Chapter

Enhanced Oil Recovery: Chemical

Flooding
Ahmed Ragab and Eman M. Mansour

Abstract

The enhanced oil recovery phase of oil reservoirs production usually comes after
the water/gas injection (secondary recovery) phase. The main objective of EOR
application is to mobilize the remaining oil through enhancing the oil displace-
ment and volumetric sweep efficiency. The oil displacement efficiency enhances by
reducing the oil viscosity and/or by reducing the interfacial tension, while the volu-
metric sweep efficiency improves by developing a favorable mobility ratio between
the displacing fluid and the remaining oil. It is important to identify remaining oil
and the production mechanisms that are necessary to improve oil recovery prior to
implementing an EOR phase. Chemical enhanced oil recovery is one of the major
EOR methods that reduces the residual oil saturation by lowering water-oil interfa-
cial tension (surfactant/alkaline) and increases the volumetric sweep efficiency by
reducing the water-oil mobility ratio (polymer). In this chapter, the basic mecha-
nisms of different chemical methods have been discussed including the interactions
of different chemicals with the reservoir rocks and fluids. In addition, an up-to-date
status of chemical flooding at the laboratory scale, pilot projects and field applica-
tions have been reported.

Keywords: enhanced oil recovery, EOR, chemical flooding, alkaline, surfactant,

polymer, interfacial tension, IFT

1. Introduction

The Average oil recovery after the primary recovery phase is about 5–20% of the
original oil in place (OOIP) and can be increased by applying the secondary recov-
ery phase up to 40%. Usually, the EOR application stage will be after the secondary
recovery when the main challenge is not the reservoir pressure only, but also the
reservoir fluids relative mobility compared to the injected fluids during the second-
ary recovery phase [1].
There are different EOR methods such as thermal recovery, miscible
Gas Injection, Chemical flooding and Microbial EOR as shown in Figure 1.
This chapter covers the fundamentals and the mechanisms of the recovery
enhancement of the chemical flooding EOR as one of the main EOR methods
[2]. The feasibility study and design for EOR projects require integrated work
between different disciplines such as reservoir engineers, petroleum geologists,
petrophysits, geomodellers, chemical engineers, and production engineers whom
are responsible to start with the screening phase of the different EOR methods and
come up with the shortlisted one in order to go for the next step which is lab testing
phase that requires PVT/core labs capable to implement the various EOR lab tests,

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then, analyze the lab scale results to be coupled with the reservoir simulation
model in order to estimate the incremental recovery for the different EOR methods
under study. For any EOR project, the initial stage is the screening criteria in
order to identify the best EOR application for the candidate reservoirs in terms of
incremental recovery that will be added and the economics of the project [3]. For
any EOR project, the initial stage is the screening criteria in order to identify the
best EOR application for the candidate reservoirs in terms of incremental recovery
that will be added and the economics of the project. The screening criteria is
based on both reservoir rock and fluids properties such as oil gravity, oil viscosity,
oil composition, remaining oil saturation (target), formation type, reservoir
thickness, depth, and temperature. In Table 1, a summary of screening criteria for
the chemical EOR methods based on lab and applied field data. So, in this chapter
we are assuming that the screening criteria was done and it has been found that
the chemical flooding is the optimum EOR method that can be applied for the
reservoir under study [4].

Figure 1.
Oil production mechanisms.

Table 1.
A summary of screening criteria for the chemical EOR methods.

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2. Chemical EOR flooding classification

The chemical flooding EOR can be categorized into the following:

1. Polymer flooding.

2. Surfactant flooding.

3. Surfactant-polymer flooding.

4. Alkaline flooding.

5. Alkaline-surfactant-polymer flooding.

The next sections of this chapter will discuss individually each method in order
to illustrate the fundamentals, the reservoir-fluids interactions processes, and the
field applications [5].

2.1 Polymer flooding

In concept, a water-soluble polymer is used to reduce the mobility ratio of

water-oil by increasing the water viscosity which improves the volumetric sweep
efficiency. The mechanism of polymer flooding is to increase the water viscosity
and also to reduce the permeability of the rock to water, in other words, to reduce
the water-oil mobility ratio close to unity or less [6]. Over the past years, polymer
floods projects have been applied over a wide range of conditions:

• Reservoir temperatures [46–235]°F.

• Average reservoir permeability [0.6–15,000] mD.

• Oil viscosity [0.01–1494] cP.

• Net pay thickness [4–432] ft.

• Remaining oil at start-up [36–97] % of OOIP.

