ENHANCED OIL RECOVERY

TECHNIQUES

Dr. Ajay Mandal

Professor
Dept. of Petroleum Engineering
Indian Institute of Technology (Indian School of Mines), Dhanbad, India
OBJECTIVES OF CHEMICAL FLOODING

 Increase the Capillary Number Nc to

mobilize residual oil
 Decrease the Mobility Ratio M for better
sweep
 Emulsification of oil to facilitate
production

2
CLASSIFICATION

4
Chemical Floods -
CURRENT STATUS WORLDWIDE
Venezuela USA
Indonesia
India

France

China

Total Number of Projects: 27

OGJ April 12, 2004

5
Chemical Floods -
PRODUCTION WORLDWIDE

France Indonesia

USA

China

Total oil production: 300,000 B/D

OGJ April 12, 2004

6
CHEMICAL EOR TARGET IN SELECTED
COUNTRIES
180 173
160 Assumed:
Primary Rec. 33.3 %OOIP
140
Chem. Flood Rec. 33.3 %OIP
120
Billion Bbls

100
100
84
77
80
63 61
60 51
40
40 26 24
20 12 10 10 9
7 6 4 4 3 3 0.9
0.6 0.3 0.2
0

Germany
Norway
Venezuela

Oman
Iran

Qatar
Mexico

India
Iraq

Russia

UK
USA

Brazil
Kuwait

Denmark
S. Arabia

Libya

Romania

France
China
Abu Dhabi

Dubai
Nigeria

Canada

7
Chemical Flooding -
GENERAL LIMITATIONS

• Cost of chemicals
• Excessive chemical loss: adsorption, reactions with
clay and brines, dilution
• Gravity segregation
• Lack of control in large well spacing
• Geology is unforgiving!
• Great variation in the process mechanism, both
areal and cross-sectional

8
The major considerations, that must be dealt with, before
application of a chemical EOR technique, are:

• Gas injection or water-flood provides useful information

pertaining to reservoir characterization, which serves a useful impetus
for effective EOR planning.
• Chemical flooding study requires detailed laboratory studies,
pilot test facilities and strategic analysis from a functional viewpoint.
• Designing a chemical EOR project requires long preparation
time, simulation and prediction studies, technical planning and facility
installment.
• A greater degree of technical skill, competence and training is
required for engaging oil field managers, engineers and other workers.
• EOR project requires more time for approval from decision-
makers, which depends on proposed technical specifications,
increasing oil demand, ease of implementation, feasibility and cost-
profitability.

9
Enhanced Oil Recovery by Polymer Flooding

10
 Why Polymer Flooding?

• Reservoirs are porous media with heterogeneity in permeability and

porosity
• When water or other fluids are injected under pressure, they follow
the path of least resistance.
• High permeability zone and fractures offer the least resistance to
flow.
• Most of the oil remaining in lower permeable zones is by-passed.
• Residual oil saturation in high permeable zones decreases drastically.
• Relative permeability to water increases in high permeable zone.
• Resulting ever-increasing water-cut.
• Polymer can reduce the detrimental effect of permeability variations
and fractures and thereby improve both the vertical and areal sweep
efficiency. 11
 Polymer Flooding

(a)

(b)

Fig. 6. Structure of (a) polyacrylamide (left); (b) xanthan gum (right)

12
• Polysaccharide is a bio-polymer
• Higher degree of rigidity and immune to mechanical
degradation
• However it is highly susceptible to bacterial action

• Polyacrylamide is a long chain straight polymer

• Highly susceptible to mechanical degradation
• Relatively immune to bacterial action

13
 Mobility of injected fluid
M =
Mobility of displaced fluid

K W / W
M=
K O / O

14
Rheology of polymer solutions
The rheological behaviour of polymer solution is very important for its application in enhanced
oil recovery. Polymer solutions are generally classified as pseudoplastic fluids under most
conditions. A pseudoplastic material is one which exhibits a smaller resistance to flow as the
shear rate increases. Mathematically the formula is known as the Power Law model (Barnes et
al., 1999) [eq. 3.2]:

𝜏 = 𝐾𝛾 𝑛 (3.2)
n=1, K=μ, Newtonian fluids
n <1.0 Shear thinning, pseudoplastic fluids
n ˃1.0 Shear thickening, Dilatant
where  is the shear stress (Pa) and  is the shear rate (s-1), K is consistency index (Pa.sn) and n
is the flow behavior index (dimensionless). Note that if n=1 the equation reduces to the
Newtonian case with K equivalent to dynamic viscosity, μ. As shown in Fig. 3.4, the flow of
these non-Newtonian fluids may follow one of the following complex fluid models:
15
 Figure 3.4: Newtonian and non-Newtonian flow.
The Eq. (3.2) may be converted to the logarithmic form as:
𝑙𝑜𝑔𝜏 = 𝑙𝑜𝑔𝐾 + 𝑛𝑙𝑜𝑔𝛾 (3.3)
Thus, a plot of log shear stress against log shear rate will produce a straight line, the slope of
which will equal the flow-behavior index and the intercept on the shear stress axis will be equal
to the logarithm of the consistency coefficient.
16
Apparent Viscosity:
The equation 3.2 can be rewritten as,
𝜏 = (𝐾𝛾 𝑛−1 )𝛾
or, 𝜏 = 𝜇𝑎𝑝𝑝 𝛾 (3.4)
where, 𝜇𝑎𝑝𝑝 = 𝐾𝛾 𝑛−1 is apparent viscosity which is the ratio of shear stress to shear rate.
Inspection of the formula above shows that the apparent viscosity for a pseudoplastic fluid
decreases as the shear rate increases, though it is true for a certain shear rate range.

To predict the viscosity-enhancing power of a polymer solution, the empirical

Mark−Houwink−Sakurada (MHS) equation is used,

η = 𝐾 ′ 𝑀𝑝𝛼 (3.5)
where [η] is the polymer’s intrinsic viscosity, the parameters K′ and
and α are dependent on the polymer-solvent system and temperature, MP is the polymer
molecular weight. For solvents, a value of α=0.5 is indicative of a theta solvent. A value of
α=0.8 is typical for good solvents. For most flexible polymers, α≥0.5.
17
The empirical Flory equation can be used to estimate the mean end-to-end distance of a polymer
in solution. The Flory equation is
.......

where dp is in Angstroms (10−10 m), and [η] is in dl/g.

18
Question

Determine the consistency index (k) and power law index (n) for Power
Law Model, from the rheology data of a polymer solution as given
below:

Shear Rate (1/s) Shear Stress (mPa)

1.05 63.8379
1.87 71.54059
3.35 145.3398
5.99 224.002
10.7 306.7155
17.1 427.5513
30.5 638.792
54.6 921.375
110 1453.32
Solution

Shear Rate (1/s) Shear Stress (mPa) Log [Shear Rate] Log [Shear Stress ]
1.05 63.8379 0.021189 1.805079
1.87 71.54059 0.271842 1.854553
3.35 145.3398 0.525045 2.162384
5.99 224.002 0.777427 2.350252
10.7 306.7155 1.029384 2.486736
17.1 427.5513 1.232996 2.630988
30.5 638.792 1.4843 2.805359
54.6 921.375 1.737193 2.964436
110 1453.32 2.041393 3.162361
Solution

3.5
𝜎 = 𝑘𝛾 𝑛
3
𝐿𝑜𝑔 𝜎 = 𝐿𝑜𝑔(𝑘) + 𝑛𝐿𝑜𝑔(𝛾)
Log [Shear Rate]

2.5 Y = nx + c
y = 0.6952x + 1.7646
2 R² = 0.992 From curve,
1.5 𝑛 = 0.6952
1 c = 𝐿𝑜𝑔 𝑘 = 1.7646
0.5
𝐾 = 101.7646
= 58.157
0
0 0.5 1 1.5 2 2.5 Calculate the apparent Viscosity at
Log [Shear Stress ] at 2.5 s-1 shear rate.
 Fig. 3.6: Apparent viscosity vs. shear
rate (flow velocity)

In a good solvent the polymer molecules extend fully to maximize its contact with the
solvent. For application in chemical EOR, the polymer must be water soluble. In water,
the polymers with polar functional groups are extended to form H-bonding which gives
a flexible and gel-like appearance of the solution. With the polymer molecules
extended, the polymer-polymer entanglements are maximized, which leads to increase
in apparent viscosity of the polymer solution.
22
23
 10 1000 ppm
1500 ppm
2000 ppm
2500 ppm
5000 ppm
Viscosity, Pa.s

0.1

0.1 1 10 100 1000

-1
Shear Rate,s
Fig. 7: Viscosity of different PHPAM solution at 28.50c

24
 0.2

0
28.5 c
0
40 c
0
0.1 50 c
Viscosity, Pa.s

0.02
30 100 1000
-1
Shear Rate, s

Fig 4: Viscosity of 2500 ppm PHPAM solution at different temperature

25
 1000
PickedY
APPARENT VISCOSITY 5 pts SG
IN DISTILLED H2O

100

10

1
0 10 20 30
% HYDROLYSIS
Figure 3.8: Typical Apparent viscosity in distilled water vs. hydrolysis 26
General: In polymer solutions, a macromolecular network structure is formed by the
associating effect of hydrophobic tail chains of polymer molecules.
Effect of concentration: With increasing polymer concentration, the degree of entanglement
of polymer chains increase significantly, resulting in increased inter-molecular
interaction/associations and formation of denser macromolecular network structure within
bulk liquid/aqueous phase. This causes increase in viscosity of polymer solutions with
increasing concentration.
Effect of temperature: PHPA viscosity decreases with increasing solution temperature due to
decrease in (cohesive) inter-molecular association effect among polymer chain molecules.
This is responsible for disentanglement of polymer chain molecules upto a certain extent,
and loosening of the PHPA network structure in aqueous phase.

