A STUDY OF CYCLOHEXANE MANUFACTURE

AND SAFETY PRECAUTIONS

A PROJECT REPORT

Submitted by

ADARSH S ANANDAN 815020219001

ASWIN K M 815020219003
MAHEEN T 815020219007

in partial fulfilment for the award of the degree

of

BACHELOR OF TECHNOLOGY

in

PETROLEUM ENGINEERING

DHANLAKSHMI SRINIVASAN INSTITUTE OF RESEARCH &

TECHNOLOGY, SIRUVACHUR – 621113.

ANNA UNIVERSITY: CHENNAI – 600025

MAY- 2024

i
 A STUDY OF CYCLOHEXANE MANUFACTURE
AND SAFETY PRECAUTIONS
A PROJECT REPORT

Submitted by

ADARSH S ANANDAN 815020219001

ASWIN K M 815020219003
MAHEEN T 815020219007

in partial fulfilment for the award of the degree

of

BACHELOR OF TECHNOLOGY

in

PETROLEUM ENGINEERING

DHANLAKSHMI SRINIVASAN INSTITUTE OF RESEARCH &

TECHNOLOGY, SIRUVACHUR – 621113.

ANNA UNIVERSITY: CHENNAI – 600025

MAY- 2024

ii
 ANNA UNIVERSITY: CHENNAI 600 025

BONAFIDE CERTIFICATE

Certified that this report “A

STUDY OF CYCLOHEXANE
MANUFACTURE AND SAFETY PRECAUTIONS” is the bonafide
work of “ADARSH S ANANDAN 815020219001, ASWIN K M
815020219003, MAHEEN T 815020219007” who carried out of the project
work under any supervision.

SIGNATURE SIGNATURE

Mr.VENGADESAN R M.Sc., M,Phil., Mr.VENGADESAN R M.Sc., M,Phil.,

HEAD OF THE DEPARTMENT SUPERVISOR

Department of Petroleum Engineering, Department of Petroleum Engineering

Dhanalakshmi Srinivasan Institute of Dhanalakshmi Srinivasan Institute of
Research and Technology, Research and Technology,
Siruvachur-621 113. Siruvachur-621 113.

Submitted for project Viva-voce examination held on: ………………..

INTERNAL EXAMINER EXTERNAL EXAMINER

iii
 ACKNOWLEDGEMENT

I express my deep sense of gratitude to our chairman SHRI.A.

SRINIVASAN for his vital guidance and blessings in the project.

I am very grateful to our principal DR.T.ANBARASAN for providing us

with an environment to complete our project successfully.

I am deeply indebted to our HOD Dr. D. RAMYADEVI, Ph.D., Department

of Petroleum Engineering, who modeled us technically and morally for achieving
great success in life.

It is my privilege to express my heartfelt thanks to our guide Mr. R.

VENGADESAN, ASSISTANT PROFESSOR for his constant encouragement,
valuable guidance, and timely help for the progress of this project work.

A special thanks to our coordinator Mrs. S. LALITHA, ASSISTANT

PROFESSOR whose help, stimulating suggestions, and encouragement helped
me to coordinate my project work.

I am also thankful to all staff members of our college and technicians for
their valuable assistance in carrying out my project work.

ADARSH S ANANDAN 815020219001

ASWIN K M 815020219003
MAHEEN T 815020219007

iv
 ABSTRACT
India is currently producing crude oil from matured fields because of insufficient
discoveries of new fields. Therefore, to control the energy crisis in India, enhanced oil
recovery (EOR) techniques are required to reduce crude imports from the OPEC
(Organization of the Petroleum Exporting Countries). This review mentions chemical EOR
techniques (polymers, surfactants, alkali, nanoparticles, and combined alkali-surfactant-
polymer flooding) and operations in India. Chemical EOR methods are one of the most
efficient methods for oil displacement. The efficiency is enhanced by interfacial tension
(IFT) reduction using surfactants and alkali, and mobility control of injected water is done
by adding a polymer to increase the volumetric sweep efficiency. This paper also reviews the
current trend of chemical EOR, prospects of chemical EOR in Indian oilfields. The outcome
of this review depicts all chemical EOR operations and recovery rates both at the laboratory
scale and field scale around the country. The additional recovery rates are compared from
various chemical EOR methods like conventional chemical flooding methods and
conventional chemicals combined with nanoparticles on a laboratory scale. The analysis
provides an idea about enhanced recovery screening and implementation of chemical EOR
methods in existing fields will significantly reduce the energy crisis in India.

v
 TABLE OF CONTENTS

CHAPTER TITLE PAGE NO

NO
ABSTRACT vii
LIST OF TABLES xi
LIST OF FIGURES xii
LIST OF SYMBOLS xiii
LIST OF ABBREVIATIONS xiv
1 INTRODUCTION 1
1.1 Overview 1
1.2 Selecting Prepare EOR Method 4
1.3 Aim of the Project 4
2 LITERATURE REVIEW 5
2.1 General Classification of EOR 5
3 STUDY AREA 10
3.1 Introduction 10
3.2 Location 10
3.3 Geological features 13
3.4 Climate 13
3.5 Vegetation and Land Uses 13
3.6 Oil reservoir 13
3.7 Environmental Consideration 14
4 BACKGROUND OF SURFACTANT 25
4.1 Definition of Surfactant 15
4.2 characterization of Surfactant 15
4.2.1 Critical micelle concentration 15
4.2.2 Cloud Point 17
4.2.3 Hydrophile-Liphophile Balance 17
4.2.4 Solubilization Parameters 18
4.2.5 Microemulsion System 19
5 BACKGROUND OF ROCK SAMPLE 20
5.1 Introduction 20
5.2 Characterization of Sandstone 20
6 ROLE OF SURFACTANT IN OIL 24
RECOVERY
6.1 Interfacial Tension Reduction 24
6.2 Wettability Alteration 25
6.3 Emulsification 25
7 MATERIAL AND METHODOLOGY 27

vi
 7.1 Introduction 27
7.2 Experimental Setup 27

7.3 Methodology Procedure 27

7.4 Formula Used in the Experiment and 31
Measurement
7.5 Calculation 31
8 SURFACTANT FLOODING 33
8.1 Introduction 33
8.2 Surfactant 34
8.3 Classification of Surfactant 35
8.4 Surfactant Flooding in EOR 36
8.5 Development of Chemical-Enhanced Oil 38
Recovery
8.6 Current Status Of Chemical EOR of India 39
8.7 Challenges of Chemical-Enhanced Oil 41
Recovery in India
8.8 Implementation Methodology & Future 41
Prospect of Chemical-Enhanced Oil Recovery
in India
9 WETTABILITY AND PERMEABILITY 43
9.1 Wettability and Relative Permeability 43
9.1.1 Factor affecting the wettability 44
9.1.2 Wettability alteration chemical 44
injection
9.1.3 Measurement of relative permeability 47
9.1.3.1Unsteady State 47
9.1.4 Wettability Measurement 48
9.1.4.1 Relative Permeability Method 48
10 RESULT & DISCUSSION 50
10.1 Overview 50
10.2 Non-ionic Surfactant (Ethoxy – Alcohol) 51
10.3 Anionic Surfactant Ethoxy-Sulphate 54
CONCLUSION 57
RECOMMENDATION 58
REFERENCE 59

vii
 LIST OF TABLES

TABLE TABLE NAME PAGE

NO NO
2.1 General EOR methods classification 11
7.1 Crude oil Properties 30
7.2 List of Experiments Conducted & Properties of Cores 30
used in this Study
8.2 List of Surfactant molecules with different types of charge 36
10.1 Core Flooding Results and Non-Ionic Surfactants 50
Concentration with Kro/Krw
10.2.1 Comparison between the effect of various concentration 51
surfactant
10.2.2 Core Flood Simulator Results at various non-ionic 52
surfactant concentrations with Kro / Krw
10.2.3 Core Flood Simulator Results at various non-ionic 53
surfactant concentrations with fw
10.3 Comparison between the Effect of various concentrations 54
of surfactant
10.3.2 Core Flood Simulator Results at various ionic surfactant 55
concentrations with Kro / Krw
10.3.3 Core Flood Simulator Results at various ionic surfactant 56
concentrations with fw

viii
 LIST OF FIGURE

FIGURE NO FIGURE NAME PAGE NO

1.1 Chemical EOR Classification 2
4.2 Micelle formation 16
4.2.1 Determination of kraft point 16
4.2.4 Determination of Salinity 19
4.2.5 Winsor’s classification 19
5.1 XRD graph sandstone (Reddish) 21
5.2 Optical photomicrography sandstone 22
5.3 XRD graph sandstone (Blackish) 23
7.1 Core Flood Apparatus 28
7.2 Block diagram of Core Flood Apparatus 29
8.1 Principle of Flooding Residual Oil 33
8.2 Surfactant Block diagram 34
8.4.1 Chemical Flooding 36
8.4.2 Miscible Process control 37
8.4.3 ASP chemical flooding 38
8.5.1 Future EOR production 39
8.6.1 Mangala-Bhagyam Field Production 40
8.6.2 Oil production Performance in ASP flooding 41
9.1 Relative Permeability Curve for alkaline surfactant 45
TX-100
9.2 Relative Permeability Curve for alkaline surfactant 46
CTAB
9.3 Relative Permeability Curve for alkaline surfactant 46
SDS
9.4 Wettability curve for alkaline Surfactant 49
10.2.1 Effect of Surfactant Concentration fw 52
10.2.1 Effect of Surfactant Concentration Kro/Krw 53
10.3.1 Effect of Surfactant Concentration fw 55
10.3.2 Effect of Surfactant Concentration Kro/Krw 56

