ENHANCED OIL RECOVERY TECHNIQUES Syllabus

UNIT-V
Use of surfactants in oil recovery: Chapter 10 (Pages 255-307)
Introduction- Classification of EOR surfactants- Mechanism of
oil displacement by surfactant flooding- Ultra low interfacial
tension in relation to oil displacement by surfactant flooding-
Factors influencing oil recovery- Surfactant gas flooding for oil
recovery- Interfacial phenomena in surfactant gas flooding-
Mechanism of surfactant loss in porous media- Present status
of the use of surfactants in oil recovery.
 USE OF SURFACTANTS IN OIL RECOVERY
INTRODUCTION:
 Surfactant molecules are composed of lipophilic (has sufficient solubility
in the solvent) & lipophobic ( is rejected by the solvent) groups.
 These group structure is known as amphipathic structure.
 The lipophilic group usually consists of a long hydrocarbon chain.
 A polymer can also act as a surface active molecule if it has two
functional groups, one lipophilic ( solvent loving) and the other
lipophobic (solvent hating). Both are shown in fig. 10.1
 If the surfactant contains a hc chain with less than 12 carbon atoms, it is
called water soluble. When hc chain length is greater than 14 carbon
atoms, the compounds are called water-insoluble surfactants.
 The lipophilic group is ionic or highly polar. Surfactants can be classified
as anionic, cationic, amphoteric or non-ionic. Anionic surfactants widely
used in EOR due to their lower adsorption on the reservoir rocks.
CLASSIFICATION OF EOR SURFACTANTS:
Petroleum sulfonates:
 Most of the surfactant formulations for EOR contain petroleum
sulfonates, obtained from refinery products.
 The pet. sulfonates were prepared by sulfonating gas-oil fractions with
sulfuric acid. To avoid sludge disposal problem from this process, crude
oil was sulfonated with SO3 to provide cost effective process.
Synthetic sulfonates:
 The synthetic sulfonates may lead to effective improvements in EOR
surfactants even though more expensive. They have better resistance to
metal ions particularly Ca2+ & Mg2+.
 The first one commercially developed was alkyl benzene sulfonates. The
olefin & aromatic feedstocks are the major sources for preparation of
alkylates. These were sulfonated with either SO3 or H2SO4 .
 The mixed petroleum sulfonate & synthetic sulfonate formulations have
resulted in improved oil recovery.
MECHANISM OF OIL DISPLACEMENT BY SURFACTANT FLOODING:
Capillary forces and capillary number:
 The residual oil is in the form of immobile globules distributed through
the pores of reservoir rock. The two major forces acting on these
immobile globules are capillary & viscous forces.
 Fig.10.2 shows a correlation between the capillary number and the
residual oil saturation in a porous medium. The ratio of viscous forces
to capillary forces is called capillary number.
 Nc = µwφq / ϒo/w ………….10.1
where Nc = capillary no. µw & q are the viscosity and flow rate per unit
cross-sectional area of water, ϒo/w is interfacial tension between oil and
water, φ is the porosity of the reservoir.
 At the end of water flooding the capillary no. is in the range of 10 -6—
10-7. As it increases, the displacement efficiency also increases.
 To displace 100% oil it is necessary to increase N c by 4 orders of
magnitude (10-2 to 10-1), shown in fig.10.2
 For the most efficient displacement of residual oil, the porous media
should be water-wet.
Interfacial phenomena:
Oil recovery efficiency can be influenced by producing ultra-low
interfacial tension between crude oil & brine. The interfacial tension
depends on interfacial charge, interfacial viscosity and wettability.
Interfacial tension:
o The flow of trapped oil droplets or oil ganglia through the narrow necks
of pores is shown in fig.10.3. In the presence of a suitable surfactant, an
ultra-low interfacial tension can be achieved at an oil-brine interface.
o The main conclusion was the preferred value of R (alkyl chain length)
corresponding to a minimum in interfacial tension increases with
increasing equivalent weight of the surfactant.
 There are two regions of UL-IFT (ultra low interfacial tension) in TRS 10-410-IBA-
dodecane-brine system. In the low surfactant conc. (around 0.1%) region, the
system forms two phases, oil-brine in equilibrium with each other, where as
high conc. (around 4-8%) region, a middle phase microemulsion is in equilibrium
with excess oil and brine, Fig.10.4. The formation of a L-IFT requires an
optimum electrolyte conc. and salinity, and the value of alkyl chain length (R)
corresponding to minimum IFT is the same for alkylbenzene sulfonates and
alkylsulfonates.