27
 n
0 0.05% NaCl sol
T= 28.5 C n
0.2% NaCl sol
1 PHPAM concn.= 1000 ppm n
0.5% NaCl sol
n
1% NaCl sol
n
1.5% NaCl sol
n
5% NaCl sol
Viscosity , Pa.s

0.1 n
8% NaCl sol

0.01
Fig 11: Effect of NaCl in rheology of 1000 ppm PHPAM
solution at 300c temp

1E-3

0.1 1 10 100 1000

-1
Shear Rate, s

The partially hydrolyzed polyacrylamide chain is stretched in deionized water because of the
repulsive forces between the negative charges (carboxylate groups) on the chain. This means
that the hydraulic radius of the polymer chain is large in deionized water and consequently
polymer solution viscosity is high. As the concentration of the sodium ion in solution is
increased, the repulsive forces within the polymer chain decrease, due to charge screening
effects, and the chain coils up. This change in the polymer conformation causes the hydraulic
radius of the chain to decrease and the degree of polymer chain entanglement to diminish. Both
factors cause the polymer solution viscosity to decrease. Also, the reduction in the polymer
chain size, due to the charge shielding, would increase the critical shear rate. 28
Viscoelasticity of polymer solution and EOR
❖ Viscoelasticity is defined as the ability of particular polymer solutions to behave as a
solid and liquid simultaneously in certain flow conditions.
❖ Complex viscosity basically represents the overall resistance to deformation of a
fluid, irrespective of whether that deformation is elastic (recoverable) or viscous
(non-recoverable).
❖ It is measured as a function of angular frequency under forced (oscillatory) shear
conditions.
❖ This represents the ability of injection fluid to flow and ultimately exceed capillary
pressure within a pore-throat.
❖ Initially, a chemical fluid enters a rock pore section with variable throat diameter but
is unable to exceed its capillary pressure (force).
❖ However, the fluid possesses an internal energy, which undergoes gradual oscillation
(under dynamic flow) under the injected force to ultimately exceed the capillary
29
pressure and displace crude oil from rock pores.
❖ The EOR mechanism of viscoelastic polymer flooding is twofold. On the one hand,
additional viscosity further prohibits viscous fingering so that volumetric sweeping is
expanded macroscopically.
❖ At the same time, the oil displacement efficiency is enhanced due to the deformation of
long-chained molecular structure microscopically so that the residual oil can be hauled out
in dead ends or pore throats and on the rock surface.
❖ During polymer flooding, the polymeric chain entanglements formed within the injection
fluid gradually improve their elastic and viscous characteristics during displacement
process; and are gradually able to block/plug high permeability pores (where capillary
effect is low); and forcibly mobilize trapped oil in low-permeability zones (wherein high
capillary forces exist). This is the effect of complex viscosity/rheology of fluid on
enhanced oil recovery in porous media.
❖ When polymer solutions flow through porous media, polymer molecules are distorted by
the flow through tortuous and converging or diverging pore channels. The curly molecules
need enough time to relax and change their configurations, so the polymer solution will
show an elastic response in addition to the viscous one. 30
 Figure 3.10: Complex viscosity η*, storage
modulus Gʹ, and loss modulus Gʺ for a linear
polymer at 70 ᵒC

Fig. 3.10 depicts the complex viscosity, η*, storage modulus, Gʹ, and loss modulus Gʺ, for a
linear polymer. There is a decrease in the complex viscosity at high frequency which is a
typical shear thinning behaviour. The shear thinning behaviour indicates the pseudoplastic
behaviour of the polymer. The storage modulus, Gʹ is a measure of the elasticity of materials, at
low frequencies. However, at high frequency, there is a slight elastic behaviour. On the other
hand, the loss modulus, Gʺ reveals the viscous nature of the material which dominates and
varies linearly with frequency. The Gʺ indicates the energy lost to the viscous deformation in
the course of the deformation of materials; it reveals the viscosity of materials. The higher the
Gʺ value, the higher the viscosity of the polymer. 31
32
 Polymer Adsorption

