A34

Surfactant Flooding Evaluation for Enhanced Oil

Recovery in Sandstones Reservoirs
F.C. Bonilla* (State University of Campinas - UNICAMP) & R.B.Z.L. Moreno
(State University of Campinas - UNICAMP)

SUMMARY
This research work considered surfactants for chemical oil recovery applications. Surfactant flooding is an
EOR technique applied for decreasing capillary effects by molecular performance alterations on water-oil
interface between injected water and displaced oil. In most situations, this method is implemented as a
tertiary flood near of the end of waterflooding but it could be conducted after the initial stage of field
production when oil saturations are high in the porous media. By an injector well, required volumes are
introduced to the reservoir with the defined surfactant formulations for developing a new stabilized oil
bank via ultralow interfacial tension between oil and water phases.
The experimental methodology included Phase Behavior and Coreflooding tests for making comparative
analyses between oil production responses of different configurations of surfactant flooding method. The
phase behavior tests were conducted to select the best surfactant formulations through interfacial tensions
and solubilization ratios determinations of different concentrations of five commercial surfactants: three
anionic surfactants (Stepanol, sodium dodecyl sulfate and ammonium dodecyl sulfate) and two no-ionic
surfactants (SPAN-20 and TWEN-20). Previously, it was performed surface tensions measurements to
identify the critical micellar concentration (CMC), characteristic of each surfactant. The selected primary
surfactant and co-surfactant formulations were tested for enhanced oil recovery using coreflood tests on
high permeability sandstones from Bocatutu Formation. In these tests, the primary formulation solutions
were followed by polymeric drive solutions injection. The tested formulations were also tested for porous
media adsorption, evaluating surfactant losses during a surfactant flooding.
The results are useful for running numerical simulation cases and single well field projects.

IOR 2013 – 17th European Symposium on Improved Oil Recovery

St. Petersburg, Russia, 16-18 April 2013
Introduction

Surfactants have been widely used for different purposes since the early years of petroleum industry
because of their ability for altering the interfacial behaviour between two immiscible fluids in contact
with each other. Interfacial phenomena have influence on rock-fluid interactions and interactions
between fluids occurring from the reservoir to distribution pipelines; therefore, surfactants can be
used for several petroleum industry activities. Several laboratory experiments, pilot-scale projects and
field-scale projects all over the world have shown different results about surfactants application for
enhancing oil recovery since the 1970’s (Iglauer et al, 2010). Several types of surfactants have been
studied to determine high efficacy chemical EOR formulations. Anionic and non-ionic surfactants are
commonly used in sandstones reservoirs since they provide the lower solid adsorption onto reservoir
sandstones whose surface charge is negative (Green and Willhite, 1998).

Surfactants are amphiphilic molecules with both hydrophobic and hydrophilic parts in their structure.
Basically, hydrophilic part is a polar or ionic group (i.e., sulphates, sulfonates, carboxylates,
phosphates) while hydrophobic part is a linear or branched hydrocarbon chain (Holmberg et al, 2002).
Surfactants molecules are absorbed by the water-oil interface due to strong forces between the polar
group of hydrophilic part and dissolved ions in the aqueous phase. Thus, the required energy for
increasing the surface area of the interface is reduced and, consequently, the water-oil interfacial
tension is diminished (Samanta et al, 2011).

There are a considerable number of involved variables in the injection process from microscopic to
macroscopic scales (Santanna et al, 2009). Consequently, it’s necessary to design certainly the
surfactant formulations for obtaining successful results, taking into account the most important
variables as interfacial tension reduction, brine tolerance, chemical stability, solid adsorption and even
economics (Wu et al, 2005).

Experimental methodology was developed for studying the effect of surfactant flooding on oil
recovery using phase behavior tests and core flooding experiments to compare the responses of
different anionic and non-ionic surfactants.

Surfactant Flooding

Residual oil is dispersed in aqueous phase as micron-size droplets and trapped within the porous
media because of the capillary and viscous forces (Sheng, 2011). A determined surfactant aqueous
solution is injected for reducing capillary forces via ultralow interfacial tension between oil and water
phases (i.e. 0.001 mN/m). That reduction is equivalent to increasing the capillary number , a
dimensionless group which represents the ratio between the viscous and capillary forces, at least three
magnitude orders (Green and Willhite, 1998).