Fig. 10.5 delineates the effect of salt conc., oil chain length and surfactant
conc. on the IFT of pure and impure alkylbenzene sulfonates. It is
evident that the ultra-low IFT occurs at a specific surfactant
concentration.
 Interfacial Charge: Fig.10.6 summarizes the relevance of surface charge in the oil
displacement process from the reservoir channels. A better understanding of the
magnitude and nature of interfacial charge in the oil -displacement process can
contribute significantly to the design of surfactant formulations for optimum
performance under given reservoir conditions.
• A low surface charge density causes
high IFT & high IFV as well as low
electrical repulsion between the oil
globules and sand particles Fig.10.6
• The addition of a suitable surfactant
would increase IF charge density.
• This high charge density in the
presence of surfactant would result
in a decrease in IFT & IFV, and would
also result in an increase in electrical
repulsion between oil globules &
sand particles.
• This facilitates the movement of oil
ganglia through the pore channels if
the oil does not adhere to the sand
particles fig.10.6.
Interfacial Viscosity:
• The efficient oil recovery, the
displaced oil ganglia must coalesce
and form an oil bank (fig.10.7). A very
low IFV is required for the coalescence
of the oil ganglia to form an oil bank. .
• Fig.10.8 shows the movement during
surfactant injection of an oil bank
which coalesces with more oil ganglia
resulting in further displacement of
residual oil towards the producers.
• The high IFV in crude oil-brine systems
containing a mixture of natural
surfactants in the oil phase can be
attributed to the presence of polar
asphaltenes & resins.
• Further increase in conc. of sulfonates
reduces IFV, because more natural
surfactants are displaced from the
interface.
Wettability: # The wettability of rock surfaces can be changed by adding a
simple salt, acid or base to the flood water. NAOH can effectively change rock
surfaces from oil-wet to water-wet.
# Fig.10.10 illustrates the role of the wettability of the solid surface on oil
ganglia. The oil-wettable surfaces lead to poor oil displacement whereas the
water-wettable surfaces lead to efficient oil displacement.
# The proper choice of surfactant can selectively alter the rock wettability.
# The oil recovery at water breakthrough in water-wet systems is much
higher than in oil-wet systems.
# The mobilization of trapped oil is
most difficult for rocks having
intermediate wettability.
# Under given reservoir conditions a
lower apparent viscosity is
required for mobility control in
water-wet systems.
# The use of additives to alter the rock
wettability is a promising approach
for enhanced oil recovery
ULTRA-LOW IFT IN RELATION TO OIL DISPLACEMENT SURFACTANT FLOODING:
Effect of salt concentration on IFT :
 The IFT is strongly dependent on the solid of the aqueous phase and at a
critical salt conc. the IFT approaches its minimum value.
 By changing the salinity of the aq phase, the relative solubilities of the
surfactant in the oil and water can be varied significantly.
 By replacing paraffinic crude with naphthenic crude, the region of minimum
IFT would move down and to the right as indicated by the arrow in fig.10.11.
 A specific surfactant conc. and salinity is required for the formation of ULIFT.
As the salt conc. is varied in the aq phase, the partition coefficient of the
surfactant between oil and water is altered, which seems to be responsible
for achieving ULIFT.
 In order to delineate the effect of salt on IFT and partition coefficient a
molecular mechanism (Fig.10.12) has been proposed.
 The surfactant conc. in the oil phase increases with increasing salt conc. in aq
phase. At low salt conc., most of the surfactant stays in aq phase. At high salt
conc. the surfactant dissolves into oil phase. At intermediate conc. the
surfactant conc. (highest) is the same in both oil & water (optimal salinity).
 The partition coefficient at optimal salinity was also found to be unity.
Effect of oil chain length on IFT:
• The nature of the oil plays an important role in producing ultra-low IFT.
• The conc.s of both salt & surfactant required to produce a minimum in IFT vary
significantly with the properties and chain length of oil.
• It was shown that crude oils with high aromatic H2 content produced lower IFT compared
to crude oils with lower aromatic H2 content.
