a ood, which is expressed as the residual oil
saturation Sor (oil saturation So is volume fraction of oil within the
pore space). Typically, to reduce Sor further, the value of Ca should
exceed 104 [5].
For a typical crude oil/brine waterood Ca is of the
order of 107 to 106 (with  10 mN m1 ,  1.0 mPa s, and
U 3.5 106 m s1 , i.e., one foot per day). Increasing Ca to
between 104 and 103 can reduce So in water-wet sandstones by
up to 90% [5]. This increase can be achieved by increasing the viscos-
ity or velocity of the ooding phase, or by reducing the interfacial
tension. The maximum viscosity and velocity are limited by prac-
tical considerations. If the ooding phase is pumped at a very high
pressure or the uid is very viscous the rock can fracture. Reduction
in the interfacial tension  is therefore a more practical solution and
is achieved by injecting surfactant formulations.
The present understanding of surfactant cEOR is mostly based
on a quasi-equilibrium approximation wherein the local surfactant
phase structure is taken to be the equilibrium structure for that
local composition and temperature. Information on the distribution
of surfactant in a ood was inferred from studies of efuent chemi-
cal composition in combination with various modelling approaches
[6]. In this study we are interested in the application of surfac-
tants as cEOR agents; the efcacy of surfactant enhanced recovery
depends on the rock/oil/injectant system and the interplay of cap-
illary and viscous forces [7].
It is common practice when formulating solutions for surfac-
tant cEOR to determine the phase volume ratios of equi-volume
mixtures of oil and water in the presence of a low concentration
(of order 1%, v/v) surfactant. Surfactants form micelles in either the
aqueous or oil phase. The more hydrophobic the surfactant and the
higher the aqueous salt concentration, the greater the tendency
for the micelles to form in the oil phase. These micelles solubilise
some of the discontinuous (excess) phase to form a microemulsion.
At intermediate salt concentrations, a middle phase (bicontinuous)
microemulsion can exist in the presence of excess oil and brine
phases. For systems with excess water and oil, the microemul-
sion phase behaviour was categorised by Winsor, who identied
three congurations [8]. Winsor 1 (L1): the surfactant is soluble as
micelles in the aqueous phase which solubilise some of the oil phase
in their core. Winsor II (L2): the surfactant is soluble as inverse
Please cite this article in press as: A.M. Howe, et al., Visualising surfactant enhanced oil recovery, Colloids Surf. A: Physicochem. Eng.
Aspects (2014), http://dx.doi.org/10.1016/j.colsurfa.2014.08.032
micelles in the oil phase solubilising some of the aqueous phase in
their core. Winsor III (L3): the oil and aqueous phases form a uctu-
ating bicontinuous network stabilised by the surfactant. The length
scales of these microemulsion systems are typically 10100 nm [9].
The afnity of the surfactant for the oil and water phases is well
balanced near the Winsor III compositions. In studies of a system
with anionic surfactant and no co-solvent, Aveyard et al. showed
that the interfacial tension between alkanes and NaCl brines was
lowest under conditions where the afnity of surfactant for oil and
aqueous phase was similar [1012]. For systems with a co-solvent
added, the interfacial tensions between the L3 middle phase and
the excess aqueous or oil phases was measured to be ultra-low
( ow < 0.01 mN m1 ) [13].
The presence of L3 phase behaviour and the degree of solubili-
sation within the surfactant-rich phase is often used in the oileld
industry to estimate interfacial tension by the relation  = c/Ro Rw ,
where c is a constant (typically 0.3 mN m1 ) and Rw and Ro are
respectively the ratios of water and oil to surfactant in that phase
[14,15]. Thus formulations that would give rise to high solubilisa-
tion and L3 behaviour are thought to be most likely to generate
(1) an ultra-low interfacial tension (ULIFT) and hence effectively elim-
inate the capillary trapping force to promote oil recovery [16].
However, whilst the presence of middle-phase implies a ULIFT, the
middle phase can trap large quantities of surfactant, which is not
economically desirable.
Adoption of cEOR by the industry relies on reservoir simulators
providing sensible estimates of recovery enhancement. To date,
continuum fractional-ow models of oil and water displacement
within porous media have been developed and applied in a wide
range of situations [1]. The extensions required to allow analysis
of three-phase ow with three components were rst set out by
Helfrich [17]. Falls [18] developed the model for three-component,
three-phase displacement with general fractional-ow curves.
Hirasaki [6] gives a detailed account of the application of the model
to the three-component two-phase situation. For this case it is
assumed that the phases are in local equilibrium and that partial
molar volumes of components are constant. Of course, the distri-
bution of components between the phases is variable. In Hirasakis
calculation, the surfactant is injected as an aqueous slug into a
rock containing a residual oil saturation SOR . The slug then moves
through the porous material with a particular front speed. It is
assumed that the surfactant is able to solubilise oil which implies
that a solubilisation shock develops between the injected compo-
sition and the two-phase region ahead. Subsequently, Khan et al.
[19] provided a complete numerical scheme for micellar porous
ow problems, which today forms the basis of both commercial
and academic simulators.
In the present work we use nuclear magnetic resonance (NMR)
to monitor oil recovery in a sandstone rock plug during the injection
of surfactant solutions designed to form particular microemulsion
phases in situ. To help explain the observations in these experi-
ments we turn to microuidic models (ideal 2D representation of
a porous structure) in which the oil displacement is imaged using
optical microscopy. We discuss our results in light of the existing
literature and fractional-ow models used to simulate oil recovery
by cEOR.
2. Experimental
2.1. Materials
For this work we use a model system consisting of NaCl brine,
n-decane, and a formulation of commercial anionic surfactants
designed for application in enhanced oil recovery. The use of
decane means that results are not complicated by saponication
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Table 1 1
Petrophysical data for Bentheimer cores. (a)
0.8

