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UCSI UNIVERSITY
Faculty of Engineering, Technology and Built Environment
Chemical and Petroleum Engineering Department

Enhanced Oil Recovery

Petroleum engineering BSc program - EG412
January 2019

Lecture (7)
Chapter 3- Chemical Flooding – Alkaline

3 Jan to 5 Apr 2019 First semester/fourth Years

Chapter-3 Outline
Introduction to CEOR Alkaline Flooding Further Reading

Principals

Polymer CEOR Alkaline

Surfactant

Surfactant Flooding Polymer Flooding Exercises

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Lesson Outcomes

At the end of this lesson, students will be able to:

• Investigate the processes of chemical flooding (Alkaline /

Caustic ) in EOR.

• Propose suitable EORs methods in the application of oil

recovery activities.

Chemical Methods of Enhanced Oil Recovery

• Alkaline chemicals such as sodium carbonate to react

with crude oil to generate soap and increase pH.
• Surfactants to lower the interfacial tension between the
oil and water or change the wettability of the rock.
• Surfactants to generate foams or emulsions.
• Water soluble polymers to increase the viscosity of the
water
• Polymer gels for blocking or diverting flow.
• Combinations of chemicals and methods.
• others 4

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Current Research
• New polymers and surfactants
• New ways of making and using foam for mobility control
• New chemical EOR methods for fractured reservoirs
• New reservoir simulators for full field models of chemical
flooding
• Understanding and exploiting the role of low salinity on
oil recovery in polymer floods
• Understanding and exploiting the role of viscoelasticity
on polymer performance
• Understanding and modeling the role of alkali and insitu
surfactant generation on phase behavior 5

What is Chemical enhanced Oil recovery

• Chemical EOR is the process where
or more of chemicals are mixed with
water and injected to reservoir.
• Main objective is to increase oil
recovery beyond water levels.
• Most often, chemical flooding means
use of surfactants and/or polymers.
Alkaline can added to their mixture.
• Sometimes, foam EOR and low-
salinity water flooding are classified
as chemical.
• Figure here demonstrate a graphical Watch Vidio: Alkaline Surfactant Polymer
example of chemical flooding where Flooding - (ASP) Enhan
alkaline surfactant and polymer are
used. 6

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Target and fundamental principle of EOR

EOR and specifically Chemical EOR may improve:
• Macroscopic displacement efficiency
• Microscopic displacement efficiency
• Water-oil or gas-oil IFT
• Alter wettability
• Change relative permeability
• Reduce water cut or water-oil ratio
In essence, EOR change fluid-rock system modifying one of two parameters:
• Mobility ratio
• Capillary number
Fundamental principles of CEOR(and first-level screening):
Lower mobility ratio Enhance macroscopic displacement  Use Polymers
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Increase Capillary number Enhance microscopic displacement  Use Surfactants

Case study for chemical EOR feasibility evaluation

The water cut and stage EOR of different cases within 1 injected PV,
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(Xianchao Chen etal 2015)

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Alkaline Flooding
Caustic Flooding

Introduction

Among several chemical methods, alkaline flooding is

probably the cheapest method. Overall, however, past field
applications did not show significantly high incremental oil
recovery over water flooding.
Currently, there seems a research interest to investigate
the alkaline injection in heavy oil reservoirs, because heavy
oils have high contents of organic acids (saponifiable
components) to react with alkalis so that surfactants called
soap are generated in situ.

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Mechanism
lower interfacial: because of The chemical reaction between chemicals
such as sodium carbonate and sodium hydroxide (most common alkali
agents) and organic acids (saponifiable components) in crude oil to
produce in situ surfactants (soaps) that can lower interfacial tension.
Emulsification: In alkaline flooding, stable emulsions can be formed
because alkali reacts with crude oil to generate in situ surfactant
(soap). improved oil recovery through the formation of emulsions.
Emulsification mainly depends on the water/oil IFT. The lower the IFT,
the easier the emulsification occurs.(emulsification increased the oil
recovery factor by about 5%).
lowers the surfactant adsorption: The addition of the alkali increases
pH and lowers the surfactant adsorption so that very low surfactant
concentrations can be used to reduce cost.
Other mechanisms include wettability alteration, mobility control by
divalent precipitates, co-injection or alternate injection of alkaline
solution and gas to improve sweep efficiency.
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Alkalis used in Alkaline flooding

Alkalis used for in situ formation of surfactants include sodium hydroxide,
sodium carbonate, sodium orthosilicate, sodium tripolyphosphate, sodium
metaborate, ammonium hydroxide, and ammonium carbonate. In the past, the
first two were used most often.

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Effects of Alkali precipitation with different

hardness solutions
under equivalent experimental conditions of porosity and
flow rate, sodium carbonate shows less degree of
permeability damage in the presence of hard water, see
the figure below

Notice :Because
of ion exchange
processes,
alkalinity loss is
significant.