ix
 LIST OF SYMBOLS

SYMBOLS NAME OF THE SYMBOLS

μ Fluid Viscosity
μw Viscosity of Water
μo Viscosity of oil
Ko Effective permeability of Oil
Kro Relative Permeability of Oil
Krw Relative Permeability of water
Kw Effective Permeability of water
Fw Fractional flow to water
K Permeability
So Oil Saturation
Sw Water Saturation
Swi Initial water saturation
Sor Residual Oil Saturation

x
 LIST OF ABBREVIATION

IOR Improved Oil Recovery

WAG Water Alternating Gas

CTAB Cationic Trimethyl Ammonium Bromide

SDS Sodium Dodecyl Sulfate

DDDC Dual Drop Dual Cristal

HABSA Hexadecyl Amino Benzene Sulphonic Acid

USBM United States Bureau of Mines

OOIP Original Oil In Place

IFT Interfacial Tension

ASP Alkaline Surfactant Polymer

EOR Enhanced Oil Recovery

PV Pore Volume

N Produced Oil

xi
1
 CHAPTER-I

INTRODUCTION

Overview
Oil and gas resources remain the world’s major contributor to energy supply even
with the recent energy generation from renewable sources. As global energy demand
increases in juxtaposition to dwindling energy resources, maximizing oil recovery from
previously under- exploited reserves becomes crucial to meet the ever-increasing energy
demand.

The processes of oil recovery are majorly in three stages namely: primary, secondary, and
tertiary (EOR) stage. After the application of primary and secondary oil recovery techniques,
two-thirds of the original oil in place (OOIP) remains in the reservoir.

This is either because the oil is trapped by capillary forces (residual oil) or bypassed in
some other way. The bypassed oil arises due to reservoir heterogeneities or because of an
unfavorable mobility ratio between the aqueous and oleic phases.

On the other hand, the residual oil is made up of discrete ganglia that are produced
when a finger-like protrusion of the oleic mass forms a narrow neck by the combined effects
of local pressure gradient and interfacial tension (IFT).

To enhance the overall oil displacement efficiency, numerous EOR methods have been
devised and utilized. During oil recovery, the overall oil displacement efficiency is a
combination of macroscopic (volumetric sweep) and microscopic (pore scale) displacement
efficiency.

Macroscopic displacement efficiency is a measure of the effectiveness of the injected

fluids in contacting the oil zone volumetrically concerning the total reservoir volume while
microscopic displacement efficiency is the efficiency related to the ability of the displacing
fluid (s) to mobilize oil trapped at the pore scale when it contacts the oil. Summarily, any
mechanism that can increase oil recovery efficiency at either the micro or macro-scale or
both is beneficial for EOR.

The devised and utilized EOR methods are majorly categorized into thermal and non-
thermal EOR methods. Unfortunately, thermal EOR methods are unsuitable for reservoirs
with great depth and thin pay zones.

1
 Thus, nonthermal EOR has received prodigious attention for recovering oil by passed
trapped in the reservoir.

Amongst all the EOR techniques, the chemical EOR method, a non-thermal EOR
method, has been adjudged as the most promising because of its higher efficiency, technical
and economic feasibility, and reasonable capital cost.

The application of this EOR method became popular in the 1980s due to higher oil prices
and technological advancement that enables an understanding of their mechanism. Chemical
EOR methods increase oil recovery by increasing the effectiveness of water injected into the
reservoir to displace the oil.

Dependent on the type of chemical EOR process, chemicals injected with the water slug
alter the fluid–fluid and/or fluid–rock interaction in the reservoir. This includes lowering the
IFT between the imbibing fluid and oil or an increment in the viscosity of the injectant for
improving mobility and conformance control.

Besides, the injected chemicals result in wettability alteration of the rock to increase oil
permeability. The well-known traditional chemical EOR methods are polymer flooding,
surfactant, and alkaline flooding.

However, conventional chemical EOR methods have their limitations. Polymers, whose
main recovery mechanism is to increase the viscosity of injectants and consequently
mobility, suffer viscosity loss in the presence of reservoir brines and elevated temperature
conditions.

2
Figure 1.1 Chemical EOR Classification

3
 Surfactant and alkali lose their efficiency during their flow in porous media due to adsorption
phenomena. Subsequently, different modes of chemical food injections were devised, studied, and applied
for EOR processes. These include the binary mix of alkali–surfactant (AS), surfactant/polymer (SP),
alkaline/polymer (AP), and alkaline/surfactant/polymer (ASP) slug (see Fig. 1).

The synergy of the combined conventional chemicals recorded an improved efficiency during their
applications in oil wells. Recently, the use of foam enhanced by surfactants and polymers, for improved
stability and mobility control has been studied and found to improve oil recovery. More recently, the
evolution of nanotechnology and its applications to improve the efficiency of various processes in the fields
of metallurgy, electronics, medicine, aeronautics, catalysis, and fuel cells have prompted its use and
application in the oil and gas industry.

The field of nanoscience and nanotechnology describes the creation and exploitation of materials with
structural features having at least one of its dimensions in the nanometer range (1–100 nm). The
“engineered nano-material” is called a nanoparticle. The resultant improvement in the functional properties
of a process generated due to the addition of nanoparticles is attributed to their scalable and quantum
effects.

The application of these functional materials requires a base fluid such as gas, oil, water, or any other
suitable liquid substance, hence, they are termed nanofluid. The application of nanotechnology has
proffered solutions to various oil and gas problems ranging from drilling operations, petroleum exploration,
inhibiting asphaltene depositions and gas hydrate formations, hydraulic fracturing jobs, and EOR. For EOR
processes, nanofluid flooding has been evaluated and explored as a chemical EOR process with field
application reported in Colombia.

The mechanism of the improved oil recovery was identified as structural disjoining pressure, wettability
alteration, IFT reduction, and improved viscosity of the injectant.

More recently, the addition of nanoparticles to conventional EOR chemicals has been studied and
reported to yield novel materials with excellent and fascinating properties. For example, polymeric
nanofluid, a synergistic combination of nanoparticles and polymers was found to possess improved
rheological properties and stability for application in the presence of high-temperature and high-salinity
conditions.

Furthermore, the synergistic application of nanoparticles with surfactant lowers their adsorption via a
competitive adsorption mechanism, while their applications with foams generate stable foams with longer
half-life. This overview is a fundamental study that presents the current scenario of available research on
chemical EOR. First, a survey of the conventional chemical EOR method was carried out.

The conventional EOR chemical types were identified and the mechanism of their EOR applications was
discussed, and their limitations were highlighted.

Thereafter, the binary application of conventional chemical EOR methods was also defined and analyzed.
Afterward, the recent trend of incorporating nanotechnology for chemical EOR was also explored. The
various nanofluid types, the mechanism of their application, and laboratory studies were outlined.

Finally, the challenges associated with chemical EOR methods were enumerated and recommendations
for future works were proffered.

4
 Selecting prepare EOR method

EOR implementation depends on the characteristics of the oil Light oils, EOR refers to the techniques
after primary and secondary recovery that include surfactant flood, polymer flood, miscible drive, and even
thermal methods For heavy oils, EOR implies techniques after primary recovery which include steam
injection and in-situ combustion.

The application of enhanced oil recovery techniques allows the economic value of existing hydrocarbon
resource fields to be maximized, through increasing oil recovery and field life extension. Identifying
appropriate projects in any field can be a difficult task because of the large number of EOR techniques and
reservoir combinations that need to be considered

Since the production of oil by the EOR process is rather difficult, risky, and requires huge capital costs,
the proper selection of the EOR method for a certain reservoir is important to attaining a successful and
profitable project. The most difficult problem that faces reservoir engineers and experts is how to select the
most appropriate method to enhance oil production based on technical and economic factors. To achieve
this mission, many reservoir factors must be studied carefully such as reservoir depth, reservoir area,
reservoir temperature, porosity, permeability, oil gravity, and oil viscosity, and also how these factors may
affect each other

Aim of the project

 Designing and building up a system to obtain experimental results of application of

the parameters of EOR

 Investigate the effects of Viscosity in water flooding on oil recovery and

sweep efficiency of the simulated reservoirs.

 To study the effects of surfactants, and polymers on wettability and oil recovery

 To understand the factors affecting wettability and oil recovery during the
EOR process with chemical injection.

 To study the comparison between the effects of various concentrations of

surfactants on oil recovery.

 To distinguish between the effects of Non-ionic surfactants and xanthan gum

polymer on oil recovery.

5
 CHAPTER- II

LITERATURE SURVEY

General classification of EOR processes.