volume fraction
Plug name Porosity (vol%) Permeability (mD)

BN1 22.5 2977 0.6

BN2 23.0 3236
BN3 23.4 3317
0.4

0.2
L1 L3 L2
of oleic acids. The liquid ows have been analysed in a core plug of 0
Bentheimer, a high-permeability outcrop sandstone, and a trans- 0 1 2 3 4 5 6 7 8
parent plastic micromodel. The sandstone core plug is expected [NaCl] wt%
to have a hydrophilic surface with a negative surface charge and
-2
hence anionic surfactants are not expected to adsorb signicantly. 10

interfacial tension, , N/m

Thus the potential complicating factors of adsorption and chem- (b)
-3
ical contributions from oil are avoided, permitting the factors of 10
microemulsion phase behaviour of the surfactant formulation and
ow (convectiondiffusion leading to compositional gradients) to 10
-4

be probed with greater clarity.

Two commercially available surfactants were used (C12,13 -5
10
alcoholpropoxy-sulfate and C20-24 internal olen sulfonate),
which are produced by Shell Chemicals under the ENORDET trade -6
name [2022]. These materials are representative of surfactants 10
0 1 2 3 4 5 6 7 8
used for multi-well and full-scale oods. There is a low concentra- [NaCl] wt%
tion of residual salts (NaOH, Na2SO4 ) in the produced surfactant
but the total is only a few % relative to the surfactant and so will Fig. 1. (a) Volume fraction of equilibrated tubes containing decane, surfactant, and
not have a signicant inuence on phase behaviour. The synthesis H2 O brine. The red circles mark the boundary between the oil phase and lower
phases, the blue circles mark the boundary between the brine phase and the upper
and structures of the IOS surfactants is well described in reference
phases. Between the red and blue points there exists the microemulsion phases.
[21]. (b) Interfacial tension measurements between equilibrated oil and aqueous phases;
The aqueous formulation contained 1% (w/w) (active) of each dashed line is a guide for the eye. (For interpretation of the references to colour in
ENORDET surfactant and 8% (w/w) butan-2-ol (SigmaAldrich, this gure legend, the reader is referred to the web version of the article.)
>99.5% purity) cosolvent. In phase studies, these formulations
were mixed with decane at 1:1 volume ratio. In the absence of where  is the oil/brine density contrast and g is the accelera-
cosolvent, no microemulsions are formed. Reagent grade n-decane tion due to gravity, so that we expect oil ganglia to remain trapped
(SigmaAldrich, 99% purity) was used as the oil and sodium chlo- against gravity, except when an ULIFT is achieved.
ride (Fisher Chemical) was used as the electrolyte.
In the microuidic studies, the oil-soluble dye Oil Red EGN
2.2. Methods
(Aldrich) was added to decane at 0.25 g L1 to distinguish the uids
colorimetrically. In the NMR studies, the aqueous solutions were
Phase studies were performed by mixing 7.3 g of n-decane with
formulated in D2 O (heavy water). No change in interfacial tension
10.0 g aqueous phase (a xed mass of aqueous surfactants/butan-
was measured in the presence of the dye.
2-ol and variable mass of aqueous NaCl and water) in a 20 mL
Bentheimer sandstone has a uniform texture with large grains.
graduated glass tube. The mixtures were shaken and the phase
Cylindrical rock plugs were cored from a block of quarried mate-
boundaries recorded after separation. The phase behaviour is
rial, trimmed, washed in deionised water, and dried in an oven
summarised in Fig. 1(a) for H2 O as the aqueous solvent. The limit
overnight at 60 C. The plugs were vacuum-saturated in n-decane
of aqueous solubility for 8% butan-1-ol, 2% surfactant was 4% (w/v)
prior to use in the NMR monitored recovery studies. The plugs had
NaCl in H2 O and 3.2% (w/v) in D2 O. The L1L3 transition occurred at
typical dimensions of 3.8 cm (diameter) and 5.0 cm (length). The
2.2% (w/v) NaCl in H2 O and at 1.8% (w/v) NaCl in D2 O. Solutions
pore throat distribution from mercury intrusion porosimetry [23]
at 1.6% (w/v) and 3.2% (w/v) NaCl in D2 O gave equivalent phase
contains a single peak with a median throat diameter dt = 38.8 m
behaviour to 2.0 and 4.0% (w/v) NaCl in H2 O.
[24]. The porosity and gas permeability of the plugs were deter-
The original studies were made on a w/w basis in H2 O and con-
mined using a helium expansion porosimeter and steady-state
centrations for D2 O were adjusted to allow for the higher density of
nitrogen permeameter, respectively (see Table 1). The results of
the latter and hence are expressed as w/v so volume concentrations
petrographic analysis indicate that this outcrop sandstone is pri-
of surfactant and cosolvent are constant throughout.
marily composed of monocrystalline quartz (61.3%), polycrystalline
Interfacial tension measurements were made using a DataPhysics
quartz (3.7%) and quartz overgrowths (3.3%). Also present are
SVT20N Spinning Drop Tensiometer (SDT) at 20 C in which the
K-Feldspar (4.0%), igneous rock fragments (2.7%) and a small pro-
shape of a drop of lower-density phase is followed within a spin-
portion of clays: kaolinite (1.0%) and chlorite (0.3%). The remaining
ning capillary of higher density uid. Refractive index and density
24% is porosity. The pore system shows extensive dissolution that
at 20 C were determined using an Index Instruments PTR 2a X
removed cements and unstable grains and left almost clean sand-
refractometer and a DMA 4500M Anton Paar Density Meter. The
stone with very good pores.
interfacial tension values for the H2 O-based formulations are given
Bentheimer sandstone is strongly water-wet and no attempt
in Fig. 1b. Formulations had been equilibrated and for 02% (w/w)
was made to alter the wettability. Despite the large permeability,
NaCl describe oil vs microemulsion while for 2.54% (w/w) NaCl
the Bond number is sufciently small, with
describe that between the excess phases (the middle phase volume
was small).
gdt2 (3.8 106 ) NMR was used to monitor the oil saturation along the length
Bo = , (2)
4  of the Bentheimer plugs during in situ injection of the surfactant