Effect of Polymer Adsorption on Permeability

Reduction

Because of polymer adsorption, relative permeability to water decreases and relative33

permeability to oil decreases
Polymer Retention:
Polymer retention has a major influence on the rate of propagation of polymer solution
through porous media during polymer flooding, and hence affects the oil recovery. It has two
opposite effects on additional oil recovery. The retention of polymer by adsorption on
reservoir rock improves the relative permeabilities as discussed in last section. On the other
hand, it has a significant effect in porous media on the transport and performance of polymer
solution. High polymer retention can dramatically delay oil movement and recovery during
polymer flooding.
Mechanical Entrapment:
Polymer molecules are large relative to the size of the narrow pores. Entrapment of polymers
occurs in porous media as the polymer molecules are large relative to the size of the pores.
Hydrodynamic Retention
Another type of polymer retention is hydrodynamic retention. Some polymer molecules enter
in areas (e.g., corners or dead ends) where they are shielded from the driving forces due to
laying outside the flow streamlines.

Inaccessible Pore Volume:

When the polymer molecular size is larger than some pores in a porous medium, the polymer
molecules cannot flow through those pores. The volume of those pores that cannot be
34
accessed by polymer molecules is called inaccessible pore volume (IPV).
 Hydrodynamically
trapped polymer
in stagnant zones
Adsorbed
Polymer

Mechanically
entrapped
polymers in
narrow pore
throats

Figure 3.16: Schematic diagram of polymer retention mechanisms in a porous

medium.

35
 Mobility reduction imparted by polymer-solution flow is the
resistance factor, Rf, which is defined as
RF =
where, is the mobility of water, is the mobility of polymer solution.

5
2500 ppm
RF
𝑘𝑏
2000 ppm 𝐹𝑅𝑅 =
1500 ppm 𝑘𝑎
4 1000 ppm
500 ppm
Where 𝐹𝑅𝑅 is residual
3
resistance factor; kb is brine
permeability measured before
RF and RRF

RRF polymer flooding, and ka is

2 brine permeability measured
after polymer flooding
The residual resistance factor is
1
Polymer injection Water injection the ratio of the permeability to
brine to that after the injection
0
of a polymer solution, which is
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 a measurement of the
Pore Volume Injected
permeability reduction caused
by polymer solution. 36
Fig. 5 Plot of RF and RRF with different concentration of polymer solution.
.
The thickness of adsorbed layer of polymer (p) can be calculated from the permeability
reduction data. The calculation is based on the assumption of Poiseuille’s fluid flow through a
capillary having its cross-section reduced by a uniform layer (Masuda et al., 1992). The
thickness of adsorbed layer of polymer is calculated as follows:
p = rp (1-RRF-1/4) (3.12)
where RRF is the residual resistance factor and rp is the average pore diameter, which can be
calculated as:
rp = (8kw/)1/2 (3.13)
where kw is the effective permeability to water and  porosity of the sand pack.

37
To establish whether or not a polymer solution has suitable injectivity, one can compare the
injectivity of the polymer solution to the injectivity of water (or brine) in the same reservoir.
If the volumetric injection rate and the differential pressure are known (for both the primary
brine injection and the polymer solution injection), the injectivity loss (Iloss) can be
calculated as per Equation (3.14) (Scott et al., 2020):

𝑖𝑝
𝐼𝑝 ൗ∆𝑃𝑝
𝐼𝑙𝑜𝑠𝑠 = 1 − 𝐼 = 1 − 𝑖𝑏 (3.14)
𝑏 ൗ∆𝑃
𝑏

Where, I represents the injectivity, i represents the volumetric injection rate, and
∆𝑃𝑝 represents the pressure drop for the polymer solution (p) and brine (b). Han et al.
(2012) suggested that a range of injectivity loss from 0.5 to 0.9 is acceptable but that
adjustments should be made if the injectivity loss is higher than 0.9.

38
 Chemical degradation
• The mechanism of chemical degradation is the formation of free
radicals that cut the chain
• These free radicals are formed by the reaction of an oxidizer with a
reducer (redox)

Oxydizer Reducer
O2 H2S
Fe2+, Fe3+ Scavenger
Hydrocarbon Fe2+
Peroxydes Sulfato reducing
bacteria
NH3

• The high molecular weight chains are more sensitive to chemical

degradation, especially those above 15 million MW
• The best polyacrylamide stability is found in a reducing media
Example of chemical degradation
Mechanical degradation

• High shear will cut the polymer chains in pieces

• High MW giving a certain viscosity with few chains will be more

sensitive to shear than a low MW providing the same viscosity with
more chains

• This shear degradation is amplified by the formation of free radicals

as a mechanism of degradation
 Example of mechanical degradation

• Low MW polymers are less sensitive to shearing

Example of mechanical degradation
Influence of time on shear

• The shear at the injection side is normally very limited in time

(seconds to minutes)

• It is also dependent, at the beginning of the injection, on the

structure of the reservoir

• During injection time, solids come from the injected water or are
precipitated
• (CaCO3, MgOH, FeS, S2 or biological molds)