EOR processes are often classified into four different categories, these are thermal
methods, gas injection, chemical flooding, and emerging processes (Taber et al. 1997). The
main driving mechanism is the major reason to fall into one of the subdivisions presented in
the general classification of EOR processes that is described in Table (2.1) The EOR
processes that are described in the table are:

 Chemical EOR processes

 Gas EOR processes

 Thermal EOR processes

 Emerging EOR processes

Gbadamosi et al., (2019) recently, nanotechnology is also attracting researchers

in India for developing new EOR techniques to increase oil recovery from the depleted
reservoirs. Different types of nanoparticles like SiO2, ZnO, TiO2, Al2O3, ZrO2, carbon
nanotube, graphene, MgO, NiO and Fe2O3 are now used in the laboratory for investigating
their effectiveness in oil recovery.

Saleh et al., (2014) in this review, the impact on chemical EOR operations in India for
future oil production, challenges, and the prospect of chemical EOR in India have been
mentioned. The fine outcome of this review is that chemical EOR operations are
implemented in Indian oil fields, and the future prospect of implementation and challenges
of chemical EOR in the Indian scenario will help future petroleum engineering students and
researchers.

6
Table 2.1 General EOR Classification

Surfactant flooding, Polymer flooding, Alkaline

flooding
Chemical EOR Processes Alkaline/surfactant/Polymer (ASP)
Gels for water diversion/shut off Solvent flooding

Hydrocarbon injection
(miscible/immiscible) CO2
Gas EOR Processes flooding(miscible/immiscible) Nitrogen
injection
Flue gas injection (Miscible and
immiscible) Water-Alternating-Gas (WAG)

Steam-flooding
Cyclic steam stimulation
Thermal EOR processes In-situ combustion
Hot waterflooding
Steam-assisted
Gravity drainage

Smart water
Low salinity water
Flooding carbonated waterflood
Emerging EOR Processes Microbial EOR
Enzymatic EOR
Electromagnetic heating
Surface mining and extraction
Nanoparticles

7
 Rellegadla et al., (2017) Polymer flooding has several benefits like mobility control of
injected water, and at the same time, it decreases the relative permeability of water,
increasing vertical and area sweep efficiency and making the process economically feasible
in oil recovery

Rai et al. (2015) investigated the laboratory results of surfactant flooding and surfactant-
polymer flooding with simulation results using STARS (CMG). Therefore, they got almost
the same results from both laboratory and simulation work, i.e., surfactant flooding results
with simulation are 17.6%, and surfactant-polymer flooding results are 24% after water
flooding. They finally concluded that using a single surfactant only reduces IFT but using SP
flooding reduces IFT and improves the overall sweep efficiency for a better recovery.

Liu et al. (2007) conducted core flooding studies on Canadian heavy crude oil with 14
API to investigate the tertiary oil recovery by alkaline surfactant flooding. They found 24%
OIIP (oil initially inplace) additional oil recovery by injecting a 0.5` PV of a chemical slug.
Results showed that a significant reduction in IFT by the formation of oil/water emulsion
(O/W) is necessary to improve additional oil recovery.

Pei et al. (2012) conducted sand pack flooding experiments for heavy oil to investigate the
effectiveness of alkaline flooding and alkaline surfactant (AS) flooding. They found that
additional recovery in AS flooding is lower than alkaline flooding because the coexistence
of surfactant and alkali can reduce IFT between heavy oil and aqueous solution but not in
ultralow level IFT reduction. However, in alkaline flooding, the alkaline solution can
penetrate the oil phase to form O/W droplet flow to improve sweep efficiency. Therefore,
ultimate oil recovery in alkaline flooding is greater than in AS flooding.

Sheng, (2015); when it reacts with crude oil, it will help reduce IFT, change rock
wettability, and emulsify favorably for oil recovery. So, adding alkali into surfactant is to
generate soaps because alkali provides electrolytes, which helps reduce the amount of
surfactant injection and adsorption of surfactant.

Sharm, (2013). Therefore, the combination of alkali and surfactant gives a synergetic
effect on wettability alteration and IFT reduction, and alkali is much cheaper than surfactant.
So, using the mix will help reduce the cost of chemical EOR.

8
 Jung et al. (2013) examined the effect of alkali-polymer flooding on heavy oil
unconsolidated sandstone formations through core flooding studies. Flooding results showed
an increase in additional oil recovery of 30% OIIP over water flooding. The synergy
(combined action) between alkali and polymer has its own properties, like alkali produces
in- suit surfactants when it reacts with crude oil that helps for wettability alteration and
emulsification. Additionally, polymer gives enough mobility control. Alkali-polymer
flooding can displace more residual crude when compared with individual polymer or
alkaline flooding.

Saha et al. (2019) worked on natural surfactants and polymers (xanthan gum), and
nanoparticles (silica) for heavy oil recovery investigation. In this process, they got better
results of IFT reduction, wettability alteration (intermediate wet to vital water wet),
rheological characters, emulsification, and finally, through core flooding experiments, they
got 27.33% OIIP. Therefore, they concluded that natural surfactant polymer (xanthan gum),
and silica nanoparticles are good signs for heavy oil recovery. In EOR applications,
Pickering emulsion is an essential method that gives good stability to the emulsion addition
of nanoparticles.

Kumar et al. (2017) characterized the surfactant polymer and nanoparticles (SNP) for
harsh reservoir conditions. They indicated that IFT reduction, emulsion stability, .nd better
mobility control are possible in this case. The additional recovery of 24% OIIP was obtained
by conducting core flooding experiments after conventional water flooding.

Rellegadla et al. (2018) determined the recovery by implementing the nanoparticles

(nickel) and xanthan gum blend. Core flooding results show a recovery of 5.98% OOIP.
Finally, the results show that polymer-assisted nanoparticles are significant enough for EOR
applications.

Pal and Mandal (2021) recently developed a simulation and experimental model on
this issue by using surfactant-polymer with nanoparticles in the EOR application. This
combined chemical helps to improve the static stabilization of dispersed polymer molecules
and the mechanical barrier effect around the dispersed oil phase by contributing to
electrostatic repulsion and steric stabilization. Some core flooding tests give better oil
recovery by using this combined chemical.

Dong ( 2011). The fraction of organic acids in oil reacts with alkali becoming ionized,
and the rest remains neutral with a hydrogen bond. Thus, hydrogen interacts with ionized
and neutral acids to form complex acid soaps. Therefore, acid soaps' formation will help
reduce the interfacial tension between two immiscible fluids, wettability alteration between
rock surface and oil (oil-wet to water-wet), emulsification, and entrainment. Alkali is not
only good enough for IFT but also for spontaneous emulsification and wettability that
depend on rock and crude properties.

9
 Bera et al., (2021). As it is mentioned before production by chemical EOR from
different fields in India operated by different operators, the main EOR implemented fields
by chemical EOR in India are polymer flooding and ASP flooding. Apart from chemical
EOR, thermal and gas injection plays a major in Indian fields. Mangala, Bhagyam, and
Aishwariya fields in Rajasthan have a conventional recovery of 50.22% of the total
recovery, its peak production was recorded in 2014 with 175.77 BPD. Based on economic
assumptions, production will continue until it reaches its economic limit in 2061. Initially
project was implemented with polymer as a pilot field then; after getting excellent results, it
was decided to implement ASP as a full commercial EOR project. The field is located in
block RJeONe90/1 and the production forecast of the field.

Bhaskar, (2020). Apart from EOR development, Indian E&P companies discovered
various new fields in various states in India. Therefore, hopefully, these fields are furtherly
help to implement EOR techniques for more energy production.

1
0
 CHAPTER- III

STUDY AREA

Introduction
Nestled in Tamil Nadu, India, the Trichy Kollidam River Basin is a diverse landscape
marked by the flow of the Kollidam River. Rich in biodiversity and geological significance,
it's a hub of agriculture, industry, and vibrant ecosystems. With its fertile lands, intricate
geological formations, and cultural heritage, the basin beckons exploration and promises
insights into the dynamic interplay between nature and human activity.
Location:
The Trichy Kollidam River Basin is situated in the southern part of India, primarily
within the state of Tamil Nadu. It encompasses a diverse landscape, ranging from fertile
plains to hilly terrains, and is intersected by the Kollidam River, a major tributary of the
Cauvery River.
Longitude= 78.820266o
Latitude= 10.980976o

10
11
12
 Geological Features:

1. Sedimentary Formations: The basin is characterized by sedimentary rock formations,

including sandstones, shales, and limestones, which are conducive to the formation of oil
reservoirs.

2. Structural Complexity: Geological structures such as anticlines, fault zones, and

stratigraphic traps contribute to the trapping and accumulation of hydrocarbons within the
basin.

3. Porosity and Permeability: The presence of porous and permeable rock layers allows for
the migration and storage of oil and natural gas within the reservoirs.

Climate:
The climate in the Trichy Kollidam River Basin is predominantly tropical, with hot
and humid conditions prevailing throughout the year. The region experiences distinct wet
and dry seasons, with monsoonal rains typically occurring between June and September.

Vegetation and Land Use:

1. Vegetation: The basin supports a variety of vegetation types, including tropical forests,
grasslands, and agricultural crops such as rice, sugarcane, and cotton.

2. Land Use: Human activities in the basin primarily revolve around agriculture, with
extensive cultivation of crops along the riverbanks and surrounding plains. Additionally,
there may be some industrial and urban developments in certain areas.

3. Hydrology: The Kollidam River, originating from the confluence of the rivers Cauvery
and Kollidam, serves as a lifeline for the region. It provides water for irrigation, domestic
use, and industrial activities, supporting agricultural productivity and livelihoods in the
surrounding areas.