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solutions. Quantitative oil saturation proles were obtained using a
frequency encoded, multi-echo imaging method [25]. Details of the
NMR techniques have been reported elsewhere [26,27]. The plugs
were mounted in an NMR-transparent sample holder in the cen-
tre of a GeoSpec2-75 spectrometer from Oxford instruments. The
plugs were mounted with the long axis vertical and injected uids
were pumped from the bottom upwards. Thus the natural buoy-
ancy of the oil relative to the brine was preserved. All ow lines
were ushed with liquid to remove trapped air bubbles. Liquids
were injected at a ow rate of 0.055 mL min1 to give an approx-
imate ood front velocity of 3.5 m s1 . For this experiment, the
pressure differential was not recorded but the injection pressure
was <50 Pa throughout the ood; the outlet of the core holder was
at atmospheric conditions.
For decane and brine, the 1 H NMR signals overlap so D2 O was
substituted for H2 O so that the NMR signal was obtained almost
exclusively from the oil phase. Some signal was obtained from the
protons of the surfactant and cosolvent, as these components of the
ooding formulation were not deuterated. To rst order, assuming
no partitioning of the surfactant and that the cosolvent partitions
equally, we may expect that the actual oil saturation, So , can be
recovered from the measured saturation SoN via
SoN = So + f (1 So ),
and hence
SoN f
So =
1f
where f is the fraction of the oil signal that is arising from the sur-
factant package. In the data below, the surfactants and butan-2-ol
were assumed to account for 6% of the oil (i.e., proton) signal.
Efuent analysis for total anionic surfactant content was car-
ried out on aliquots collected after passing through the core plug.
The methylene blue ion-exchange technique [28] was used to give
precise values with small (sub pore-volume) sample volumes.
Microuidic models were supplied by Epigem Ltd. and comprise
SU8 channels embedded in PMMA. There are two inlets and two
outlets to facilitate lling of the device. Each inlet and outlet is
provided with an in-line last-chance lter that should trap any
material that would otherwise block the model, rendering the mea-
surements void. The entrance manifold has a tapered shape to
present a uniform pressure gradient across the inlet comb. The
inlet comb itself is a set of channels 200 m wide positioned on
a 480 m pitch. There are 32 inlet channels. The model channels
have a uniform depth of 100 m and width of between 80 m
and 250 m. The surface of the SU-8 as provided is oil-wet. The
total volume of the network is approximately 17 L (excluding inlet
and outlet channels) and the uid injection rate was 0.1 L min1
(0.35 PV/h). The micromodel is a physical realisation of the pore-
network model of Hammond and Unsal used to study surfactant
ooding [29] (Fig. 2).
The micromodels are illuminated in transmission by a Dolen-
Jenner QVABL bre optic light source together with a Fostec bre
optic light table. Images were captured using an AVT F-505C (Pike)
rewire camera together with a Navitar lens stack. The image
acquisition was controlled by a LabView programme. The resulting
colour images contain 2452 1200 pixels. Images are captured in a
time-lapse mode and subsequently analysed by separate software,
also written in LabView.
The analysis software uses colour classication techniques to
assign either oil or clear to each pore and pore-throat within the
model. This process was not sensitive enough to distinguish what
we interpret as middle-phase microemulsion. The resulting array
of lls is subsequently analysed for saturation, front roughness,
remaining oil ganglia size, and size distribution.
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2.3. Results
For the data presented in this section, the injection formula-
tions were aqueous: they contained 2% (w/v) total surfactant 8%
(w/v) butan-2-ol formulation at two different salinities in D2 O and
in H2 O. The salinities were 1.6% and 3.2% (w/v) NaCl in D2 O and
2.0 and 4.0% (w/v) NaCl in H2 O. At the lower salinities, the equi-
librium state of the surfactant formulation (at 1:1 volume ratio)
with decane is L1; the higher salinities give L3 behaviour. Hence for
shorthand, we refer to injection of the rst solution as L1 injection
and of the second as L3 injection despite only injecting the aqueous
surfactant formulation. The oil in the pore networks was n-decane.
For the NMR and most of the micromodel experiments presented,
the surfactant formulation was injected into a fully oil-saturated
pore system. It should be noted however, that the micromodel
is initially oil wetting whereas Bentheimer is water wetting. The
injected surfactant formulation was able to change the wettabil-
ity character of the micromodel as directly observed by the change
in contact angle. The NMR measurements are made with aqueous
D2 O only, while the micromodel experiments include some data
in which the corresponding H2 O-based systems are investigated.
The interfacial tension values for the L1 and L3 systems in H2 O at
equilibrium are 0.10 and 0.006 mN m1 , which at the ow rates
(3) used here give corresponding capillary numbers of 3.5 105 and
6.0 104 , compared to a surfactant-free ood value of 1 107 .
The H2 O and D2 O samples were selected at corresponding salinities
with respect to the phase diagram and solubility. Although studies
(4) were more limited with the D2 O system (e.g., interfacial tension
was only measured with H2 O), we suggest that the systems at the
selected salinities make for a good comparison of L1 and L3 ood
behaviours.
3. Core oods
3.1. L1 and L3 Injection
For the rst core ood experiment (BN1, see Table 1),
the injected surfactant package formulations (1% (w/v) of each
ENORDET surfactant, 8% (w/v) butan-2-ol) in a D2 O brine solu-
tion contained 1.6% (w/v) NaCl, which at equilibrium at 1:1 (v/v) of
brine:decane, gives rise to L1 phase behaviour. The result is shown
in Fig. 3. In the left hand colour plot, sequential 1-D oil saturation
proles from the NMR measurement are stacked such that the pro-
gression of oil saturation can be followed as a function of volume
pumped (i.e., time). Note that the ow is left to right across the
plot. This plot is scaled such that deep red corresponds to So = 40%.
The initial saturation is much higher (100%) but the chosen colour
scale highlights the remaining oil saturation SOR after the initial
front has moved through the system. The injection front velocity
matches that estimated from consideration of the change in satu-
ration across the shock front. Breakthrough of the ooding phase
occurs at 0.75PV with a mean saturation across the core of 12%.
Even at the end of the ood, after 4PV of the surfactant solution
has been pumped, about 8% oil remains. The yellow/green region
indicating elevated saturation near the entrance of the core is unex-
plained, but is indicative of locally inhomogeneous oil saturation.
The 8% saturation after ooding with the L1 surfactant demon-
strates greater recovery than with a (surfactant-free) brine ood
(SOR 27%, Fig. 5) [3032].
The oil saturation integrated over the whole plug is shown in the
plot on the right hand side of Fig. 3 (blue line/circles). Also shown is
the total anionic content of the efuent (red line/squares) expressed
as a percentage of the injected anionic content, i.e., surfactant
concentration. This latter curve is zero until water break-through
and then rises rapidly to nearly 100% recovered surfactant. At
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Fig. 2. The design layout of the micromodel channels.