In adequate conditions, the surfactant is dissolved in either oil or water to form a new
thermodynamically stable phase called “microemulsion”. Microemulsions are created for obtaining
ultra-low interfacial tensions in the interfaces oil-microemulsion and water-microemulsion. In
microemulsions systems, the phases coexist in equilibrium with excess oil or excess water.

In surfactant flooding, a chemical slug (surfactant and co-surfactant slug) is injected into reservoir.
Usually, this chemical slug is displaced for an aqueous phase slug or, sometimes, for a polymer bank
which in turn is displaced by water (Lake, 1989).

CMC Tests

Surfactants can be defined, from the chemical viewpoint, as special molecules which are able to form
spontaneously molecular aggregates in solution known as micelles. When the surfactant concentration

IOR 2013 – 17th European Symposium on Improved Oil Recovery

St. Petersburg, Russia, 16-18 April 2013
is increased, interfacial area covered by the surfactants molecules also increases and surface energy
(surface tension) reduces. There is a limit concentration known as Critical Micelle Concentration
(CMC) above which addition of surfactants will just increase the number of micelles and the surface
tension stays more or less constant. After reaching CMC, most of physicochemical solution properties
(e.g. Surface/Interfacial Tension, conductivity, osmotic pressure and solid adsorption) show strong
variations (Tadros, 2005).

CMC is a characteristic property of each surfactant or mixtures of them. There are many methods that
have been developed to determine the CMC of surfactants. The typical method considers surface or
interfacial tension measurement of surfactant solutions using force tensiometers (Du Noüy ring
tensiometer, Wilhelmy Plate Tensiometer or Platinum Rod Tensiometer), optical tensiometers
(Pendant drop tensiometer) or dynamic tensiometers (Spinning drop tensiometer).

A graph of surface tension versus log concentration is produced. The CMC is found as the point at
which two lines intersect; the baseline of minimal surface tension and the slope where surface tension
shows linear decline.

Phase Behavior Tests

Ultralow interfacial tension between fluids is an important variable to select the appropriate surfactant
formulation. Water and Oil Solubilization Parameters are defined as the ratio of the solubilized phase
( , ) volume to the surfactant volume ( ) in the microemulsion phase (Healy, 1975).

= =

Solubilization parameters are closely related to interfacial tension (Huh, 1979) because when the
solubilization parameter for oil is equal to that for water = , the interfacial tension reaches its
minimum for most of surfactants. The solubilization ratio and interfacial tension at the middle phase
can be predicted using the Chun-Huh equation at middle phase, as the following (Kanan, 2012):

0,3 0,3
= =
( ⁄ ) ( ⁄ )

Phase behavior tests are conducted for evaluating surfactant formulations for a specific crude oil by
qualitative and quantitative criteria including (Tabary et al, 2012):
• Relative volumes of the phases.
• Stability of surfactant solutions without phase separation and precipitation.
• Stabilization time of microemulsion in equilibrium.
• Formation of undesired phases.

By producing a graph of solubilization parameter for oil and water versus electrolyte concentration,
it’s possible to identify the Optimal Salinity as the point at which two solubilization ratio curves
intersect (Kumar et al, 2012).

Experimental Study

The oil selected for surfactant studies was a mixture of dehydrated oil from Marlim reservoir
(Oliveira, 2008) with kerosene (MRL-K 70/30). This mixture has a density of 0.89 g/cm3 and a
viscosity of 50.3 cp, both at 24°C. A synthetic brine (5% NaCl Solution) was used to saturate the
samples and as displacement fluid in the coreflood test. A large array of surfactants was pre-selected
from literature and the specific surfactants used in this study were three anionic surfactants and 2 non-
ionic surfactants (Table 1). The structures of the surfactants are shown in Figure 1.

IOR 2013 – 17th European Symposium on Improved Oil Recovery

St. Petersburg, Russia, 16-18 April 2013
Surfactaant solutions were freshly y prepared too avoid degraadation and stirred
s by usiing magneticc stirrers.
The visccosity of surffactants soluttions varies ffrom 1.0 to 1.5
1 cp dependding on the cconcentration
n.