3.6. Oil Reservoirs:

1. Existing Reserves: The Trichy Kollidam River Basin is known to contain significant oil
reserves, which have been partially exploited through conventional extraction methods.

2. Untapped Potential: Despite the presence of known reserves, there remains substantial
untapped potential for further oil recovery through enhanced methods such as water
flooding, chemical injection, and thermal techniques.

13
3.7 Environmental Considerations:

1. Biodiversity: The basin supports diverse flora and fauna, including several endemic and
endangered species. Careful consideration of environmental impacts is essential to minimize
disturbances to ecosystems.

2. Water Resources: The protection of water resources, including rivers, lakes, and
groundwater aquifers, is paramount to ensure sustainable development and minimize
contamination risks associated with oil extraction activities.

14
 CHAPTER-IV

BACKGROUND OF SURFACTANT

Before discussing surfactants about EOR, a brief background on surfactants is

provided in this section. This background includes the definition of surfactants and the main
parameters examined during surfactant characterization.

Definition of surfactants

Surfactants (surface active agents) are usually organic compounds consisting

of two distinctive parts: a hydrophilic head and a hydrophobic tail. There are four
classifications of surfactants according to the charge existing on the hydrophilic head. These
classifications include non-ionic (without any charge), anionic (carrying a negative charge),
cationic (carrying a positive charge), and zwitterionic (carrying both negative and positive
charges).

Generally, surfactants have a chain structure which is mainly attributed to the structure of the
hydrophobic tail. the tail group of a surfactant is often formed of a short polymer chain, a
long hydrocarbon chain, a siloxane chain, or a fluorocarbon chain. The head group, on the
other hand, is formed of moieties such as sulfates, sulfonates, polyoxyethylene chains,
carboxylates, alcohols, or quaternary ammonium salts. The presence of these groups dictates
the amphiphilic nature of the surfactant.

Characterization of surfactants
It is necessary to characterize surfactants for technical and
economic reasons. Before using a surfactant in any application, it is important to ensure its
effectiveness and stability over its period of use. In this part of the review, the main
parameters studied to characterize surfactants are presented.

Critical micelle concentration

A micelle forms when surfactant molecules gather in a liquid
colloid. The critical micelle concentration (CMC) is the point where enough surfactant is
present for micelle formation to begin. At the CMC, various solution properties like thermal
and electrical conductivities, viscosity, and surface tension experience sudden changes. The
CMC depends on factors such as the molecular structure of the surfactant (like the length of
the hydrophobic chain), pressure conditions, solution salinity, ionic composition, pH, and
temperature (Fig4.2.1).

15
 Fig 4.2 Micelle's formation upon reaching the CMC.

There are over 30 methods available for measuring CMC. These methods can be broadly
classified into direct and indirect approaches. Direct methods involve observing changes in
solution properties (such as viscosity, electrical conductivity, refractive index, and osmotic
pressure) in response to alterations in surfactant concentration. Indirect methods, on the other
hand, involve monitoring changes in a certain property of a probe substance added to the
surfactant solution.
In the realm of surfactant applications, particularly in enhanced oil recovery (EOR), one
common technique for determining CMC is measuring interfacial tension (IFT) between the
surfactant solution and the oil phase. This method provides valuable insights into the
effectiveness of surfactants in altering interfacial properties, crucial for optimizing EOR
processes (Fig 4.2.1).

Fig. 4.2.1 Determination of the Krafft point from the phase diagram of surfactant solutions

16
 Cloud Point
The cloud point is the temperature at which aqueous solutions of nonionic surfactants
become cloudy due to phase separation. Nonionic surfactants, like polyethoxylated types,
rely on hydrogen bonding with water molecules for solubility. However, increasing
temperature weakens these bonds, leading to dehydration of the surfactant's polyoxyethylene
chains and phase separation.

Above the cloud point, the solution separates into a surfactant-rich phase and a bulk
aqueous phase. This phenomenon adversely affects EOR performance, especially in high-
temperature reservoirs. Combining nonionic surfactants with anionic surfactants, like internal
olefin sulfonate (IOS), can mitigate this issue, as IOS exhibits higher solubility in aqueous
solutions with increasing temperature, and counteracting phase separation.

Hydrophile–lipophile balance
An important criterion for surfactant characterization is the
hydrophile–lipophile balance (HLB). This criterion measures the extent to which a surfactant
is lipophilic or hydrophilic. The HLB is a number on a scale from 0 to 20 that indicates
relatively the tendency of a surfactant to dissolve in oil or water. On that scale, a value of 0
correlates with a completely hydrophobic (lipophilic) molecule, while a value of 20
correlates with a molecule composed entirely of hydrophilic components. Table 2 shows
surfactant properties predicted using the HLB values. To form proper microemulsions during
oil recovery, a low-HLB surfactant needs to be selected.

Table 2: Relation between HLB values and the expected properties/applications of

surfactants.

HLB value Property/application

0–3 Antifoaming agent

4–6 W/O (water in oil) emulsifier
7-9 Watting Agent
8–18 O/W emulsifier
13–15 Detergent
10–18 Hydrotrope or solubilizer

for low-salinity formations. Analogously, a high-HLB surfactant should be selected for high-
salinity formations. Researchers developed some equations to calculate the HLB values of
surfactants. Griffin’s equation to calculate the HLB for nonionic ethoxylated surfactants is as
follows:

17
 HLBGriffin = 1/5 (( MH/MT) ∗ 100) (1)

where MH denotes the molecular mass of the hydrophilic part of the surfactant molecule and
MT denotes the total molecular mass of the surfactant molecule found that HLB values for
surfactants can be calculated from their chemical formulae based on group numbers, as
shown in the following equation:

HLBDavies = 7 + ∑(hydrophilic group numbers) – (2)

∑(lipophilic group numbers)

n a surfactant containing a number n of –CH2– groups, the HLB value is calculated as follows:

HLBDavies = 7 + ∑(hydrophilic group numbers) –

n(group number per CH2 group) (3)

where the value of the CH2-group number is substituted as 0.475 and the hydrophilic group
numbers are obtained. Later, other researchers developed experimental methods to determine
the HLB values. Some of these methods are based on the emulsion inversion point (EIP), the
phase-inversion temperature (PIT), and others.

Solubilization parameters
The oil (or water) solubilization ratio is defined as the volume of oil (or water)
solubilized per surfactant volume in a microemulsion. the solubilization ratio (SR) can be
expressed as follows:
SRoil = Volumeoil
Volumesurfactant (4)
SRwater = Volumewater
Volumesurfactant (5)

the optimum solubilization, which produces the ideal microemulsion formulation needed
for oil recovery, occurs when SRwater and SRoil are equal. This is obtained by drawing the oil-
SR curve and water-SR curve, where the intersection point between the two curves
represents the optimum solubilization occurring at the optimum salinity studying the
solubilization parameters is important to optimize the oil recovery process. This is because
the lowest oil– water IFT is normally observed at the optimum salinity.

18
 Fig. 4.2.4 Determination of the optimal salinity for an oil-water–surfactant system using
the solubilization-ratio curves

Microemulsion systems
At equilibrium, microemulsion systems are classified into four main
types. These systems are shown in Fig.2.2.6. Winsor’s Type I systems consist of an O/W (oil
in water) microemulsion that coexists with an excess oil phase. Conversely, in Type II
systems, a W/O microemulsion coexists with an excess water phase. In Type III systems,
three separate phases coexist including microemulsion, water, and oil. Finally, Type IV
systems can be described as homogeneous, single-phase systems formed entirely of one
microemulsion phase. Type IV microemulsions are extensions of Type III systems.
However, they are formed by increasing the concentration of the surfactant until the whole
liquid transforms into a single phase. For EOR applications, microemulsions of Type III are
usually preferred as they provide the lowest IFT compared to the other systems.

Fig..2.5 Winsor’s classification of microemulsion

19
 CHAPTER – V

BACKGROUND OF ROCK SAMPLE

INTRODUCTION
The characterization and identification of minerals are fundamental in the
development and operation of mining and minerals processing systems. Worldwide,
sandstones have been used as construction material for centuries and are still being used for
this purpose. Although, sandstones show similar appearances and properties; a geological
background may cause differences in color, mineral composition, granulometric properties,
pressure strength, and/or weathering behavior . On the other hand, the mineralogical
properties of sandstones could predict their mechanical properties such as the uniaxial
compressive strength. The inherent parameters of sandstones can be characterized by their
petrographical properties . There is a large deposit of sandstones kollidam basin . The
presence of this large deposit of sandstones in the kollidam region was the motivation to
initiate this study on the characterization of sandstones. On the other, the knowledge on the
physical such as the compressive strength of Indian sandstones will help the booming
construction industry in India by providing the characteristics of sandstones

Sandstones have been used as construction material worldwide and are still used for this
purpose. On the other hand, the mineralogical properties of sandstones could predict their
mechanical properties such as the uniaxial compressive strength. The mineral composition,
the void space, the degree of grain interlocking, the packing density and the grain size is
known to be affected by the petrographic characteristics. However, contradictory results
have been reported relating the influence of mineral content on the geomechanical properties
of sandstones . It has been reported that rocks containing quartz as binding materials

Characterisation of Sandstones:
Mineralogy and Physical Properties are the strongest materials
followed by calcite, and ferrous minerals; but rocks clayey binding materials are the weakest
ones. Furthermore, the shape of the grains is another petrographical property. The shape of
the grains is usually expressed in terms of the roundness or sphericity, roundness being
distinct from sphericity in that, it is concerned with the curvature of the corners.