• Fig.10.13 shows IFT for a petroleum sulfonate (TRS 10-80) in 1.5% NaCl as function of oil
chain length. The partition coefficient of surfactant corresponding to minimum in IFT is
found to be unity (fig.10.13).
• Fig.10.14 illustrates the proposed molecular mechanism for the effect of oil chain length
on IFT. The partitioning of the surfactant in the oil phase decreases with increasing oil
chain length.
• The conc. of surfactant in the brine phase must increase as the oil chain length is changed
from C6 to C16 . It was confirmed from ST & IFT measurements that the conc.s of surfactant
in aq phase equilibrated with C6 to C8 oils below the CMC, whereas the surfactant conc. in
the aq phase would be smaller as the chain length of the dissolved oil is increased.
• The molecular mechanism proposed in Fig.10.14 explains clearly the effect of oil chain
length reported by previous investigators.

•
Fig.10.14 illustrates the proposed molecular mechanism for the effect of
oil chain length on IFT. The partitioning of the surfactant in the oil phase
decreases with increasing oil chain length.
.
Effect of surfactant concentration on IFT:
• The IFT decreases with increasing surfactant conc., and at a critical conc. IFT
approaches its minimum value. Beyond this, the IFT increases with an increase
in surfactant conc.
• The aq phase is predominantly responsible for the ultra-low IFT.
• From surfactant partition measurements, it was shown the no. of surfactant
monomers in oil and brine phase increases with increasing conc. of surfactant.
• The molecular mechanism for the effect of surfactant conc. on IFT minimum
was proposed for the TRS 10-80-n-octane brine system (fig.10.15).
• The molecular mechanisms for the effects of salt conc. (fig.10.12), oil chain
length (fig.10.14), and surfactant conc. (fig.10.15) explain all results of U-L IFT.
• This unified understanding of the molecular mechanisms for producing ultra –
low IFT could be utilized in designing surfactant formulations for EOR under
particular reservoir conditions.
Effect of interfacial charge on IFT:
• The IFC influences IFT. For several systems, a minimum in IFT and a maximum
in electrophoretic mobility (EM), which is an indirect measure of IFC density,
has a definite correlation with the IFT for oil-surfactant systems.
• Fig.10.16 shows the electrophoretic mobility and IFT as a function of
surfactant conc. For the TRS 10-80-n-octane-brine system.
• This system exhibits a minimum in IFT at 0.05% TRS 10-80 conc., whereas the
electrophoretic mobility exhibits a striking maximum.
• A particular conc. of NaOH, the IFT between crude oil and caustic solution
exhibits a minimum. In order to understand the mechanisms of U-L IFT in
crude oil-caustic systems, electrophoretic measurements were also carried
out for these systems.
• Fig.10.17 represents the IFT & EM of a crude oil at several conc.s of NaOH. It is
evident that the region of minimum IFT coincides with that of the max. EM.
• The natural surfactants containing carboxylic groups present in the oil react
with NaOH & determine the magnitude of the charge at oil-caustic interface.
• These results suggest that the higher IFC density is responsible for the
minimum in IFT in crude oil-caustic systems.
FACTORS INFLUENCING OIL RECOVERY:
 The oil displacement efficiency (DE) depends upon several variables like optimal
salinity, mobility control, microstructures of surfactant formulations and
interactions between surfactant and polymer.
Optimal salinity (OS):
• The relative solubilities of petroleum sulfonates in oil and water phases are
strongly dependent on the salinity of the aq phase.
• In a certain salinity range, the systems consisting of surfactant, cosurfactant, oil
and brine form three phases; lower, middle & upper phase microemulsion
• The salinity at which an equal volume of oil & water is solubilized in middle-phase
microemulsion is termed optimal salinity.
• If one considers only the IFT , the oil DE should be max. at the optimal salinity.
• The oil recovery efficiency is a max. at OS for 0.5 PV slug of 5% TRS+ (Fig.10.18).
• A correlation between oil DE & capillary no. is illustrated in fig.10.19. At OS (1.5%
NaCl), the max. amount of oil 72% was recovered.
• It was observed that at OS the DE of crude oil & pure alkaline mixture in sand
packs was a maximum. Fig.10.19 shows the surfactant conc. in the effluent is a
function of the no. of pore volumes of fluid injected. The surfactant breakthrough
was earliest when the injected surfactant slug contained brine of higher than OS.