Polymers have been used in oil production in three modes; as near-well

treatments to improve the performance of water injectors or watered out producers
by blocking off high conductivity zones, agents that may be cross-linked in situ to
plug high conductivity zones at depth in the reservoir and agents to lower water
mobility or water-oil mobility ratio. Polymer flooding is suited for reservoirs where
normal water floods fail due to one of the two reasons: High Heterogeneity and
High oil water mobility ratio which is targeting the oil in areas of the reservoir that
have not been contacted efficiently [7]. The main economic limitation is the cost
of polymers is. For example, if the cost of acrylamide/acrylate copolymers and
xanthan polymers were substantially lower and higher polymer concentrations
with larger polymer flood bank sizes could be granted in a given application. It
would improve oil-recovery efficiencies, wider ranges of potential applications,
and higher profits. Polymer flooding is showing promising results, specifically, if
flooding projects are started at high remaining oil saturations. Polymer flooding has
been conducted in sandstone and carbonate reservoirs, and oil-wet, water-wet, and
mixed-wettability reservoirs [8].

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2.1.1 Mechanism

The main effect of the polymer is the enhancement of the water-oil mobility
ratio to be unity or less, the mobility ratio is defined as the ratio of the mobility of
displacing phase to the mobility of displaced phase which is calculated from the
following equation [6].
​ ​  ​​
M ​ ​  ​​
K ​μ​  ​​ ​ ​  ​​
K ​μ​  ​​
​​M​ w−o​​​ ​=​ _
​​  w ​​ ​=​ ​​ _w ​  ∗ ​ _ o _ _o
​μ​ w ​​​​ ​=​ ​​   ​  ∗ ​  ​μ​ w ​ ​ ​​
rw
(1)
​Mo​  ​​ ​Ko​  ​​ ​Kr​  o​​

where
​​M​  w−o​​  : the water − oil mobility ratio ​
​​M​  w​​  : the water mobility​
​​M​  o​​  : the oil mobility​
​​K​  w​​ : the effective permeability to water​, mD
​​K​  o​​ : the effective mobility to oil, mD​
​​μ​  o​​  : the oil viscosity, cP​
​​μ​  w​​  : the water viscosity, cP​
​​K​  rw​​  : the relative permeability to water​
​​K​  ro​​  : the relative permeability to water​

As per this equation, it is clear that in order to drive the mobility ration to be
unity or less, the water viscosity is increased by adding the water-soluble polymers
to the injected water as shown in Figure 2, when the displacing fluid (water)
viscosity is lower than the oil, the recovery efficiency decreases as the remaining
oil after this flooding is about 45% of the OOIP at 0.1 viscosity ratio. On the
other hand, once the viscosity ration reached to 1 (polymer added to water) the
remaining oil after the flooding will be reduced to 20% of the OOIP. As summary,
the highest viscosity ratio is the highest oil recovery [9].

2.1.2 Polymer flooding advantages

The advantages of polymer flooding could be summarized as following [10]:

I. Applicable over a wide range of conditions.

II. A reduction in the quantity of water required to reduce the oil saturation to
its residual value in the swept portion of the reservoir.

III. An increase in the areal and vertical coverage in the reservoir due to a reduced
water flood mobility ratio.

IV. Diverting the injected from swept zones.

V. Promising for heavy oil application.

VI. Cost-effective.

Polymer flooding limitations are:

I. High oil viscosities require a higher polymer concentration.

II. Results are normally better if the polymer flood is started before the water-
oil ratio becomes excessively high.

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III. Clays increase polymer adsorption.

IV. Some heterogeneity are acceptable, but avoid extensive fractures.

V. Lower injectivity than with water can adversely affect oil production rates in
the early stages of the polymer flood.

VI. Xanthan gum polymers cost more, are subject to microbial degradation, and
have a greater potential for wellbore plugging.

2.1.3 Field projects statistical data of some polymer flooding

A summary statistical data for field projects of polymer flooding as shown in

Table 2.

2.2 Surfactant flooding

Correctly designed surfactants can create micro emulsions at the interface

between oil and water phases, which cause a reduction in the interfacial tension
(IFT) that consequently will mobilize the residual oil which improving the oil
recovery as shown in Figure 3. This method of EOR is a challenging one by many
factors such as rock adsorption of the surfactant and co-surfactant, and the
chromatographic separation of the surfactant during the injection in the reservoir.
The designed surfactants should be resistant and active at reservoir conditions
which could by at higher pressure, temperature and water salinities [11]. In the
surfactant flooding the phase behavior is the most important factor to make it
successful. Currently, there is no EOS model to describe the phase behavior in these
systems. Consequently, phase behavior studies should be observed experimentally
which is challenging to mimic the reservoir conditions. Surfactants solutions are
used to reduce the oil-water IFT, while the co-surfactants are mixed with these
solutions in order to enhance the properties of the surfactant solutions. The
co-surfactants added to the solutions are serving as an active agent or a promoter

Figure 2.
Effect of viscosity ratio on the fractional flow curve.