20
Fig.5.1. XRD graph of Reddish sandstone showing the minerals identified (Q= Quartz, crl=
Crysobilite

Table5.1. Chemical composition of six of sandstones samples using XRF

Concentration %
Element Yellowish Greyish
Al 4.01 4.66
Ca 0.09 0.10
Fe 0.83 1.44
K 1.87 1.58
Mg 0.19 0.32
Mn - -
Na 1.52 0.66
P - .03
Si 39.10 39.48
Ti 0.14 0.19

21
Optical photomicrograph of the surface of the yellowish sandstone showing fine grains size

Fossile ferous

22
Fig.5.2 . XRD graph of blackish sandstone showing the minerals identified (Q= Quartz, alb =
Albite, Gl = Glauconite, Kl= Kaolinite)

carbonate sandstone

23
 CHAPTER – VI

THE ROLE OF SURFACTANT IN OIL RECOVERY

Introduction
Generally, surfactants affect the processes of oil recovery through four main
mechanisms: interfacial tension reduction, wettability alteration, foam generation and
emulsification. In this part of the review, a brief discussion of these mechanisms is
presented.

Interfacial Tension Reduction

The interfacial tension is generally defined as the attraction force between the
molecules existing at the interface of two fluids. The interfacial tension between
hydrocarbons and water molecules causes an increase in the capillary force that plays an
essential role in hydrocarbon trapping within porous media. Therefore, surfactant injection is
used as an option to reduce the interfacial tension. Studies showed that many types of
surfactants can be used at low concentrations (∼0.05– 0.2%) to achieve low interfacial
tension on the order of 10−2 dynes/cm or less. In the absence of oil, the presence of a
surfactant in water reduces the surface tension because the molecules of the surfactant
replace part of the water molecules at the water surface.

The attraction forces between the water and surfactant molecules are less than the attraction
forces between the water molecules themselves. Subsequently, the contraction force
responsible for the surface tension is reduced. In water–oil–surfactant systems, on the other
hand, surfactant molecules replace some of the oil and water molecules at the original oil–
water interface in a process called surfactant adsorption.

This new arrangement of molecules involves an interaction between the hydrophobic

components of the surfactant and oil on one side of the interface and between the hydrophilic
components of the surfactant and water on the other side. The new interaction across the oil–
water interface is significantly stronger than the original interaction between water and oil
before surfactant addition. Therefore, the interfacial tension is reduced.

The ability of surfactants to reduce the interfacial tension between crude oil and brine is
highly sensitive to the type and concentration of ions existing in the brine. As stated earlier,
there is an optimal salinity at which the interfacial tension between crude oil and brine is
reduced to ultra-low values. Usually, this optimal salinity is expressed in terms of the NaCl
content that is dissolved in the solution. However, research studies showed that introducing
divalent/multivalent cations to a surfactant solution containing a given NaCl concentration
reduces the value of the optimal salinity .

24
 This means that the surfactant becomes less tolerant to NaCl salinity in the presence of these
divalent/multivalent cations, which adversely affects the interfacial tension between oil and
brine. The effect of divalent cations on the interfacial tension properties of a surfactant
formulation was investigated. The formulation contained petroleum sulfonate and
ethoxylated sulfonate. It was demonstrated that increasing the concentration of divalent
cations (Ca2+ and Mg2+) in surfactant–oil–brine systems drastically reduces the optimal
salinity. Increasing the concentration of Ca2+ and Mg2+ in surfactant solutions containing
petroleum sulfonate and lignosulfonate was detrimental to their ability to reduce the oil–
brain interfacial tension.

Therefore, this effect should be considered during surfactant screening because natural
connotate water normally contains these divalent cations. This phenomenon is mainly
observed with anionic surfactants that tend to precipitate out of the bulk solution upon
reacting with the divalent/trivalent cations, and thus, oil recovery is expected to be reduced.

Wettability Alteration
Wettability alteration involves changing how fluids adhere to solid surfaces, crucial in oil
recovery. Sandstones are typically water-wet to intermediate-wet, while carbonates tend
towards intermediate-wet to oil-Wettability alteration involves changing how fluids adhere to
solid surfaces, crucial in oil recovery. Sandstones are typically water-wet to intermediate-
wet, while carbonates tend towards intermediate-wet to oil-wet. Techniques like surfactant
injection, nanofluid injection, low salinity waterflooding, and thermal recovery alter
wettability towards water-wet states.

In fractured carbonate reservoirs, waterflooding effectiveness depends on spontaneous

imbibition, more successful in water-wet reservoirs. Carbonates' oil-wet nature impedes
recovery, necessitating wettability alteration, often achieved through surfactant injection.
Surfactants alter wettability via coating (anionic) or cleaning (cationic) mechanisms, with
cationic surfactants usually more effective due to stronger interactions.

Carbonate wettability is influenced by pH, with carboxylates in crude oil contributing to oil-
wetness. Targeting carboxylates is crucial for effective wettability alteration. Studies have
shown cationic surfactants' efficacy in desorbing carboxylates, returning the surface to a
water- wet state.
salinity waterflooding, and thermal recovery alter wettability towards water-wet
states.
Emulsification
Emulsification is one of the mechanisms that can increase oil recovery in the tertiary
phase. Emulsions mostly form during alkaline and/or surfactant flooding under the
conditions of low/ultra-low IFT and under shear resulting from fluid flow in rock pores.
Emulsification usually improves oil recovery through two main mechanisms:

25
(1) emulsification and entrainment; and (2) emulsification and entrapment. In the case of
emulsification and entrainment, the IFT is significantly reduced allowing the droplets of
crude oil to be emulsified into the water phase. Then, the droplets are transported along with
the water phase. This means that oil bulks are gradually produced in the form of fine
particles. Usually, the emulsification-entrainment mechanism occurs when the formed
emulsion droplets have sizes that are equal to or smaller than the pore sizes. On the other
hand, the emulsification- entrapment mechanism involves the formation of emulsion droplets
that plug pore throats and water channels.
As a result, the water-to-oil mobility ratio is reduced and surfactant solution is diverted to
upswept areas, which improves the areal and vertical sweep efficiencies. This effect is
important, particularly in the production of viscous oils where the sweep efficiency of
waterflooding is poor. It is noteworthy that the entrapment in this mechanism occurs because
the IFT is not low enough to reduce the average size of the emulsion droplets below that of
the pores in the reservoir rock.

26
 CHAPTER-VII

MATERIAL AND METHODELOGY

Introduction
In this experiment, we will measure all the properties of the fluids and the core samples.
Such as length, area, porosity, and permeability for the core and density and viscosity for the
fluids. Fluids are mainly water, crude oil, and chemical solvents. We will inject the water
into the core first and then oil to get a water-oil system. Then we inject the water or chemical
solvents into the core to recover the oil.

Recently, in the operation, we measured the relative permeability and wettability and
recorded their efficiency in increasing oil Recovery. Also, the efficiency of different
chemicals in changing the relative permeability between oil and water and changing the
wettability. In our experiments, we will use Darcy's law to find the relative permeability and
for wettability, we will use (the relative permeability method).

Experimental Setup
A core flood apparatus was built to measure relative permeabilities (Figure 1). It
consisted of a pump for injecting different fluids into the core, a pressure gauge to measure
the pressure drop across the core during the floods, a core holder inside which the core is
placed, and a measuring cylinder to measure the flow rates at the outlet. The dead volumes of
all the flow lines were measured and accounted for in all the material balance calculations.

Methodelogy & Procedure

Preparing the core with the proper length and diameter. That needs the cutting and
drilling processes to get the right length and diameter.

• Cleaning process that will be done by Soxhlet tube by using benzene or toluene drying
process using the electrical oven for 24 hours or more.

• Preparing the injection fluid and measuring all the related properties such as density and
viscosity.

• Saturating the core with the injection fluid and measuring the porosity. It will be done by
measuring the dry weight before the saturating and the wet weight after the saturating.

• Injecting the fluid that already the core is saturated with and measuring the pressure
difference on the sides of the core. That pressure difference can be used to measure the
permeability.

27
• Injecting the oil into the core and measuring the weight of the core after oil injecting. The
relative weight change can be used to measure the Swi. And also measuring the pressure
difference that can be used to measure the relative permeability.

• Injecting water with various concentrations of used materials and measuring the pressure
difference that can be used to determine the relative permeability and measuring the weight
that can be used to determine the saturation. And then identifying the wettability.

• Kirkuk field crude oil sample is used in all core floods. The core flood apparatusis used to
estimate oil recovery, saturations of oil and water and the end-point effective permeabilities.
A core flood simulator uses these data to estimate oil/water relative permeabilities. The
series of experiments are conducted in this study.