2.5 PV of injected uid, a sudden fall in surfactant concentration is
recorded. Visual inspection of the efuent sample from this section
of the core ood revealed the presence of a light-scattering emul-
sion phase, which was not sampled using the analytical method
deployed. We think that this emulsied phase sequestered a sig-
nicant portion of the surfactant present in the sample thereby
interfering with the quantitation of surfactant at this stage of the
core-ood.
The equivalent results (core ood of BN2) for injection of a solu-
tion with an increased NaCl concentration (3.2% (w/v)) are shown
in Fig. 4. This system, in equilibrium, will form an L3 phase. It is
important to recognise that the only change between the exper-
iments represented in Figs. 3 and 4 is a change in salinity of the
injectant from 1.6% (w/v) to 3.2% (w/v).
In the colour plot on the left hand side of Fig. 4 the initial shock
front moves more slowly than seen in Fig. 3. The initial front veloc-
ity again matches within experimental error that predicted from
saturation change at the shock. In addition to the BuckleyLeverett
front [33] in Fig. 4, a saturation shadow is seen with an increasing
width that follows the initial front. In this case the efuent shows
no surfactant at brine break-through and indeed surfactant appears
only after nearly 1.5 PV of volume injected. When the surfactant
does appear, it only reaches about 80% of the initial concentration,
in contrast to nearly 100% for the L1 case. Just after the tail end
of the saturation shadow exits the core, a high concentration of
surfactant is seen at 3.5 PV (note this sample was clear and did
not show a macroscopic emulsion). Subsequent aliquots of efu-
ent showed the same surfactant concentration compared to the
injected solution. By this point in the ood essentially all the oil
had been removed from the core.
In Fig. 5 we show the result for the injection of D2 O brine only
(1.6% (w/v) NaCl) into core BN3, i.e., no surfactant/co-solvent, but
otherwise identical to the microemulsion oods described above.
In this case we do not see a clean BuckleyLeverett front develop.
However, ignoring the signicantly inhomogeneous end distribu-
tions, we do see a nal saturation across the middle third of the
core of around SOR 27%, consistent with the literature relative
permeability curves [30].
We suggest that the poor uniformity of the front in the brine-
only ood may result from capillary imbibition of the brine, leading
to ngering of brine into the core prior to the start of the controlled-
ow-rate ood sequence. For the estimated pore size and interfacial
tension between decane and water, we may estimate the capil-
lary pressure at about 600 Pa. This pressure is signicantly greater
than the gravitational pressure across the (vertical) plug of approxi-
mately 132 Pa. It is clear therefore that capillary imbibition can have
a signicant effect on the ooding process for this short core. In
comparison, for the signicantly lower interfacial tension of the L1
case, the capillary pressure is estimated at only about 10 Pa, hence
it should be expected that only the rst few millimetres of the plug