• The solids increase the shearing time by forming channels, where the
polymer solution can be under high degradation conditions for a
length of time
 Final viscosity
• The mechanical degradation is generated directly at the injection
point
• The chemical degradation happens a few hours after injection
• Biodegradation occurs in presence of Bacteria and polymer solution
is then stable
Viscosity
cps Factors
Brine (TDS)
Temperature
Mechanical Oxydo reduction equilibrium
Oxydo reduction reactions
degradation Flow
Differential pressure, Shear
Permeability
Chemical Precipitation (salts, sulfur, SRB, Fe)
degradation Viscosity of injection
Viscosity at different steps of degradation
Bio degradation
Stable fluid

Time
New types of polymers
• Many types of polymers are known from the 70s in laboratory
developments. Some of them are now produced in pilot or industrial
quantities. The main ones are:
• Thermostable polymers which increase the stability of the polyacrylamides
from 75°C to 90°C with new monomers
• FLOPAAM AN 125-132
• Associative polymers with a main polyacrylamide chain and statistic
repartition of hydrophobic groups. There is an association of these
hydrophobic groups in a specific brine to give a high viscosity
• SUPERPUSHER
• Star polymers with 3 or more branches on a central polymer group. These
polymers are normally associative to have a high viscosity
• ST5030
• Comb and T shape polymers with a main hydrophobic chain and end
hydrophobic chain
• Block associative polymers with multiple hydrophobic groups inside an
hydrophylic chain
• Structured polymers with hydrophilic branches in a main hydrophilic chain
• Soft or Movable gels are totally insoluble yet injectable gels mainly used in
profile modification but with high potential in EOR
• FLOPERM 2000
Figure 3.12. Typical flow of flood front of (a) Water flooding process with viscous
fingering, and (b) Polymer flooding process.

47
Injection Well Production Well

Only Oil and

Water are Only Oil
flowing is flowing

Residual Oil

Oil Bank Oil Bank

Chase Buffer Polymer

Water Zone Slug
Water
Bank Connate
Water

Figure 3.13. Polymer flooding as a secondary recovery process.

48
Fig. 1: Schematic of experimental set-up for polymer flooding in sandpacks.

49
 110

100
% Oil Recovery and % Water cut

90

80

70

60
% oil recovery of 1500 ppm PHPAM
50 % water cut of 1500 ppm PHPAM
% oil recovery of 2000 ppm PHPAM
40
% water cut of 2000 ppm PHPAM
30 % oil recovery of 2500 ppm PHPAM
20 % water cut of 2500 ppm PHPAM
% water cut of 5000 ppm PHPAM
10 % oil recovery of 5000 ppm PHPAM
Water
0 Chase Water
P
-10
0 1 Pore volume
2 injected
3 4 5

Fig. 8: Production performance of Polymer flooding

50
Sandpack Porosity Permeability, k (Darcy) Design of Recovery Additiona % Saturation
sample (%) chemical slug of oil after l recovery
No. for flooding water (% OOIP)
kw (Sw=1) ko (Swi) flooding at Swi Soi Sor(w)

95% water
cut
(%OOIP)

P1 37.265 0.5 PV 1500ppm 52.6471 16.12 18.519 81.482 22.963

1.235 0.218 PHPAM+ Chase
water
P2 37.265 0.5 PV 2000ppm 52.522 20.578 17.284 82.716 21.827
1.236 0.217 PHPAM + Chase
water

P3 37.725 0.5 PV 2500ppm 52.79 20.91 19.512 80.488 20.976

1.234 0.216 PHPAM + Chase
water
P4 37.265 0.5 PV 5000ppm 52.9 20.9 18.845 82.155 20.525
1.235 0.213 PHPAM + Chase
water

51
Figure 3.19: Oil recovery factor (%) and differential pressure as a function of PV
injected during oil recovery (Alfazazi et al., 2019).

52
DATA: Pore volume PV = 81 ml,
The core is first saturated with brine and then flooded with crude oil.
oil left in core after oil flooding VP = 68 ml,
Oil produce after brine flooding V1 = 35.2 ml,
Oil produce after polymer flooding V2 = 15 ml
Oil produce after brine flooding in end V3 = 2.5 ml
Calculate the initial oil saturation in %. Calculate the oil recovery in % of OOIP.
Calculate the additional oil recovery after polymer flooding % of OOIP.
Calculate the additional oil recovery after chase water flooding % of OOIP.

53
54
 Table 3.2: General screening guide for polymer flooding (Saleh et al.,
2014)

Author Publishe Gravity Oil Oil Average Temperatur Depth, ft SPE Paper
d Year OAPI Viscosity, cp Saturation Permeability, e, OF No.
,% md

Brashear and 1978 15 <200 50 >20 <200 NC 6350

Kuuskraa

Carcoana 1982 - 50 - 80 >50 >50 <180 <6,562 10699

Goodlett et 1986 >25 <100 >10 >20 <200 <9,000 15172

al.