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Table 2.
A summary of statistical data for field projects.

Figure 3.
Principle of flooding, where residual oil is trapped in the reservoir, for the movement of oil through the narrow
capillary pores, very low oil/water interfacial tension (IFT) is required.

in the mixed solution in order to enhance the surfactant effectiveness with respect
to temperature and water salinity as it is well known that surfactant flooding is
sensitive to reservoir temperature and salinity [6].

2.2.1 Mechanism

A surfactant is added to an aqueous fluid and co-surfactant is also added

in order to prepare the surfactant solution and injected into the reservoirs as
surfactant flooding reduces the interfacial tension between the oil and water
phases and also alters the wettability of the reservoir rock in order to mobilize the
residual oil trapped in the reservoir which improves the oil recovery as shown in
Figure 3 [12].
The surfactant selection is a critical stage in designing the surfactant flooding
projects as the Anionic surfactants preferred due to the following reasons [13]:

• Low adsorption at neutral to high pH on both sandstones and carbonates.

• Can be tailored to a wide range of conditions.

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• Widely available at low cost in special cases.

• Sulfates for low temperature applications.

• Sulfonates for high temperature applications.

• Cationic scan be used as co-surfactants.

On the other hand, the Non-ionic surfactants have not performed as well for
EOR as anionic surfactants. Sulfonated hydrocarbons such as alcohol propoxylate
sulfate or alcohol propoxylate sulfonate are commonly used for Surfactant flooding.

2.2.2 Surfactant flooding advantages

The surfactant flooding has several advantages and some of them are listed
below [5]:

1. Very effective in lab test [high oil recovery].

2. Surfactant modeling is relatively simple with only a few well-designed experi-

ments needed to provide the most important simulation parameters.

3. Current high-performance surfactants cost less than $2/lb. of pure surfactant.

4. Recent developments in surfactants solutions for EOR have effectively reduced

the required surfactant concentration which lowering the chemical costs re-
quired.

5. Recently, new and effective surfactants are derived from plant resources such
as sunflower oil, soy and corn oil. It is non-toxic, non-hazardous, and readily
biodegradable.

The disadvantages of surfactant flooding could be listed as following:

1. Complex and expensive system.

2. Possibility of chromatographic separation of chemicals.

3. High adsorption of surfactant.

4. Losing its effectiveness at higher pressure, temperature, and salinity.

2.2.3 Field projects of the surfactant flooding

Many technically successful pilots have been done in addition to several small
commercial projects have been completed and several more are in progress.
Relatively, homogeneous reservoir formation is preferred. The presence of
high amounts of clays, gypsum, or anhydrite is undesirable. For commercially
available surfactants, formation-water chlorides should be less than 20,000 ppm
and divalent ions (Ca++ and Mg++) should be less than 500 ppm. The problems
encountered with some of the old pilots are well understood and have been solved
and the new generation surfactants will tolerate high salinity and high hardness so
there is no practical limit for high salinity reservoirs [14].

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2.3 Surfactant-polymer (SP) flooding

Surfactant-polymer flooding process is injecting a chemical slug that contains

water, surfactant, electrolyte (salt), usually a co-surfactant (alcohol), followed
by polymer-thickened water. In this process a surfactant is added to the polymer
solution that has the affinity for both water and oil. The use of the micellar solution
is to reduce the interfacial tension of the water-oil system in the reservoir in order
to displace the residual oil [15]. SP flooding method was patented for Marathon oil
co. by Gogarty and Tosch known as Mara-flood. The injection profile of the method
consists of injecting a pre-flush (to achieve the desired salinity environment),
followed by micellar slug (surfactant, co-surfactant, electrolyte), and followed by
polymer solution along with drive water.
The micellar solution composition that ensures a gradual transition from the
displacement water to the displaced oil without interface is as following [13]:

• Surfactant 10–15%.

• Water 20–60%.

• Oil 25–70%.

• Co-surfactant 3–4%.

Usually, the co-surfactant is alcohol which enhances the possibility for the micel-
lar solution to include oil or water. This surfactant-polymer flooding reduces the
oil-water IFT through the surfactant portion and reduces the mobility ratio through
presence of polymer.

2.3.1 Mechanism

The micellar solution is prepared using inorganic salts (water-soluble

electrolytes) in order to gain better viscosity control of the solution. A polymer
slug is used to drive the micellar solution slug in order to get a mobility control.
The injection process is shown in Figure 4. The technique establishes low oil-water
IFT and controls the mobility ratio which forming a considerable oil bank to be
produced [11].

2.3.2 Surfactant-polymer flooding advantages

The SP flooding advantages are listed below:

• Interfacial tension reduction (improves displacement sweep efficiency).

• Mobility control (improves volumetric sweep efficiency).