Fig. 3. Left: 1D NMR scans of oil saturation along the core as a function of L1 volume pumped. Right: squares are fraction of injected surfactant found in efuent, circles are
integrated oil saturation after correction for surfactant package as per equation 2. See text for details. (For interpretation of the references to colour in the text, the reader is
referred to the web version of the article.)

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L3 flood oil saturation whole core saturation | effluent surfactant conc.

4 40 4

3.5 35 3.5

3 30 3
Volume pumped / PV

Volume pumped / PV
Local saturation / s.u.
2.5 25 2.5

2 20 2

1.5 15 1.5

1 10 1

0.5 5 0.5
saturation
surfactant
0 0 0
20 30 40 50 0 20 40 60 80 100 120 140 160
Profile position / pixels Saturation / s.u. | surfactant conc. %input

Fig. 4. Left: 1D NMR scans of oil saturation along the core as a function of L3 volume pumped. Right: squares are fraction of injected surfactant found in efuent, circles
are integrated oil saturation after correction for surfactant package as per Eq. (2). See text for details. (For interpretation of the references to colour in the text, the reader is
referred to the web version of the article.)

are affected by capillarity. For the L3 case, the interfacial tension is
sufciently low that there should be no observable capillary effect.
4. Micromodel oods
The primary purpose of the micromodel experiments is to
provide insights into the core ood observations so as to help enable
development of improved models of surfactant cEOR. There have
been some recent theoretical studies using pore network models
[29]. Whilst they encompass transport and trapping of the surfac-
tant, they do not allow for solubilisation into a middle phase. There
have been relatively few other micromodel studies of surfactant
displacement [3436].
4.1. L1 and L3 injection into oil-lled model
The rst results are for oods with L1 and L3 formulations (1%
(w/v) of each ENORDET surfactant, 8% (w/v) butan-2-ol with 1.6
or 3.2% (w/v) NaCl in D2 O) injected into decane-lled micromod-
els. These oods are a direct comparison with the NMR-monitored
core oods. The aqueous solutions were injected on the left of the
micromodel and the red-dyed oil is displaced. The progress of the
oods is shown in Fig. 6 with pairs of images taken. The left images
correspond to the L1 oods and the right image to L3 oods. Each
pairs (top to bottom) is taken after a 30 min interval. Some obvious
differences are apparent:
The front in the L1 case is signicantly rougher than in the L3
case.
There are large patches of oil trapped behind the front in the L1
case that are not seen in the L3 case.
The L1 front moves faster than the L3 front, as would be expected
from the amount of trapping (more oil trapped, faster front).
For the L1 case, for the most part, the patches of oil remain sta-
tionary once trapped; whereas for the L3 case patches of oil are

Fig. 5. Left: 1D NMR scans of oil saturation along the core as a function of brine volume pumped. Right: circles are integrated oil saturation.