Taber et al. 1997 >15 10 - 100 >50 >10 <200 <9,000 35385

Al-Bahar et 2004 - <150 >60 >50 <158 - 88716

al.

Dickson et al. 2010 >15 10-1000 >30 >100 if <170 800 - 129768
(10<μ<100) 9,000 55
56
 Surfactant-Polymer Flooding

Fig.9: Surfactant molecule and surfactant orientation in water

57
Gemini surfactant Gemini surfactant
Category Charge on Functional groups Examples
hydrophilic head
Nonionic No charge ethoxylated Tween 20, Span 40, Brij 35
alcohol/alkylphenol
and polysorbate
Anionic Negative sulfate, sulfonate, Sodium dodecyl sulfate,
phosphate, carboxylate, Sodium stearate, Sodium
sulfosuccinate, isethionate, dodecylbenzene sufonate
taurate, and sarcosinate
Cationic Positive quaternary ammonium, Benzyldodecyl
pyridinium and guanidium dimethylammonium
bromide, Cetylpyridinium
chloride, Cetrimonium
bromide
Zwitterionic Positive and carboxybetaine, Cocamidopropyl betaine,
negative sulfobetaine, Lauryl sultaine, Lauryl
59
hydroxysulfobetaine hydroxysultaine
Interfacial tension
Interfacial or surface tension exists when two phases are present. These phases
can be gas/oil, oil/water, or gas/water. Interfacial tension is the force that holds the
surface of a particular phase together and is normally measured in dynes/cm. The
surface tension between gas and crude oil ranges from near zero to
approximately 34 dynes/cm. It is a function of pressure, temperature, and the
composition of each phase.

60
61
Criteria for Surfactant Selection
Most of the chemical flooding processes use petroleum sulfonates or mixtures of them with
property-modifying additives. The choice of surfactant(s) which has been surveyed by
various authors (Iglauer et al., 2010; Jamaloei et al., 2011) is made based on several criteria
which may be classified into two groups: performance criteria versus economic ones.

62
(a) Performance criteria
A chemical flooding surfactant formulation must exhibit the following properties:
Ability of the surfactant to reduce the surface tension of its solution and IFT between
oil and surfactant solution system.
1. Hydrophilic-Lipophilic Balance of Surfactants: The hydrophilic-lipophilic balance
(HLB), often used to describe surfactants, is calculated from the weight
percentage of the hydrophilic groups to the hydrophobic groups in a molecule,
with values ranging from 1–20 (Kralova and Sjöblom, 2009). The HLB value of a
surfactant should match the HLB value of the oil phase based on the notion of
“like dissolves like”. In the range of 3.5 to 6.0, surfactants are more suitable for
use in W/O emulsions. Surfactants with HLB values in the 8 to 18 range are most
commonly used in O/W emulsions (Griffin, 1949).
2. The CMC, thermodynamic and surface-active properties, and solubilization
parameters.
3. Good displacement efficiency, i.e., it must produce a low interfacial tension
against crude oil.
4. Low adsorption on reservoir rocks and clays in order to reduce the surfactant
losses.
5. Good compatibility with reservoir fluids, especially tolerance to divalent cations
such as Ca2+ and Mg2+.
63
(b) Economical aspects
The current research, effort may soon lead to formulations having excellent
performances.
However, economic considerations might restrict their use. Economic criteria
include:
1. Availability of raw material may be a problem since enormous quantities of
surfactants, and additives which will be required for extensive application of
chemical flooding.
2. Efficient manufacturing and low cost of production of surfactants.
EOR demand may then unbalance the market because of a potential shortage of
raw material and this demand for EOR chemical has been estimated and will
require a careful production planning.

64
Effectiveness of surfactants (ΠCMC)
The difference between the surface tension values of the prepared surfactant solutions at their
CMC and that of pure water is known as their effectiveness (ΠCMC). The surface pressure or
the effectiveness of surface tension reduction of surfactant is calculated by Eq. (3.18). ΠCMC
defines the minimum surface tension value, hence signifies the capability of surfactant in
lowering the surface tension of the solution.
𝛱𝐶𝑀𝐶 = 𝛾𝑜 − 𝛾𝐂𝐌𝐂 (3.18)
where, γo and γCMC are the surface tension values for a pure solvent and solutions at CMC
respectively, at the air-liquid interface. A large value of ΠCMC or lesser value of γCMC denotes
a better ability of surfactant to reduce the surface tension of solutions. ΠCMC defines the
ability of surfactant in reducing the surface tension of the solution. With rise in temperature
there is an increase in ΠCMC value (Table 3.4). This signifies the enhanced capability of
surfactant in surface tension reduction with increase in temperature.