Fig 7.1 Core flooding apparatus

28
 Figure 7.2 Block diagram of the Core flood Apparatus

From the Block diagram, we can see the parts of the system that are as follows:

a-Core holder

b- Hydraulic pump

c- Pressure gauge Pi (Measuring the Core Holder Pressure)

d- Syringe pump

e- Pressure gauge P1 (Measuring Inlet Pressure)

f- Pressure gauge P2 (Measuring Outlet Pressure)g-

Regulator

h- Cylinder

29
Table 7.1.Crude Oil Properties.

Crude No Density(ppg) API GRAVITY Viscosity SP.GR

(cp)
Crude 1 7.28 30.21 0.95 0.875

7.2 List of Experiments Conducted and Properties of Cores Used in this Study

30
 Formulas used in the experiment and the measurements:
Darcy law:
qi = A.Ket ∆p (2-1)
μ L
and for calculating effective permeability we have to multiply the absolute permeability by the
relative permeability:
Ket =K.Kri (2-2)
To find porosity we have to find bulk volume and pore volume:
Bulk volume =3.14*r2*h (3-1)

wet weight – dry weight

Pore volume =
Density of water (3-2)
Porosity is equal to pore volume divided by bulk volume

Porosity =(pore volume / Bulk volume )* 100% (3-3)

In the experiment, we measured the wet weight and dry weight of the plug to be able to
measure the porosity as follows:

Dry weight of the core= 33.54 grams

Wet weight of the core= 33.88 grams

To find density we have to divide the weight over the volume of the fluid, we will measure the
density of Brine, Oil, and surfactant solutions.

Density = weight /volume (3-4)

We can find permeability from Darcy equation

K=q+L-viscosity (3-5)
A.(pf-pl)

Calculations:

Bulk volume=3.14*r^2*h
3.14 2.85 22.85
-14.43

wet weight - dry weight

Pore volume =
density of water
= 33.80-33.54
1.02
31
=0.3333 cc

32
Porosity =(pore volume / Bulk volume)*100%
=03333 *100%
14.43
=2.3%

Density = weight
volume

Since the volume = 50 ml

And the Mass=43.75 gm

Then: Density = 43.75 gm

50 ml
=0.875 gm/ml*8.33
=7.28 ppg
To find the Permeability of the plug, the following parameters are known:

Q=0.1~ml/min=0.016666~cc/s

L=2.85~cm And A=5.016~m^{2}

P=46.11~psi=3.1375~atm

μ =0.8~cp for brine water

Then: k = q*L*mu
A*(pf-p)
K = 0.016666*2.85*0.8
5.046*(3.1375)
K = 0.9763md

Recovery of oil=N/OOIP, Since N is Produced Oil

To find the Original Oil In Place at initial and abandonment pressures, We have to measure
the oil injected into the Plug and the oil recovered from it. So in our calculations:
The volume of Oil injected into the plug = 0.199 ml = OOIP
The volume of Oil produced = 0.09599 ml

Then: Recovery (0.09599/0.199)=0.48=48%. And so on for other cases.

33
 CHAPTER-VIII

SURFACTANT FLOODING

8 .1 INTRODUCTION

Surfactant flooding is the injection of one or more liquid chemicals and surfactants. The
injection effectively controls the phase behavior properties in the oil reservoir, thus
mobilizing the trapped crude oil by lowering IFT between the injected liquid and the oil. The
principle of surfactant flooding is illustrated in Figure 6.1.

Figure 8.1. Principle of flooding where residual oil is trapped in the Reservoir (O'Brien, 1982).

There is a great potential for chemical processes with surfactant flooding since there is the
possibility of designing a process where the overall displacement efficiency can be
increased. Nowadays many mature reservoirs under waterflood have decreasing production
rates despite having 50-75% of the original oil left inside the reservoir [Flaaten et al., 2008].
In such cases, it is likely that surfactant flooding can increase economic productivity.

Surfactants are added to decrease the IFT between oil and water. Co- surfactants are
blended into the liquid surfactant solution to improve the properties of the surfactant
solution. The co-surfactant either serves as a promoter or as an active agent in the blended
surfactant solution to provide optimal conditions concerning temperature, pressure, and
salinity. Due to certain physical characteristics of the reservoir, such as adsorption to the
rock and trapping of the fluid in the pore structure, considerable losses of the surfactant may
occur. The stability of the surfactant system at reservoir conditions is also of great relevance.

It is well known that surfactant systems are sensitive to high temperatures and high
salinity and therefore surfactants that can resist these conditions should be used. Surfactant
flooding creates microemulsion solutions, which may contain different combinations of
surfactants, co-
34
surfactants, hydrocarbons, water, and electrolytes. Polymers are also often added to the
injected surfactant solution, to increase viscosity, thus maintaining mobility control. In
general, there are three types of surfactant flooding for EOR shown in Table 6.1.

The optimization criterion in surfactant flooding is to maximize the amount of oil recovered,
while minimizing the chemical cost. While it is necessary to reach low IFT for the surfactant
system, minimizing only the IFT may not always coincide with optimal oil recovery, as low
IFT is not the only essential condition to meet to get a successful and efficient oil recovery.

SURFACTANTS

In surfactant flooding, the chemical system contains surface active agents, surfactants,
which are polymeric molecules that lower the IFT between the liquid surfactant solution and
the residual oil. Surfactants adsorb on a surface or fluid/fluid interface when present at low
concentrations.
The most common structural form for surfactants is where they contain a nonpolar part, a
hydrocarbon 'tail', and a polar or ionic part. The structure is shown in figure 6.2.

Figure 8.2

35
 It is the balance between the hydrophilic and hydrophobic parts of the surfactant that
generates the characteristics of the surface-active agent. In EOR with surfactant flooding the
hydrophilic head interacts with water molecules and the hydrophobic tail interacts with the
residual oil. Thus, surfactants can form water-in-oil or oil-in-water emulsions. Surfactant
molecules are amphiphilic, as they have both hydrophilic and hydrophobic moieties.
Amphiphiles adsorb effectively to interfaces and typically contribute to significant
reductions of the interfacial energy.

The primary surfactant is directly involved in the microemulsion formation of the EOR
surfactant
flooding process. The co-surfactant, if any, promotes or improves the activities of the
primary surfactant, by e.g. changing the surface energy or the viscosity of the liquids. Due to
the chromatographic separation of surfactant, co-surfactant, and any other components,
throughout the reservoir, it can be problematic to create a multicomponent surfactant system
capable of maintaining optimal properties throughout the flooding process.

CLASSIFICATION OF SURFACTANTS

Surfactants are frequently classified on the basis of the ionic nature of the head group, as
anionic, cationic, nonionic or zwitterionic. Each type possesses certain characteristics
depending on how the surfactant molecules ionize in aqueous solutions. In Table 6.3 a few
commonly used surfactants are shown.

Commonly used surfactants for EOR, are sulfonated hydrocarbons such as alcohol
propoxylate sulfate or alcohol propoxylate sulfonate. To achieve an optimal surfactant flood
for any given oil reservoir surfactants and polymers are often both included in the flooding.
Surfactants are responsible for the reduction of the IFT and the polymer is added to improve
the sweep efficiency, The demands on surfactants are numerous and it is a great challenge to
distinguish which mechanisms are most dominant. Process conditions, such as high
temperature and high pressure are often the reality in
reservoir environments.

36
Table 8.2 List of common surfactant molecules with different types of charge: anionic,
cationic and non-ionic.

Surfactant Type Name of the Surfactant

Anionic surfactant  Ethoxy Sulphate
 Sodium dodecyl sulfate(SDS)
 Sodium dodecyl benzene sulfonate
Cationic surfactant  Cetyl trimethylammonium bromide
(CTAB)
 Dodecyl amine hydrochloride
Non-ionic surfactant  Ethoxy Alcohol
 Polyethylene Oxides

8.4. SURFACTANT FLOODING IN EOR

Surfactant flooding is an example of chemical flooding. This is a complex process, where

the displacement is immiscible, as water or brine does not mix with oil. However, this
condition is changed by the addition of surfactants. The technique creates low interfacial
tension (IFT), where especially an ultra-low IFT (0.001mN/m) between the displacing fluid
and the oil is a requirement to mobilize the residual oil. The liquid surfactant injected into
the reservoir is often a complex chemical system, which creates a so-called micelle solution.
During surfactant flooding the complex system must form microemulsions with the residual
oil as this supports the decrease of the IFT and increases the mobility.

Figure 8.4.1 Chemical flooding, which is the injection of water and chemicals

37
 However, the formation of microemulsions may also be a significant disadvantage, as
microemulsions may plug the pores. It is also important to be aware of the high loss of
surfactant, occurring as a result of adsorption and phase partitioning inside the reservoir. It is
known that surfactant systems are sensitive to high temperatures and high salinity, leading to
requirements for developing surfactant systems that can withstand such conditions. Other
chemical processes have also been developed, such as alkaline flooding and various
processes where alcohols are introduced. In alkaline flooding, alkaline chemicals are injected
into the reservoir, where they react with certain components in the oil to generate surfactants
in situ. Alcohol processes have so far only been tested in laboratories and have not yet been
applied in the field.
Miscible processes are based on the injection of a gas or fluid, which is miscible with the
crude oil at reservoir conditions, to mobilize the crude oil in the reservoir. The process is
illustrated in Figure 8.4.1. This process relies on the modification of the components either in
the injected phase or in the reservoir oil phase. Modification of either injected fluid or gas or
the reservoir oil is achieved through multiple contacts between the injected phase and the oil
phase with mass transfer of components between the phases, E.g., injection of CO2 as a
liquid will entail extraction of the heavier hydrocarbons from the reservoir oil, which will
allow the displacement front to become miscible.].