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Fig. 6. Sequential micromodel surfactant ood images taken at 30 min (0.18 PV ooding uid) intervals from initial D2 O aqueous phase appearance. Left column of images
for L1 formulation (1.6% (w/v) NaCl) injection, right for L3 (3.2% (w/v) NaCl). Videos of these oods are available as Supplementary Information.

rst trapped, then mobilised and solubilised at a distance from 4.2. L1 and L3 Injectionpore-scale visualisation
the front that increases as the ood progresses.
Although not shown, the nal state of the L3 case is a clean micro- In addition to the L1 and L3 D2 O systems studied, a sequence
model with no remaining oil trapped at a macroscopic scale. of imaged oods was obtained for systematically increasing NaCl

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Fig. 7. Sequential micromodel surfactant ood images taken at 15 min intervals from initial H2 O aqueous phase appearance in a section near the middle of the micromodel.
Left column for L1 injection (1% NaCl), right for L3 (4% NaCl). Videos of these oods are available as Supplementary Information.

concentration in H2 O so that the behaviour could be mapped across column) and L3 (4% NaCl right column) oods at 15 min intervals.
the L1L3 phase boundary. As part of this series, close-up images Initially, the model is very oil wet, displaying a high contact angle
were obtained in a region about two thirds of the way across the (through the aqueous phase). For the right-hand sequence of Fig. 7,
model. These images are shown in Fig. 7 for L1 (1% (w/w) NaCl, left from the second image down, there are lighter red areas which we

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Fig. 8. Microuidic oil displacements from Fig. 6 reduced to oil saturation (expressed as volume fraction) as a function of position and frame count (at 1 frame per 10 min).
Left: H2 O brine injection; Middle: L1 D2 O formulation injection; Right: L3 D2 O formulation injection.
tentatively associate with formation of middle-phase microemul-
sion as seen in the phase behaviour studies. The quantity of these
lighter-red regions increases with time and they ow with highly
deformable interfaces. Some areas can be seen slowly to transform
from dark red to light red with an associated boundary moving
through the trapped blob. We do not think these lighter-red areas
are simply lms on the front or back of the model since they are of
a uniform colour density from wall to wall, at all menisci and from
region to region, thus implying a constant thickness which is most
simply explained as each region lling the depth of the channel. In
the left-hand column of images the menisci move rapidly through
the image region leaving ganglia with a low contact angle through
the aqueous phase, suggesting a change from oil to water wettabil-
ity on the model surface, but there is no change in colour density
within the oil ganglia and hence no detectable solubilisation.
To enable qualitative comparison with the core ood data, the
microuidic displacement images were reduced to 1-D saturation
plots, i.e., the averaged saturation plotted as a function of position in
the direction of ow and time. These data derived from the image
sequences shown in Fig. 6, together with a brine only ood, are
shown in Fig. 8 for oil saturation as a function of x-position (number
of model cells). The bright red area indicates the initial oil that is
subsequently displaced from the model at a uniform velocity.
In the middle image (L1 phase), there is a persistent oil satura-
tion at about x = 40 cells. On examination of Fig. 6, it this saturation
appears to be due to a few large, stationary oil ganglia. On the right
hand image of Fig. 8 (L3 phase), a saturation shadow trails the
main front but at a slower speed and therefore with an increasing
width. It should be noted that this image analysis is insensitive to
the solubilised oil observed by eye at the trailing edge of the satu-
ration shadow (lighter red in the images, Fig. 6). The plots in Fig. 8
exhibit the same trends as those obtained for the corresponding
surfactant core oods (see Figs. 3 and 4).
4.3. Surfactant ood into brine-ooded micromodels
Surfactant cEOR oods in reservoirs generally follow brine
oods as a tertiary recovery process, rather than the sequence
described above in which surfactant solutions were injected
directly in oil-lled media (mimicking a secondary recovery pro-
cess). We now consider the situation wherein a brine ood precedes
the surfactant injection. Brine was injected into the microuidic
network at 0.1 L min1 , followed by a surfactant formulation at
the same salinity and ow rate. The surfactant solution was injected
after brine breakthrough at the outlet of the model. The surfactant
formulations were in H2 O at salinities representative of L1 and L3
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9
type behaviour; the series of 2.0 and 4.0% (w/w) NaCl images are
shown in the left and right columns of Fig. 9, respectively.
The images captured at brine breakthrough (Fig. 9, top) show
the displacement patterns for the two brine oods; there is little
difference between the two displacement patterns, i.e., they both
show the same capillary ngering behaviour. We would expect the
patterns to be almost identical as there are no signicant differ-
ences between both the interfacial tensions and contact angles of
the two systems (all other conditions are identical). A small dif-
ference is observed: the So of the 2.0% (w/w) NaCl ood (0.27) is
slightly lower and the average size of the ganglia of trapped oil
is slightly smaller (850 pixels) than that of the 4.0% (w/w) ood
(So = 0.30 and average ganglia size = 890 pixels). However, these dif-
ferences are within the expected reproducibility of the microuidic
studies.
Although some mobilisation of trapped oil ganglia was observed
on injecting L1 formulation, on injecting L3 formulation ganglia
were both mobilised and solubilised as expected. In the L3 ood,
all the oil was eventually displaced from the network.
5. Discussion
There is a very clear difference between the saturation (oil)
distributions observed in the surfactant oods at the two NaCl con-
centrations in both the 3D rock cores (Figs. 3 and 4) and the 2D
microuidic devices (Figs. 6 and 7). There is a striking similarity
observed between the development of oil saturation proles at the
corresponding salinities in the core plugs and microuidic devices
in particular, the same relative speeds of the displacement fronts
and the saturation shadow when injecting the L3 formulation that
was not expected. While the liquids used in the two pore structures
were the same and therefore the equilibrium phase behaviour is by
denition the same, the dimensionality might be expected to lead
to signicant differences, as might the very signicant permeability
and wettability difference.
In the L3 microuidic oods we see oil solubilisation occurring
at the trailing edge of the saturation shadow. Since the solubilisa-
tion process will act as a signicant sink removing surfactant from
the brine solution, the surfactant concentration should be reduced,
possibly to a very low level, from the trailing edge of the satura-
tion shadow forward to the ood front. Thus from the microuidic
observations we would predict that, when measuring the efuent
of the L3 Bentheimer displacement experiments, the surfactant
should not reach its full concentration until sometime after the
trailing edge of the saturation shadow, which was indeed the result
obtained (Fig. 4, right).
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Fig. 9. Micromodel ood images for surfactant oods following H2 O brine ood. Top image after brine ood. Then images at 30 min (0.18 PV ooding uid) intervals during
surfactant ooding. Left column for L1 injection (2.0% NaCl), right for L3 (4.0% NaCl). Videos of these oods are available as Supplementary Information.