65
Adsorption efficiency (pC20)
The negative log of the surfactant concentration that reduces the surface tension of the
pure solvent by 20 mN/m gives the adsorption efficiency. The adsorption efficiency is
given by Eq. (3.19):
𝑝𝐶20 = − log 𝐶20 (3.19)
where C is surfactant molar concentration, C20 is amount of surfactant required for
surface tension reduction of pure solvent by 20 mN/m, that means, C20 is the minimum
surfactant concentration that denotes the saturation of the surface adsorption.

Occurrence of adsorption or micellization (CMC/C20)

To investigate the effect of structural factors on the adsorption and micellization process,
the CMC/C20 ratio is determined. The CMC/C20 value defines the occurrence of either
adsorption or micellization process. A high value of CMC/C20 ratio denotes the spontaneity
of adsorption process than micellization and vice-versa. The CMC/C20 ratio increase with
rise in temperature, indicating the adsorption process is favored with drop in the surface
tension values (Table 3.4). Thus, examination of CMC/C20 ratio imparts useful knowledge
about adsorption and micellization phenomenon.
66
Krafft and Cloud points
Krafft point indicates the temperature at which micelles are first formed in aqueous solution.

Table 3.6: Relation between HLB value and the expected

properties/applications of surfactants (Sheng, 2010)

HLB Value Property / Application

0-3 Antifoaming Agent

4-6 W/O (water in oil)

Emulsifier

7-9 Wetting Agent

8-18 O/W Emulsifier

13-15 Detergent

10-18 Hydrotrope or Solubilizer

67
Mechanisms of Oil Recovery by Surfactant Flooding

68
Schematic diagram explaining mechanism of oil recovery by IFT reduction

69
 Tween 20
Tween 40
Tween 60
1 Tween 80
[mN/m]
IFT

0.0703
0.0139 0.0293
0.0272
0.1
0.00 0.02 0.04 0.06 0.08 0.10 0.12
Concentration (mM/l)

Figure 10: IFT between surfactant solution and crude oil at different concentration of (a)
Tween 20, (b) Tween 40, (c) Tween 60 and (d) Tween 80 at 25 oC
70
 10
GS 14-3-14 GS 14-4-14 GS 14-5-14
GS 14-6-14 C14TAB C16TAB

Interfacial tension (mN/m) 1

0.1

0.01

1E-3
0 3 6 9 12 15 18 21 24 27 30
Time (Days)

Fig.. Variation of IFT over a period of days for different surfactant

solutions at corresponding CMC values at 343 K

71
Mechanism of IFT reduction by salt addition

Fig. 10. Mechanism of IFT reduction at the oil-aqueous interface in the presence of
gemini surfactant-salt systems
 60
303 K
55 323 K
343 K
50
Salt tolerance (wt.% NaCl)

45
40
35
30
25
20
15
10
5
0
3 4 5 6
Number of aliphatic carbon (C) atoms in GS spacer

Salt tolerance of 14-s-14 GSs at 303 K, 323 K and 343 K

73
74
 Wettability Alteration

Figure 11: Illustration of contact angle in three-phase system on solid surface

75
Tween 80 at t=0 sec, θ=92.7⁰ Tween 80 at t=300 sec, θ=62.3⁰

SDS at t=0 sec, θ=63.8⁰ SDS at t=300 sec, θ=40.9⁰

CTAB at t=0 sec, θ=75.4⁰ CTAB at t=300 sec, θ=40.4⁰

76
 Quartz D. water
Tween 80
SDS
Contact angle ' ' CTAB
80 all are at their CMC

60

40

0 100 200 300

Time [sec]

Fig. 12. Dynamic contact angle of different surfactants solution at their CMC
77
 Contact angle studies for wettability alteration of rock from
water-wet to oil-wet condition
• Contact angle studies were explained
with the help of DLVO theory,
postulating the preferential adsorption
of GS molecules to form a water-wet
film on rock surface.
• Rock wettability is effectively altered
from intermediate-wet to water-wet
due to the Gibbs-Marangoni effect.
• Salt addition and temperature increase
improved wetting properties.