Figure 8.4.2 Miscible process control, where the injected fluid does mix with oil

38
 Figure 8.4.3 ASP Chemical flooding

ASP chemical flooding, also known as alkaline-surfactant-polymer flooding, is an

enhanced oil recovery (EOR) technique used in the petroleum industry. It involves injecting
a combination of alkaline agents, surfactants, and polymers into an oil reservoir to improve
oil recovery efficiency.

Alkaline agents help neutralize acidic components in the reservoir, surfactants reduce the
interfacial tension between oil and water, and polymers increase the viscosity of the injected
water, improving sweep efficiency and displacing more oil towards production wells.

ASP flooding is often employed in mature oil fields where primary and secondary
recovery methods have been exhausted. It can significantly increase the amount of oil
recovered from a reservoir compared to conventional methods.

8.5 Development of chemical-enhanced oil recovery.

In developing countries like India, energy requirements increase day by day because of
the population. A decrease in supply and demand growth plays a crucial role in oil
production supply for domestic users. To fulfill the requirement for energy, it is necessary to
take advanced steps in developing oil production from existing fields. Therefore, to minimize
the gap between the supply and demand for oil and gas, the government has to implement
new development techniques like EOR and IOR (improved oil recovery) to increase
production from matured fields. Countries like the USA, India, Canada, Algeria, France,
Germany, Russia, Indonesia, and other countries are conducting EOR operations to increase
the production from matured fields; the world oil production through EOR operations and
the global EOR market was rising year by year. Development of any oil field requires EOR
screening that depends on reservoir
39
properties like porosity, permeability, oil viscosity, reservoir depth, composition, thickness,
oil gravity, type of formation, reservoir temperature, etc. Among gas injection and thermal
flooding techniques, chemical EOR is the classical EOR method. The development of
chemical EOR started in the early 1950s when polymer and surfactant flooding methods
became a well-established process. Many countries like Canada, Argentina, Albania, India,
China, Oman, and others countries conducted hundreds of pilots and field-scale
implementation on chemical EOR in the past few years with good results.

Figure 8.5.1. Future EOR production by different EOR techniques

8.6. Current Status of chemical EOR in India

In India, Enhanced Oil Recovery (EOR) techniques are becoming increasingly crucial due
to the maturity of many oil fields. Companies like ONGC, OIL, and private firms such as
Cairn India are actively implementing EOR operations, including chemical methods, to
extract additional oil. Chemical EOR involves injecting substances like polymers,
surfactants, or alkalis to alter reservoir conditions and improve oil recovery rates. Gas
injection and thermal methods are also utilized.

The government's 2018 policy supports EOR operations for fields with over three years of
production history, aiming to maximize the extraction potential of matured fields. ONGC
leads in production among government-owned entities, followed by OIL, while private firms
like Cairn India contribute significantly to overall production.

Polymer flooding emerges as a widely adopted chemical EOR technique in India, showing
promising results in various fields. Successful projects include those in the Sanand and Kalol

40
fields, where polymer flooding has significantly increased oil recovery rates. Additionally,
ASP flooding has been implemented in fields like Jhalora and Viraj, further demonstrating
the versatility of chemical EOR methods.

ONGC's achievement in employing polymer flooding on the Bechraji heavy oil field
represents a significant milestone in the Indian oil industry. This technique has traditionally
been used in a few countries like Afghanistan, Oman, Canada, and the UK, making ONGC's
successful implementation noteworthy.

Despite the emergent trend in the Indian oil and gas sector, marked by exploration operations
alongside EOR efforts in mature fields, significant opportunities remain for further
development. The focus on maximizing recovery from existing fields without the need for
discoveries aligns with India's energy security goals and contributes to its economic growth
trajectory.

Fig.8.6.1.Mangala-Bhagyam-Aishwariya field production forecast in block RJeONe90/1

41
Fig. 8.6.2. Oil production performance of Mangala field after implementing full scale ASP
flooding

8.7 Challenges of Chemical Enhanced Oil Recovery (EOR) in India include:

 Lack of expertise: India faces a shortage of skilled EOR professionals, hindering
proper screening and implementation of EOR techniques.
 Development of suitable chemicals: Researchers struggle to create effective polymers
for varying reservoir conditions, especially for high temperatures and salinities.
 Operational issues: Scaling and emulsion problems are common in ASP and
surfactant- polymer flooding, complicating injection rate design and formulation.
 Environmental concerns: Chemical injection can contaminate groundwater, posing
risks to freshwater resources and raising environmental issues.
 Economic feasibility: Limited government support and financial incentives, along with
high chemical costs, make EOR implementation economically challenging for oil
companies.
 Infrastructure and project management: Inadequate EOR infrastructure and project
management hinder smooth implementation and operation of EOR projects.
 Limited R&D facilities: India faces constraints in research and development
opportunities for EOR, including the availability of well-equipped laboratories and
experts in reservoir engineering and simulation.

Overall, overcoming these challenges is crucial for the successful adoption of chemical EOR
techniques in Indian oil fields and maximizing oil recovery.

8.8 Implementation Methodology and Future Prospects of Chemical Enhanced Oil

Recovery (EOR) in India

The 2018 EOR policy in India enables EOR operations in fields with three or more years
of commercial production, aiming to reduce crude oil imports. Recent discoveries in regions
like Rajasthan and Gujarat offer potential for future EOR applications. Premier institutions
conduct field screenings to assess EOR feasibility, followed by pilot tests to validate selected
methods. Successful pilots exceeding production thresholds receive financial incentives.

42
Chemical EOR methods, including polymer flooding and ASP flooding, hold promise for
increasing oil recovery from depleted fields. Laboratory studies over the past two decades
have demonstrated their efficacy under various reservoir conditions.

Despite challenges like chemical formulation and environmental concerns, ongoing

research efforts aim to address these issues.

Overall, chemical EOR presents a compelling opportunity to enhance India's energy

security and drive economic growth in the oil and gas sector. Through strategic
implementation and continued innovation, chemical EOR holds the potential to revolutionize
oil recovery practices in India, contributing to national energy self-sufficiency and
sustainable development.

43
 CHAPTER - IX
WETTABILITY AND PERMEABILITY

Wettability and Relative Permeability

Wettability is the relative adhesion of two fluids to a solid surface. For two immiscible
fluids in a porous medium, wettability is the measure of the preferential tendency of one of
the fluids to wet the interstitial surfaces of the porous medium in the presence of the other
fluid. The surfaces of the pores in rocks contain a wide variety of exposed minerals that have
preferential affinities for water, hydrocarbons, or constituents suspended and dissolved in the
fluids.

Wettability can be divided into four categories:

e Water-wet where the rock prefers to be cast with water and thus the rock has a high
affinity to water, allowing water to spread on the surface and hence occupy the small pores.

Intermediate-wet, where the surface has an almost equal tendency to be cast by one of the
fluids either oil or water. Oil wet, where the rock prefers to be in contact with oil.

Mixed-wet, where parts of the rock prefer to be in contact with oil and the other parts
prefer to be in contact with water.

Relative permeability is the ratio of the effective permeability of a particular fluid at a

particular saturation to the absolute permeability of that fluid at total saturation. If a single
fluid is present in a rock, its relative permeability is 1.0. So, the relative permeability of any
fluid is the ratio of how that fluid is flowing in a specific media in comparison with other
fluids.

The efficiencies of primary, secondary, and tertiary oil production are controlled by the
rock wettability. The heterogeneity in the rock and fluid composition makes the mixed
wettability in the reservoir. In other words, reservoirs may have a complex wettability
characteristic. For example, sandstone reservoirs are generally characterized as water-wet
reservoirs. Whereas carbonate reservoirs have the surface preferentially oil-wet. It is
believed that all petroleum reservoirs were initially water-wet. Later, some polar components
of oil penetrate through the thin film of water and adsorb strongly on the rock. Therefore, the
water was displaced by migrated oil.

44
 Based on the component minerals, some rocks have water-wetting or oil-wetting natures.
In a water-wet medium, the small and large pores are occupied by water and oil,
respectively. Whereas in an oil-wet system, the positions of the fluids are vice versa.

Wettability alteration can occur if the process described is reversible. It can be

implemented as a means to produce the residual unrecoverable oil and restore the original
reservoir wettability, which is presumed to be water-wet. The existing research has shown
that altering the wettability toward more water-wet increases enhanced oil recovery.

By applying water drive in primary and water flooding in the secondary oil recovery
method, wettability alteration happens. (Sala Thiel) showed that oil recovery for oil-wet
would be less than 15% compared with water-wet reservoirs through water flooding.
Because more oil can remain in an oil-wet system after a water breakthrough, therefore an
oil-wet system is not a good candidate for water flooding compared with a water-wet system.
Whereas mixed wettability has a higher oil recovery than water-wet reservoirs during water
flooding.