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Fig. 9. (Continued).

We can gain some insight into the observed behaviours by
considering the results of a network simulator model due to Ham-
mond and Unsal [29]. Although in that model there is no mechanism
for solubilisation, there is a trapping mechanism envisaged via
surface adsorption. Within the model, and as a function of ow
rate, different regimes can be discerned. (1) At low ow the sur-
factant permeates the pore network and the ood proceeds as if
it were at a uniformly higher capillary number. (2) At moderate
ow the surfactant concentration does not keep up with the dis-
placement front, thereby creating a concentration gradient and
therefore an interfacial tension gradient. This interfacial tension
gradient enables a front stabilisation mechanism, i.e., a attening
of the displacement front [29]. In our microuidic experiments for
the L3 case, the initial displacement front is quite smooth, at least
until the remaining oil starts to become solubilised, which is pos-
sibly due to a similar surfactant concentration gradient giving rise
to a low initial IFT together with a concentration gradient at the
displacement front. As the ood progresses, however, the surfac-
tant concentration at the displacement front should fall to very low
values since it is held up by the microemulsion phase formation.
Hence, toward the end of the ood, no appreciable concentration
gradient exists at the front and consequently the front rough-
ens.
For a Bentheimer core plug of this size, the internal sur-
face area is estimated to be about 5 m2 (from mercury intrusion
porosimetry). If we estimate a maximum surfactant adsorption to
be 4 mg m2 , then the total adsorption of 0.01 g would be approx-
imately 4% of the surfactant contained in 1PV ooding solution.
Therefore the observed dynamics for both the Bentheimer plug
and the microuidic model (which has signicantly less surface
area) are unlikely to be affected by surfactant adsorption beyond
any effect on surface wettability. A further consequence of the rela-
tively large surfactant concentration to surface area ratio is that any
partitioning of the different components of the surfactant solution
to the solid surface is unlikely to be of signicance.
The picture that emerges from these results is that:
(i) The brine core ood behaviour is consistent with ngering
caused by capillary imbibition effects which prevent formation
of a clean ood front (Fig. 5). Nevertheless the nal remaining
oil saturation is high and consistent with literature residual oil
saturation values [3032].