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Alkaline Reaction with Crude Oil

Alkali reacts with the petroleum acids during the alkaline flooding in the
reservoir. To form a surfactant hydroxide ion reacts with a pseudo-acid
component which is known as hydrolysis reaction (Equation 1). When
pseudo-acid is not present in the crude oil then little surfactant can be
generated.
HAo + NaOH NaA + H2O,………………………….(1)

The reaction depends strongly on the aqueous solution pH and occurs at the
water/oil interface. A fraction of organic acids in oil become ionized with the
addition of an alkali, whereas others remained electronically neutral. The
hydrogen-bonding interaction between the ionized and neutral acids can lead
to the formation of a complex called acid soap. Thus, the overall reaction,
(equation 2), is decomposed into a distribution of the molecular acid between
the oleic and aqueous phases,

HAo ↔HAw,……………………………………………..(2)

and an aqueous hydrolysis where, HA denotes a single acid species, A-

denotes anionic surfactant(as shown in Figure 1 ), and subscripts o and w
denote oleic and aqueous phases, respectively
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Alkaline application in the oil industry

Notice :Because of the alkaline reaction with crude oil, the IFT between
the oil and water becomes lower. This lower IFT makes the emulsions
more stable.

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Alkaline Reaction with Rock

When clays originally in equilibrium with formation water are contacted with
alkaline solution, the surface will attempt to equilibrate with its new
environment, and ions will start exchanging between the solid surfaces and
the alkaline solution.

where X denotes mineral-base exchange sites.

Contrary to ion exchange which is a fast reversible process, the dissolution

of rock minerals by alkalis is a long-term irreversible kinetic process. To
determine the minimum alkali requirement, a core is flushed with alkali
solution. Then the alkali consumption includes ion exchange and dissolution.

Because of the complex rock mineralogy in most petroleum reservoirs, the

number of possible reactions with alkalis is large. Reservoir rock reaction is
believed to be by far the largest contributor to alkali consumption.

Ehrlich and Wygal (1977): found high consumption rates for clay but
relatively low reaction rates for quartz, calcite.
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Alkaline Reaction with Water

The primary reaction of the alkali with the reservoir water is to reduce
the activity of multivalent cations such as calcium and magnesium in
the oilfield brines. Upon contact of the alkalis with these ions,
precipitates of calcium and magnesium hydroxide, carbonate, or
silicate may form depending on pH, ion concentrations, temperature,
etc.

precipitates : If properly located, these precipitates can cause

trancformation of flow within the reservoir, leading to better contact of
the injected fluid with the less permeable, less flooded flow channels.
This then may contribute to improved recovery.

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Application Conditions of Alkaline flooding

 Injection wells should be within oil zones not in the peripheral
aquifer to avoid alkaline consumption by reacting with divalents.

 remaining oil saturation should be higher than 40%.

 The alkaline process is not recommended if CO2 content is high.

And low-pH alkalis should be considered in carbonate reservoirs

 Thus, clay content should not exceed 15-25%.

 Formation permeability should be greater than 100 mD.

 Oil viscosity should be less than 50 -100 cP.

 Well spacing should be (2-36)x10,000 m2/well.

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Facts taken into account when designing an

Alkaline flooding Project : (1)
 Alkaline assumption in field is higher than that in laboratory,
because the contacting time of alkalis with rocks in the former is
much longer than that in the latter.

• When alkaline flooding is combined with other methods, such

polymer flooding, surfactant flooding, hydrocarbon gas injection,
thermal recovery, etc, much better effects will be obtained.

• Alkaline injection could cause scale problems in the reservoir,

wellbore, and surface facility and equipment.

• When alkaline solution contacts with oil, stable emulsions may be

formed. This will increase the cost to treatment of produced fluids
on surface.

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Facts taken into account when designing an

Alkaline flooding Project: (2)
 When designing injected alkaline concentration and slug size, first
determine the optimum alkaline concentration corresponding to the
lowest IFT. Then determine the alkaline consumption
experimentally. The injected alkaline concentration should be the
optimum concentration plus the concentration to satisfy alkaline
consumption.

• To achieve good results for an alkaline project, the IFT should be

less than 0.01 mN/m. If the IFT is higher than 0.1 mN/m, modified
alkaline flooding methods should be considered, such as thermal
alkaline flooding, gas alkaline flooding, mobility-controlled caustic
flood (MCCF) to take advantage of precipitation , or a method
combined with surfactant or polymer.

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Summary

Modified from SPE78711

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Alkaline flooding – Field Case

North Gujarat Oil Field, India

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Alkaline flooding – Field Case

North Gujarat Oil Field, India

Table : Reservoir and fluid data for North Gujarat Oil Field, India

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Things I learned
Things I confirmed
Question I still have

Be ready next lecture

with my best wishes

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