Mobility control:
• For an efficient oil displacement by surfactant flooding, the mobility controlling
polymer should be less mobile than surfactant slug and oil bank.
• Loss of mobility control in the fluid sequence causes fingering, so DE reduces.
• In designing a surfactant formulation, it is an important consideration.
• Mobility control was achieved through a reduction in both the µ and K.
• The effectiveness of the polymer solutions as mobility control agents depends on
the polymer conc., shear degradation, adsorption, gel formation, pseudodilatant
flow, salt conc. and temperature.
Surfactant-polymer interaction (SPI):
• SPI can lead to a considerable reduction in efficiency of oil recovery process.
• The SPI not only occur in the surfactant-polymer mixing zone, but also
throughout the entire surfactant slug due to invasion of micellar slug by polymer
molecules, which move more rapidly than the carrier water.
• The surfactant-polymer mixing takes place due to both dispersion effects as well
as excluded volume effects during the flow of polymer molecules.
• The mixing and invasion of the surfactant slug by polymer molecules forms two
phases of different viscosities. The entrapment of the high viscosity phase can
effectively remove some components & reduces the efficiency of the process.
The effect of several variables on SPI and oil displacement efficiency.
Microstructures of surfactant formulations:
The surfactant formulations used for EOR can be in the form of several structures:
micellar solutions, microemulsions, liquid crystalline dispersions.
The formation of these microstructures depends upon the composition of surfactant
formulation. Oil DE may be influenced by these structures.
SURFACTANT-GAS (FOAM) FLOODING FOR OIL RECOVERY:

• Steam and gases (CO2& N2) can be injected into the reservoir for heavy oil and
light oil recovery respectively in EOR systems.
• The lighter gas phase tends to flow on top and ride over the liquid phases in
the reservoir because of density differences between gas and liquid phases.
• This preferential movement of gas through the upper part of the reservoir is
called gravity override (Fig10.27A). At reservoir conditions, the viscosity of the
injected gases is often 10-100 times lower than the oil viscosity.
• At these unfavorable viscosity (Mobility) ratios, gases have the great potential
to channel (finger) through the oil (Fig.10.27B).
 .

• If the reservoir consists of rocks with variable permeability, steam or gases

have the inherent tendency to flow preferentially through the more
permeable zones compared with low-permeability zones (Fig.10.27C).
• Because of channeling and gravity override, the heat distribution is not
uniform during steam flooding. During gas-steam flooding, early break
through of the gas phase at the production wells is common.
• To minimize these uneconomical problems in gas-steam flooding processes
for efficient oil recovery, the possible mechanisms is to have steam and/or
gas present as the phase of a foam.
Role of surfactants in gasflooding processes:
• Surfactants with foaming ability can be used to reduce the mobility of the gas
phase, the channeling & gravity override can be decreased. By injecting a water
soluble solvent followed by steam or gas, it has been observed that foam
increases trapped gas saturation in porous media, so oil saturation decreases.
• Foam has a high potential for reducing gas mobility ( 80-95% gas). Foam is a
relatively low-density material which can easily overcome gravitational effects.
Foam viscosity is greater than that of its components. Both of these factors are
favorable for efficient oil displacement.
• The surface activity of foam reduces oil-water IFT and facilitates wetting of oil-
wet surfaces. Foam generation capacity is high at low oil saturation ( high water
saturation) of the reservoir.
Surfactant-steam flooding for heavy oil recovery:
• It was observed that some surfactants lose their ability to function after several
days at 1000C, whereas others are still fully effective for a period of 1 week.
• The ability of surfactants to generate foam increases with increasing temp.
• At a minimum steamflood temp (1770C), the half-lives for the most stable
surfactants evaluated were about 11 days. The effect of surfactant conc. & salt
on the stability of TRS 10-80 has been investigated at various temps.
Surfactant-CO2 flooding for light oil recovery:
 At elevated pr CO2 flooding can recover additional oil. In addition, super-critical CO 2
develops multicontact miscibility with various crude oils, resulting in a very efficient
oil displacement in porous media.
 CO2 is costly compared with water. Several methods have been tried, to minimize
the amount of CO2 required for optimum oil recovery.