The appplied methoddology consiists of threee main stagees: 1) Determ mination of CMC of su urfactants
selected. 2) Selectioon of the besst surfactant formulation
n 3) Corefloo
od with the bbest formulattion. The
stages arre described below (Fig. 2).

Taable 1 Summaary of Screen

ned Surfactants.
Namee Type
Sodiumm Dodecyl S
Sulphate (SDS) Anionic
Ammonium Dodecyll Sulphate (A ADS) Anionic
Sodium
m Laureth Suulphate (SLEES) Anionic
Sorbitaan Monolaura
rate (SPAN-2 20) Non-ionicc
P
Polyoxyethylene Sorbitan
n Monolauraate (Polysorb
bate-20, TWEEEN-20) Non-ionicc

Figure 1 Chemical structure

s of selected
s surffactants for screening.
s a) Sodium Doddecyl Sulpha
ate (SDS)
b) Ammoonium Dodeecyl Sulphatee (ADS) c) Soodium Laureeth Sulphate (SLES) d) SSorbitan Mon nolaurate
(SPAN-220) e) Polyooxyethylene Sorbitan
S Moonolaurate (Polysorbate-
(P -20, TWEENN-20). (Adap pted from
Schrammm, 2000).

Figure 2 Applied Methodology

Me for
f experimenntal analysiss.

CMC M
Measuremen
nts

A pendaant drop tenssiometer wass used to deteermine the critical

c micellle concentraation of surfaactants in
the first stage of thee research wo
ork. The penndant drop method
m is bassed on the ddeformation ofo a drop
dependinng on the innterfacial tennsion (Schram
mm, 2000). A drop is dispensed
d froom the need dle in the
tensiomeeter and an ultrafast
u mera records the images of the drop. Finally, a ddefined drop shape is
cam

IOR 2013 – 17th

1 Europeann Symposium on Improved Oil Recoveryy
St. Petersburgg, Russia, 16-18 April 2013
3
fitted to the recordedd images usin
ng the Younng-Laplace eq quation and the surface ttension of an
ny known
concentrration surfactant solution
n is determineed as the calculated averaage tension oof recorded images.
i

CMC m measurementss were perforrmed by diluuting a conceentrated surffactant solutiion with pure solvent
for eachh surfactant concentration
c n sample. Th eoretical CM
MC of each su urfactant givves an insigh
ht into the
expectedd CMC’s vallues.

IFT and
d Phase Beh
havior Tests

Phase bbehavior tests were cond ducted by addding brine solutions an nd crude oill in 5 ml piipettes to
analyse the performmance of the chemical foormulations over a rangee of salinitiees. The 1:1 waterw oil
ratio sam
mples were prepared
p addding 2 ml of aqueous phaase (surfactaant/co-surfacttant/brine) to
o 2 ml of
hydrocarrbon phase. The pipettes were stronggly shaken du uring 3 minuutes at ambieent conditionns (24 °C,
atmosphheric pressuree) for mixingg the sample s, and were allowed
a to eq
quilibrate at 42°C in a co
onvection
oven forr a minimum m of 15 dayss. The relativve volumes of aqueous, oleic and m microemulsio on phases
olubilizationn Parameters and estimatee the Interfaccial Tension between
were reccorded to esttablish the So
fluids.

Coreflooding

The expperimental appparatus is basically

b com
mposed of sy yringe positivve displacem
ment pump, cylinders
c
for fluidd storage, coore holder with
w pressuree transducerss with an au utomatic dataa acquisitionn system,
digital aanalytical scaales and grad
duated cylindders for collecting the prroduced fluidds. The expeerimental
apparatuus is shown ini Figure 3.

The correflood test was conducted in a Bootucatu Form mation sandstone samplee. First, rock k sample
characteeristics (weigght dry, lengtth and diameeter) were deetermined an
nd the core pplug was inseerted into
a core holder to measure
m osity and peermeability by using a helium porrosimeter an
poro nd a gas
permeam meter, respecctively. Tablee 2 shows exxperimental characteristic
c cs of corefloood experimennt.