• Reduce adsorption of expensive surfactants.

The disadvantages could be as follows:

• Complex and expensive system.

• Possibility of chromatographic separation of chemicals.

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Figure 4.
Surfactant-polymer injection process.

• High adsorption of surfactant.

• Interactions between surfactant and polymer.

• Degradation of chemicals at high temperature.

2.3.3 Field project of the surfactant-polymer flooding

Since 1990, polymer flood and SP flood have been applied in a few field pilots
and expanded field tests.

2.4 Alkaline flooding

Alkaline flooding is one of the EOR methods in which alkaline agents are
injected into the reservoir to produce in situ surfactants, so the alkaline flooding
will eventually have the same effect of the surfactant flooding.

2.4.1 Mechanism

In the Alkaline flooding process, the alkaline agents such as sodium hydroxide
solution is injecting into the reservoirs which react with the naturally occurring
organic acids in the oil in order to produce surfactants or soaps at the oil-water
interface. However, the alkaline agents are less expensive than the surfactant agents,
the expected incremental oil recovery by alkaline flooding has not been confirmed
by field results and still remains possibility as the process is mainly dependent on
the mineral composition of the reservoir rock and its oil [11].

2.4.2 Alkaline flooding advantages

This EOR method has the same advantages of the surfactant flooding in addition
to that its main advantage over the surfactant is the cost of the alkaline agents are
cheap compared to the surfactant agents [12].

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2.4.3 Field project of the surfactant-polymer flooding

There were several pilot tests worldwide such as in Russian Tpexozephoe Field,
Hungarian H Field, Whittier Field in California, and North Gujarat Oil Field, India.

2.5 Alkaline-surfactant-polymer (ASP) flooding

Individual chemical flooding processes, alkaline flooding, surfactant flooding

and polymer flooding, can be combined differently. The three-component
combination, alkaline surfactant-polymer (ASP). The ASP method represents a
cost-effective chemical EOR method that yielding high oil recovery (mostly for
sandstone reservoirs). ASP flooding is utilizing the benefits of three flooding
methods, where oil recovery was enhanced, by reducing IFT, improving mobility
ratio, and improving microscopic displacement efficiency. The ASP projects in
China shows that the incremental oil recovery over water-flooding is 18.9% on the
average [14].

2.5.1 Mechanism

Alkaline injection reduces surfactant adsorption and the combination of soap

and synthetic surfactant results in low interfacial tension (IFT) in a wider range
of salinity. Soap and surfactant make emulsions stable through reduced IFT which
improve the sweep efficiency. There is a competition of adsorption sites between
polymer and surfactant. Therefore, addition of polymer reduces surfactant adsorp-
tion, or vice versa and improves the sweep efficiency of ASP solution [5].

2.5.2 Alkaline surfactant-polymer flooding advantages

Several advantages can be summarized as follows:

• Alkali is inexpensive, so it is cost reduction factor.

• Alkali reacts with acid in oil to form soap.

• Provide lower IFT in a wide salinity range.

• Soaps and surfactants produce emulsions that improve the sweep efficiency.

• Polymer and alkaline are reducing the surfactant adsorption.

• The polymer addition improves the sweep efficiency of the ASP solution.

• Carbonate formations are usually positively charged at neutral pH, which

favors adsorption of anionic surfactants. However, when (Na2CO3) is present,
carbonate surfaces (calcite, dolomite) become negatively charged and
adsorption decreases several fold.

• High pH also improves micro-emulsion phase behavior.

The limitations and challenges for ASP flooding are:

• Severe scaling in the injection lines with strong emulsification of the produced
fluid.

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• Polymers are less effective under high water salinity conditions, as the high salt
waters degrade the viscosity of polymers.

• Mobility control is critical.

• Laboratory tests must be done with crude and reservoir rock under reservoir
conditions and are essential for each reservoir condition.

2.5.3 Field projects of the alkaline surfactant-polymer flooding

There are large field trials that already implemented worldwide showing
encouraging results. The following table (Table 3) shows a summary for the
ASP projects or underway since 1980 including the start-up date, oil gravity, Oil
viscosity, implementation phase as secondary or tertiary, oil recovered in % of
OOIP, and the chemical cost in USD/bbl. In Figure 3, the production results after
applying the ASP flooding at the end of the water-flooding phase [13].

Table 3.
Field cases of ASP EOR.

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Author details

Ahmed Ragab1 and Eman M. Mansour2*

1 Reservoir Department, Agiba Petroleum Company, Cairo, Egypt

2 Production Department, Egyptian Petroleum Research Institute, Cairo, Egypt

*Address all correspondence to: [email protected]

© 2020 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms
of the Creative Commons Attribution License (http://creativecommons.org/licenses/
by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,
provided the original work is properly cited.

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