 First, a CO2 slug was injected rather than continuous injection of CO 2 . This slug was
followed by water. In the second method, CO 2 slugs were injected while the
producing wells were shut in to avoid severe fingering & pr sinks. In the third
method, alternate slugs of CO2 & water were injected.
 The main objective was to reduce CO 2 channeling by reducing its mobility.
 The primary requirement for CO2 mobility control is a surfactant with proper
chemical stability, adsorption characteristics, and foaming or emulsifying capability.
An anionic surfactant was recommended for the improvement of the CO 2 process.
 For water flooded reservoirs, it is highly desirable to maintain the greatest mobility
reductions in oil-free reservoir zones. It appears, this process has a high potential to
achieve selective mobility reduction of CO 2.
 A comparison of the results of steam flooding alone and steam-surfactant
(foam) flooding shows that the latter has the potential to recover 25% more
bitumen from oil sand than steamflooding alone.
o Steam foams are more effective
than air foams in displacing oils.
o Fig.10.28 shows the effect of oil
viscosity on residual oil saturation
after air & steam foam flooding
o Compared to steam foam
flooding, the effectiveness of air
foams in recovering additional oil
decreases with increasing oil
viscosity.
o The higher oil recovery by steam
foam flooding is presumably due
to reduction in the oil viscosity
and higher foaminess of the
surfactants during steam injection
compared with air injection.
INTERFACIAL PHENOMENA IN SURFACTANT-GAS (FOAM) FLOODING:
• Fig.10.29 shows the interrelationship of molecular properties of surfactants with
EOR efficiency of steam or gas-driven processes. The molecular properties of
foaming agents can influence the microscopic characteristics of foam which in turn
can influence its flow behavior in porous media and recovery efficiency.
Surface properties of surfactant solutions: Surface tension (ST):
 Low ST foaming solutions tend to produce stable foams at lower concentrations.
ST determines the surface activity which in turn can influence the properties of
foams. In order to correlate the ST with flow behavior of foam through porous
media, STs of various surfactants have been measured.
 A decrease in ST was observed with increasing temp. A similar trend in the
variation of ST with temp was observed in the presence of NaCl.
 The effect of surfactant conc. on the ST of commercial solutions was determined.
Surface viscosity (SV):
 The SV can influence the stability of foams. A high SV reduces the rate of thinning
of liquid films resulting in high foam stability.
 For mixed surfactant systems, a max. in SV was observed when both components of
the mixed surfactants had the same chain length.
 It was observed that the SV increases with increasing surfactant conc. & these
results were also correlated with other surface properties of surfactant solutions,
microscopic characteristics of foams & flow behavior of foam in porous media.
Foaminess of surfactants:
 Among other properties of surfactant formulations for foam flooding processes, the
foaminess of a surfactant solution is more important than foam stability.
 The presence of an in-situ foam bank between the displacing gas phase and
displaced liquid improved both breakthrough time and ultimate recovery.
 The foam producing capacity of the surfactant solution increases with increasing
surfactant conc. and temp. The foaminess of the surfactant solutions as a function
of temp can be correlated by the following equation.
 F = F20 eA(T-20) ………….10.3 where A is a constant (1.6 X 10 -3 ), F is the foaminess of
surfactant solution at temp T ( 0C ) and F20 is the foaminess at 200C.
Foam stability:
 Surfactants play an important role in the foam stability & formation of foams.
Foam stability was determined by measuring half-life of foams. Half-life is the
time required to reduce foam volume to half of its initial value. It is observed that
the ethoxylated sulfonates are the most effective surfactants.
 Foam stability (e.g., half-life) decreased with increasing temp. Among all surface
properties of the surfactant solutions measured, the effect of temp on foam
stability was most pronounced.
Microscopic characteristics of foams: Average bubble size:
 The bubble size can influence the efficiency of the foamflooding process.
 Fig.10.30 shows photo micrographs of various foams containing sodium dodecyl
sulfate and dodecanol.
 Mixed surfactants of equal chain length (C12H25SO4 Na + C12H25OH) produced
smaller foam bubbles as compared to mixed surfactants of dissimilar chain length
(C12H25SO4 Na + CnH2n+1OH, where n = 8,10,14 &16).