Figure 3 Schematic diagram of experimental

e l apparatus for
f coreflooo
od test.

Tablle 2 Core prooperties and initial condiitions

Botucatu Formation Sandstone
Diaameter mm 37
7.22
Leength cm 30.1
Weight
W g 598.96
Tem
mperature °C 24
2
Saalinity mg/L 30.000
Po
orosity frac. 0.29
Perm
meability mD 56666

The correflood wass conducted horizontallly at a con nstant injecttion flow rrate. Flow rates
r for
waterfloooding and chhemical flooding were heeld constant at 0.8 ml/min.

IOR 2013 – 17th

1 Europeann Symposium on Improved Oil Recoveryy
St. Petersburgg, Russia, 16-18 April 2013
3
After establishing noo leaks with preliminary pressure tessts, a vacuum m is applied tto evacuate the
t air in
the sampple. Core is fully saturateed with brin e (50000 ppm m NaCl) in a primary im mbibition proocess and
then MR RL-K oil is injected into o the core saample until connate watter saturationn was reacheed. After
primary drainage, reesidual oil saaturation is oobtained in th
he secondary y imbibition by waterfloooding the
core andd secondary recovery waas determineed. In most cases,c sandstoones cores ddon’t strongly exhibit
the hystteresis phenoomena and it’s
i possible to perform a second drrainage proccess for returrning the
porous media saturrations to initial
i valuees ( =1 ). Subsequeently, Enhan nced Oil
recoveryy is determinned by injeccting a slug of the surfacctant formullation chasedd for brine, in a new
imbibitioon process. Table 3 su ummarizes eexperimentall conditions and operattional sequeences for
corefloood experimennt. The recovvery factor wwas calculated d via fluid mass
m balance.

Table 3 O
Operational sequences.
s
Stage Rate [ml/min] Porre Volumes to inject Fluid
1° Drainage 0.8
8 3.5 M
MRL-K
Watterflooding 0.8
8 7.0 5% wt (500000 ppm ) NaC
Cl Brine
2° Drainage 0.8
8 3.5 M
MRL-K
Surfacctant Floodinng 0.8
8 7.0 Best Surfacctant Formullation

Results

Surface tensions werre measured to identify thhe Critical Micelle

M Concentration forr selected surrfactants.
Figure 4 shows the obtained
o resu
ults in Gibb’ss adsorption isotherms fo
or every seleccted surfactaant.

Figure 4 Gibb’s inteerface absorrption isotherrms used forr determining

g CMC of seelected surfa
actants at
24°C (755,2 °F).

IOR 2013 – 17th

1 Europeann Symposium on Improved Oil Recoveryy
St. Petersburgg, Russia, 16-18 April 2013
3
Alkyl sulphates surfactants (SDS and ADS) show the highest CMC’s values which means that it
would be necessary to increase the necessary chemical amount in the aqueous solution for reaching
the lower surface tension. SLES is an ethoxylated alkyl sulphate surfactant and the main difference
with the alkyl sulphates is the additional polyethoxylated units in chemical structure. SLES exhibits
low CMC concentration value among anionic surfactants; on the other hand, it doesn’t show
meaningful surface tension reduction. Surface tension at CMC is similar for all surfactants and the
lower surface tension values are founded for ADS and SPAN-20 (Table 4). These results give an
insight about IFT reduction of the surfactants when they are in contact with hydrocarbon phases.

Table 4 CMC measurements results.

CMC value1 Surface Tension @ CMC
Surfactant
[%wt] [mN/m]
Sodium Dodecyl Sulphate (SDS) 0,1000 33,75
Ammonium Dodecyl Sulphate (ADS) 0,1800 28,30
Sodium Laureth Sulphate (SLES) 0,0300 37,50
Sorbitan Monolaurate (SPAN-20) 0,0018 29,10
Polyoxyethylene Sorbitan Monolaurate (TWEEN-20) 0,0100 39,25
1
Calculated as the intersection point between two base lines.