Fig. 16. Schematic explaining GS induced-displacement of adsorbed oil molecules from quartz surface by
Gibbs-Marangoni effect using DLVO (water-film) theory of aggregation of aqueous dispersions on solid
surface.
79
 Quartz
Oil aged quartz
IL treated oil aged quartz

691
1081 770
Transmittance

3430
2009 1620 1466
2928 2853

4000 3500 3000 2500 2000 1500 1000 500

-1
Wavelength (cm )

Understanding of wettability alteration by FTIR study

80
81
Fig. 13: Surfactant-Polymer Flooding
82
 Production
Injection

Well
Preflush
Mobility
Taper
well
Chase

Buffer
Water

Slug
Oil

Figure 3.56: Schematic of the injection plan of surfactant flooding

83
Schematic diagram of in situ emulsion formation and phase inversion process in porous media (Yang and Pu,
2020)
Mechanism of Alkaline Flooding

The oil recovery by alkaline flooding takes place in a two-stage processes

(Castor, 1979). The first stage involves the formation of in-situ surfactants.
Alkali reacts with the acidic components of crude oil to form in-situ
surfactants. The surfactants thus generated may: (1) adsorb at the oil-water
interface to lower the interfacial tension, and in some cases cause
spontaneous emulsification and phase swelling; and (2) react with or adsorb
at the rock surface, changing the wettability characteristics of the rock and
hence the configuration of the residual ganglia of the crude oil (Castor,
1979).

85
• Johnson (1976) reviewed the mechanisms by which alkaline flooding may improve
recovery of acidic crudes from partially depleted reservoirs:
(1) emulsification and entrainment: According to this mechanism, the residual oil is
emulsified by alkaline action and entrained into the flowing alkaline solution and thus,
produced as a fine emulsion (Mungan, 1981)
(2) emulsification and entrapment: In this process, the emulsified oil is trapped again
downstream in the porous medium at pore throats that are too small for the emulsion
droplets to penetrate, forcing the injection water into pores that have not been previously
displaced.
(3) wettability reversal from water-wet to oil-wet: Cooke et al. (1974) suggested this
mechanism where the alteration of wettability from water-wet to oil-wet causes the
discontinuous non-wetting residual oil phase to spread out into a continuous wetting
phase.

86
(4) wettability reversal from oil-wet to water-wet: In this mechanism, this alkali reacts
with the reservoir rocks and displaces the adsorbed oil. Thus, the oil-wet rock is
converted to water-wet and the recovery is enhanced. The displaced oil is also emulsified
and flows with the injected water.
(5) lowering of interfacial tension: The in-situ surfactant generated by alkaline action
with the acidic crude oil get adsorbed at the oil water interface and reduce the IFT, which
in turn improves the displacement efficiency.
(6) solubilization of rigid, interfacial films: Resins and asphaltenes present in the crude
oil are responsible for the formation insoluble films at the crude oil-water interface.
These interfacial films may be redissolved in the oil and thus oil is mobilized, but this
rate is very slow.
• The extent to which each of these mechanisms may contribute to increasing recovery
depends on the specific properties of the crude oil, injection water, and the reservoir
(Mungan, 1981).

87
Reservoir characteristics
The reservoirs which are responsive for water flood is favourable for alkaline
flooding. The major requirements and considerations are:
(1) The reservoir should not be very heterogeneous;
(2) Highly faulted and/or fractured reservoirs are unsuitable;
(3) The pay zone must be of a sizeable areal extent and sufficiently thick;
(5) An aquifer-connected water-drive reservoir is not suitable for alkaline flooding;
(6) The reservoir permeability and porosity should be well developed; and
(7) The reservoir should not have a gas cap.

88
 110

100

90

% oil recovery & % water cut

80

70

60
oil recovery 1.0% NaOH + 1500 ppm PHPAM
50 Water cut 1.0% NaOH + 1500 ppm PHPAM
oil recovery 1.0% NaOH + 2000 ppm PHPAM
40
Water cut1.0% NaOH + 2000 ppm PHPAM
30 oil recovery 1.0% NaOH + 2500 ppm PHPAM
20 Water cut 1.0% NaOH + 2500 ppm PHPAM

10

0 Water ASP Chase Water

P
-10
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Pore Volume Injected

Sand pack Porosity Permeability, k Design of chemical slug Recovery of oil Additional % Saturation
sample No. (Darcy) for flooding after water recovery (%
kw (Sw=1) ko (Swi) flooding at 95% OOIP) Swi Soi Sor
water cut
(%OOIP)
0.3 PV (1.0% NaOH+
0.2% SDS+ 1500PPM
1 37.725 0.315 0.002 PHPAM)+ 0.2 PV 50.6 29.5 18.293 81.707 17.445
1500PPM Buffer + Chase
Water
0.3 PV (1.0% NaOH+
0.2% SDS+ 2000PPM
2 37.265 0.319 0.002 PHPAM)+ 0.2 PV 50.7 29.7 18.519 81.482 19.112
2000PPM Buffer+ Chase
Water
0.3 PV (1.0% NaOH+
0.2% SDS+ 2500PPM
3 37.265 0.322 0.002 PHPAM)+ 0.2 PV 50.1 29.9 17.284 82.716 18.512
2500PPM Buffer+ Chase
89
Water
90