 The molecular packing at the interface is strongly influenced by the chain length
compatibility of the mixed surfactants due to the occurrence of thermal
disturbances (e.g., oscillational, rotational, vibrational motions).
 The smaller bubbles displaced more fluid as compared to the large size foams.
Effect of temperature on bubble size:
.
 The temp of most petroleum reservoirs is higher than the surface temp.
 Fig.10.31 illustrates the photomicrographs of foams containing sodium dodecyl
sulphate & dodecanol at various temps. The surfactants can produce initially
smaller size bubbles at higher temps compared with lower temps. At a particular
temp, the bubble size increases slightly in the presence of brine.
 The variation in bubble size as a function of time at various temps is shown in
fig.10.32. The bubble size increases with elapsed time due to coalescence. It
increases rapidly with time at higher temps.
 It is evident that the surfactant solutions produced smaller bubbles
Effect of pressure on bubble size:
 It is known that with increasing pr the conc. of surfactants at an interface
increases and ST decreases. The bubble size of flowing foam in a capillary tube
decreases with increasing pr. The smaller size foams are more effective in
displacing fluid and in reducing gas mobility in porous media.
Flow through porous media behavior of foams: Fluid displacement efficiency:
 The presence of foam in a porous medium considerably increases the fluid
recovery both in sand packs & Berea cores. The volume of fluid collected at gas
breakthrough at a producing site is termed as fluid displacement efficiency. The
fluid displacement efficiency increased with temp (20-400C).
Breakthrough time (BT): The BT is defined as the time required by gas to travel from
injection site to production site. As the saturation increases, the fluid saturation
decreases. The BT decreased sharply up to a pr drop of 4 psi. Beyond this pr a
gradual decrease in BT was observed in sand packs. The BT increased with
increasing temp. The decrease in BT was observed with increasing permeability
(50-200mD) of the sandstones (Fig.10.33)
Gas mobility: Fig 10.34 illustrates the effect of the K of porous media on relative air
mobility at different pr drops. As the temp and pr drop increases, the effective air
mobility in porous media decreases (Fig.10.35). A sharp decrease in effective air
mobility was observed up to 400C, and beyond this temp a gradual decreases in
effective air mobility was observed.
MECHANISM OF SURFACTANT LOSS IN POROUS MEDIA:
 Success or failure of various oil recovery process which use surfactant injection
depends on the degree of retention of surfactants during the course of flooding.
The following is a brief description several mechanisms responsible for loss of
surfactants in porous media.
Surfactant adsorption:
• In the surfactant flooding process, as the surfactant slug comes into contact with
the reservoir rock and brine, there would be a loss of surfactant due to
adsorption at solid-liquid interface. Only part of the total surfactant injected in
the reservoir, is available for oil displacement.
Surfactant precipitation:
• During surfactant flooding, the surfactant slug may contact both the connate
water & injected water. The presence of divalent cations in connate water may
result in precipitation of the surfactant. Their presence may also alter the oil-
surfactant solution IFT due to the difference in ionic content between the
injected water and connate water.
Surfactant degradation:
• Thermal stability of surfactants at reservoir temps is required for efficient oil
displacement. Thermal degradation of a sulfonate in aq media can be explained
by equilibrium hydrolytic reactions. The surfactants were found to be effective
even after heating at 2000C for 24 hrs.
Surfactant- polymer mixing:
• The loss of surfactants is the major which determines the optimum volume of
the expensive micellar fluid required to displace residual oil. Several micellar
fluids are not compatible with the polymer from the mobility buffer bank. This
surfactant loss reduces oil DE & increases chemical requirements.
Surfactant partitioning in residual oil phase:
• The mechanisms of producing ultra-low IFT between brine & oil phase is the
equal partitioning of surfactant with the brine & oil phase. If the IFT is
sufficiently high, oil phase trapping occurs in porous media, which also causes
surfactant loss due to its partitioning in oil.
PRESENT STATUS OF THE USE OF SURFACTANTS IN OIL RECOVERY:
• These EOR flooding processes have developed slowly so far because of
associated high risks, high costs, complicated technology. In US, active projects
involving surfactant injection had been started from 1977 onwards and
increased to many fold.
• At present, all of these processes are complicated and are not well understood.
• The state of the art in the use of surfactants in light & heavy oil recovery is at
the research stage so far. New developments & improvements are required for
theses processes to become economically feasible.