Phase Behavior Experiments were performed for two different surfactant concentrations above the
CMC. IFT’s for surfactant aqueous solutions were established as a function of phase salinity varying
within 0,0% wt (0 ppm) and 9,0% wt (90.000 ppm) . Table 5 shows the screened formulations and
their results. IFT values were determined by using Chun-Huh Equation (Kanan, 2012).

According to the results, some key findings could be cited (Table 5):

• IFT reduction is higher for anionic surfactants than non-ionic surfactants.

• IFT reduction increases when surfactant concentration is increased. However, these increments
• Systems with Sodium Laureth Sulphate (SLES) don’t exhibit the any microemulsion phase, and
it’s not possible calculate the interfacial tension using this method.
• The #2 Formulation (1,00% wt SDS) was selected for the coreflood experiment because it provides
the lower interfacial tension (3,7 x10-3 mN/m) for MRL-K Oil.
• Optimal Salinity for selected surfactant is very low (1,3 %wt) which could be an important
limitation on high salinity and high temperature reservoirs.

Table 5 Phase Behavior Tests results.

Po=Pw
Surfactant Optimal Salinity, IFT at σ*
# Surfactant at σ*
Concentration [%wt] σ* [%wt] [mN/m]
[ml/ml]
1 SDS 0,50 5,0 6,8 6,5E-03
2 SDS 1,00 1,3 9,0 3,7E-03
3 ADS 0,50 6,9 6,4 7,3E-03
4 ADS 1,00 5,0 7,1 6,0E-03
5 SLES 0,05 - - -
6 SLES 0,10 - - -
7 SPAN-20 0,05 5,5 5,2 1,1E-02
8 SPAN-20 0,10 6,0 6,6 6,9E-03
9 TWEEN-20 0,05 5,9 5,0 1,2E-02
10 TWEEN-20 0,10 4,9 4,0 1,9E-02

IOR 2013 – 17th European Symposium on Improved Oil Recovery

St. Petersburg, Russia, 16-18 April 2013
Experimmental resultss show the saalinity effectt on IFT redu uction for the selected foormulation (F
Figure 5)
on plots of solubilizaation parameeters and inteerfacial tension versus NaaCl Concentrration.

Figure 5 Solubilizaation parameeter and IFT

T versus Na
aCl concentrration in thee selected su
urfactant
formulattion (1,00% wt SDS) .

A 0,5 poore volume surfactant

s slug was injeccted into thee core samplee followed bby a 3,0 poree volume
formatioon brine (30.000 ppm) at constant ratee of 0.8 ml/mmin. The seleected formullation was effficient in
terms oof residual oil
o recovery because affter injecting g 75% poree volumes, rrecovery factor was
successffully increaseed from 50%
% to 60%, appproximately.

Figure 6 Oil Recoveery Factor fo

or Waterfloodding and SDS
S Surfactant Flooding.

IOR 2013 – 17th

1 Europeann Symposium on Improved Oil Recoveryy
St. Petersburgg, Russia, 16-18 April 2013
3
Conclusions

Salinity is an important variable related to the interfacial tension reduction efficience of surfactants.
Varying salinity of surfactant in phase behavior tests permits to obtain estimated interfacial tension
values via relative phase volumes.

Interaction between MRL-K Oil and SLES (Sodium Laureth Sulphate) didn’t exhibit the
microemulsion phase or any type of Winsor enviroment on the whole range of investigated salinities.
Hence, it wasn’t possible to obtain the interfacial tension values and the optimal salinity for that
surfactant.

Alkyl sulphate surfactants are effective in terms of Enhanced Oil Recovery with low surfactant
concentrations as low as 1% wt. The use of a small volume (0,5 pore volume) of surfactant can reduce
the interfacial tension and, therefore, increase the recovery factor by approxymately 10%.

The IFT reduction for higher concentrations than CMC isn’t meaningful and the amount of required
chemical could be reduced without afectting the addicional oil recovery.

Acknowledgments

The authors thank Petrobras and CAPES (Coordenação de Aperfeiçoamento de Pessoal de Nível
Superior) for their financial support for this project.

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IOR 2013 – 17th European Symposium on Improved Oil Recovery

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IOR 2013 – 17th European Symposium on Improved Oil Recovery

St. Petersburg, Russia, 16-18 April 2013