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(ii) The L1 ood proceeds simply as a low interfacial tension ood
where is sufciently low to allow mobilisation of an addi-
tional proportion of the oil.
(iii) The L3 ood proceeds with the surfactant as a middle-phase
microemulsion trailing the main displacement front with a
region of residual-oil ganglia and a low concentration of sur-
factant in between. In the microuidic models we see, at
the trailing edge of the residual oil region left by the initial
front, mobilisation of disconnected oil ganglia, and immedi-
ately behind that, solubilisation into the middle-phase. The
middle phase microemulsion is a sink for the surfactant but
does eventually exit the pore structure.
In the cases studied here, the L1 phase system might be
expected to have an underlying structure similar to Hirasakis
model [6], since it is a two-phase, three-component system. How-
ever, for the particular surfactant formulation used, here against
decane, the solubilisation is very small and the IFT, whilst low
( ow 0.1 mN m1 ), is not ultra-low ( ow < 0.01 mN m1 ). Hence,
whereas the capillary number is increased, it is not increased suf-
ciently to initiate mobilisation of much, if any, of the remaining oil.
Since little oil is mobilised, no oil bank is generated and no concomi-
tant shock is seen (Fig. 3). In contrast, the ULIFT and solubilisation
assumed by Hirasaki [6] is more consistent with our observations
of the L3, middle-phase behaviour (Fig. 4).
The Bentheimer core-ood observations are complicated by the
fact that the sandstone is strongly water-wet. In the brine-only
ood we see evidence of capillary imbibition (no clean shock front
Fig. 5). For the L3 case, the efuent analysis suggests that the water
saturation behind the displacing front has little surfactant present.
This would imply the interfacial tension at the front is higher than
expected (surfactant depletion) and capillary forces may be strong
enough to broaden the displacing front. In the data we certainly see
a broader front at the exit side of the plug than we do over the rst
half of the plug.
In the L1 case, where the surfactant keeps up with the front,
we expect a low interfacial tension and we see that a sharp front
is maintained. The slightly lower oil saturation at the exit face in
each of the experiments may also be in part due to priming the
exit pipework with brine prior to the start of the ood together
with the concomitant water wettability of Bentheimer sandstone.
These effects, whilst inconvenient in detail, do not alter the overall
behaviour observed.
Some outstanding scientic questions remain, including:
Microemulsion systems are formulated via equilibrium studies,
yet they are generated in a formation under dynamic (i.e., ow-
ing) conditions. Moreover, the phase behaviour may be altered by
the ow. It is not known how important the difference between
dynamic and static behaviour might be. Furthermore, it is conven-
tionally assumed that concentrations are locally uniform, through
the action of strong diffusion and dispersion, which may not be
the case. The assumption of a local mixing tank equilibrium used
in simulations should be questioned [6].
These same formulation studies are performed in the absence of
mineral surfaces, yet it is known that microemulsion systems can
align adjacent to interfaces [37], which also affects the assump-
tion of quasi-equilibrium. The importance of surface proximity is
unknown.
Last, the experiments presented do not revisit the wide range of
processes of interest, such as oods with step changes in salinity,
or with salinity gradients. In each case it would be valuable to
track the surfactant location, phase distribution and quantities of
solubilised materials (oil-in-brine or brine-in-oil) as well as the
dynamics of the processes as described above.
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Aspects (2014), http://dx.doi.org/10.1016/j.colsurfa.2014.08.032
6. Conclusions
We have demonstrated experimental procedures for monitor-
ing oil displacement in rock plugs and microuidic networks that
enable us to observe in detail the behaviour of a chemical EOR pro-
cess. In the present work we focussed on surfactant formulation and
how it alters the multiphase ow behaviour within a porous struc-
ture. Whilst we have not observed the surfactant directly, other
than as it appears in the efuent analysis, we are able to corre-
late the appearance of the surfactant with observed oil saturation
shocks transiting through each porous medium.
In both the microuidic and rock-core-plug ooding studies, we
observe classical BuckleyLeverett fronts as the initial oil in place
is recovered. When the aqueous components of L1-forming for-
mulation is injected, the ood proceeds simply as a low interfacial
tension ood where  is low enough to allow mobilisation of an
additional proportion of the oil. When an L3-forming aqueous for-
mulation is injected, we observe shock fronts that we associate
with both surfactant concentration gradients and solubilisation of
oil into a middle-phase microemulsion that trails the main dis-
placement front. Between this middle-phase microemulsion and
the main oil front exists a region of residual-oil ganglia and low
surfactant concentration. The middle-phase microemulsion acts as
a sink for the surfactant but does eventually exit the pore structure.
In summary, this work highlights the importance of understand-
ing the in situ phase behaviour of surfactant formulations when
injected into an oil reservoir. Careful formulation may allow sig-
nicant enhancements in oil recovery through the creation and
transport of a L3 middle-phase microemulsion.
Acknowledgements
We are particularly grateful to Paul Hammond (Schlumberger)
for his support and many stimulating discussions. We are grate-
ful to Schlumberger colleagues Rick Penney, Chris Marooney,
Leslie Zhang and Simon Andersen for their careful reading of this
manuscript. We thank Julian R. Barnes (Shell Global Solutions
International B.V.) for supplying the ENORDET surfactants and for
helpful discussions of their phase behaviour.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.colsurfa.
2014.08.032.
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