Factors affecting the wettability

At the pore scale, the amount of oil that can be displaced is affected by wettability. Factors
found to be influencing the wettability have been reported in several studies, the most
important factors are the mineralogical composition of the rock, The effects of reservoir
Fluid composition, The effects of surface-active compounds, and The effects of surface
roughness of Minerals.

Wettability alteration with Chemical injection:

It is a well-established fact that wettability alteration toward more water-wetness

conditions could result in improved oil recovery. Understanding the wettability alteration
mechanisms in multiphase flow in porous media is crucial for the efficient development of
enhanced oil recovery techniques. Chemical solutions such as surfactants increase the water
wetness of the rock surface which increases the relative permeability of the oil phase.
However, the wetting states of the reservoir determine how the fluids are distributed in the
pore space. A key aspect of the wettability alteration process is interactions in crude oil-
brine-rock system which is characterized by several methods.

The purpose of a review is to analyze critically a modification of wettability characteristics

in terms of chemical EOR methods. It consists of chemical materials, characterization
methods, and EOR mechanisms. To identify any factors that are influencing the wettability
of rock surface during chemical injection, responsible mechanisms involved in the
45
mechanism that

46
Chemicals react with the acid composition of the oil and produce surfactant that increases oil
recovery by reducing the interfacial tension between the injected fluid and oil, altering the
wettability of porous medium and forming emulsion spontaneously which releases the oil
from the pores. Relative permeability curves have an important role in the performance of
the reservoirs and are also one of the most important input data for the simulation of oil
reservoirs.

Relative permeability curves for water and alkaline-surfactant solutions are plotted in
Figures (9 .1), (9 .2) and (9 .3) By comparing relative permeability curves of water and
alkaline-surfactant solutions, a general upward movement in relative permeability curve is
observed due to improvement in effective permeability of water and oil.

An upward movement in oil relative permeability curves is due to changing rock

wettability to a higher degree of water wetness. Oil relative permeability curve in alkaline
solution and CTAB shows greater upward movement than other solutions. The surface of
carbonate rock has a positive charge, and alkaline reacts with the rock and changes the
charge of the rock to the negative.

Due to the negative charge of the surface of the rock and the negative head of the anionic
surfactant, the rock does not adsorb the anionic surfactant because of repulsion. But cationic
surfactants like CTAB with positive heads have adsorbed rock extremely, and it is the reason
for the wettability alteration of CTAB as a cationic surfactant. An upward movement in the
water relative permeability curve is due to a reduction in IFT between oil and water that
allows water to move more easily than oil. Increasing the effective permeability of water will
increase the water injection rate and thus increase the recovery rate.

Figure 9.1 Relative permeability curve for alkaline-surfactant TX-100

47
Figure 9.2 Relative permeability curve for alkaline-surfactant CTAB

Figure 9.3 Relative permeability curve for alkaline-surfactan SDS

48
 Measurement of Relative Permeability

Relative permeability describes the ability of the porous system to conduct one fluid
when two or more fluids are present. Relative permeabilities are used to predict the oil-water
flow characteristics in reservoirs. The relative permeability of rock to each fluid phase can be
measured in a core sample by steady-state or unsteady-state methods. In a steady-state
method, a fixed ratio of fluids is forced through the test sample until saturation and pressure
equilibrium are established.
The mathematical analysis of the unsteady-state procedure is more difficult. The theory
developed by Buckley and Leverett and extended by Welge is used for the measurement of
relative permeability under unsteady-state conditions.

Unsteady-state

Relative permeability measurements can be made more rapidly than steady-state

measurements. Hence, unsteady-state measurements are employed for most laboratory
measurements of relative permeability. Unsteady-state displacement is characterized by the
injection of one fluid into a core that contains a low or connate saturation of that fluid and
which is intended to displace the mobile portions of a second fluid. During two-phase flow,
the flow rate of each phase is related to a pressure drop gradient using Darcy's law,

q/L Ap (2-1)

and

Κ-Κ.Κ. (2-2)

where the subscript i denotes either the wetting or non-wetting phase. The effective
permeabilities (Kei) to each phase depend on the saturation and saturation history of the
phases. During single-phase flow when only one phase is present, the effective permeability
to that phase is a maximum and equal to absolute permeability. At any point when two
phases flow simultaneously, a difference in the pressure between the phases (i.c., capillary
pressure) usually exists. Capillary pressure depends on local curvatures of the fluid/fluid
interfaces, which in turn depend on saturation, saturation history, wettability, and pore
geometry. Laboratory unsteady-state displacement process can be affected by discontinuities
at the inlet and more importantly the outlet of the core. When only one phase is entering or
leaving the core, the capillary pressure and the effective permeability correspond to a
maximum saturation of that phase. However, when the two phases exist in the core
simultaneously, the situation is different. At the core exit, the difference in the pressure
between the phases will be extremely low. The only saturation at which this must be satisfied
is in the vicinity of zero capillary pressure. The pressure drops within each phase near the
exit must satisfy the above equation. It is usually assumed that the exit boundary condition
for simultaneous two-phase flow is zero
49
capillary pressure. By designing experiments to determine relative permeability by the
unsteady-state method, it is necessary that:

• The pressure gradient must be large enough to minimize capillary pressure effects.

• The pressure differential across the core must be sufficiently small compared with the total
operating pressure to minimize compressibility effects.

• The core must be homogeneous.

• The flow rate and the fluid properties must be held constant during the test.

Wettability Measurements

Wettability is usually defined as the tendency of one fluid to spread on or adhere to a

solid surface in the presence of another immiscible fluid. The contact angle subtended by the
oil- water interface against the rock surface is the universal measure of wettability. More
specifically, wettability is characterized by the water-advancing contact angle since it
corresponds to the oil production scenario in the reservoir. The quantitative methods of
characterizing the wettability of a porous medium are contact angle measurements, the
Amott test, and the USBM test. The qualitative methods are imbibition, microscope
examination, flotation, glass slide, relative permeability curves, capillarimetric method,
displacement capillary pressure, permeability/saturation relationships, and reservoir logs.
(Anderson)provides a brief description of all these methods along with pertinent references.
Although no single accepted method exists for accurate characterization of wettability, The
following methods are most widely used for laboratory measurements. (Contact Angle
Method, Amott Method, USBM Wettability Index, Qualitative Methods, Imbibition Method,
Microscope Examination, Floatation Methods, Glass Slide Method & Relative Permeability).

Relative Permeability Method

Wettability affects relative permeability because it is a major factor in the control of the
location, flow and spatial distribution of fluids in the core. So, this method is used in the
present study to discern wettability alterations induced by the surfactants through relative
permeability modifications. In this method, Craig's rules of thumb71 are used to distinguish
between strongly water-wet and oil-wet systems based on relative permeability curves.

50
Figure 9.4 Wettability curve for alkaline - surfactant

• Connate water saturations are usually greater than 20 to 25% PV in a water-wet rock, but
less than 10% PV in an oil-wet rock.

• Water saturation at which oil and water relative permeabilities are equal is generally greater
than 50% in water-wet rocks and less than 50% for oil-wet ones.

• The relative permeability to water at flood out is generally less than 30% in water-wet
rocks, but from 50 to 100% in oil-wet ones. These relative permeabilities are based on the oil
permeability at the connate water saturation.

51
 CHAPTER -X

RESULTS AND DISCUSSION

Overview

Two main mechanisms behind the use of surfactants for enhancing oil recovery are
reduction in interfacial tension and alteration of wettability. To discern the relative
contribution of these two mechanisms, core flood experiments were carried out in two types
of surfactants, one nonionic and the other anionic.

The complete breakdown of experiments conducted in this study is shown in Table 7.1.
Characteristics of relative permeability curves including the initial water saturation, the end-
point water relative permeability, the end-point oil relative permeability, and the water
saturation at the cross-over point were used to infer wettability alterations induced by the
surfactants. The rules of thumb used in this study to characterize wettability are
summarized in Table 10.1

.
Table 10.1.1 Rule of thumb used in this study for wettability Interpretation

S.no Criterion Water-wet Oil-wet Reference

1 Initial water Saturation, Swi >0.25 <0.15 Craig

2 Water Saturation at Cross- >0.5 <0.5 Craig

over Point

3 Endpoint Relative <0.3 >0.5 Craig

Permeability to Water at Sor

4 Endpoint Relative >0.95 <0.7- 0.8 Thomas

Permeability to Oil at Swi &Archer

52
 Non-ionic Surfactant (Ethoxy Alcohol)

Oil/water emulsion was formed during the core flood experiments in this system strongly
affecting relative permeability curves. This emulsion did not break down even for aging
times of over 24 hours. These emulsions formed at all surfactant concentrations blocked the
flow or caused very high-pressure drops. The high-pressure drops during primary drainage
caused low end-point oil permeabilities which raised concerns about the rules of thumb
(Table10.1.1).

Relative permeabilities were estimated for the system at various non-ionic surfactant
concentrations (Table 10.1.2, Figure 10.1.2 of Appendix). Only minor adjustments are made
in end-point oil relative permeabilities to obtain an acceptable history match of recovery and
pressure drop. Figures present the effect of non-ionic surfactant concentration on relative
permeability ratio and fractional water flow.

Relative permeability curves at 0 ppm surfactant concentration indicate water-wet

characteristics(Swi=39%>25%, Sw,c-o=55%>50%, Krw=7.5%< 30%). The end-point oil
relative permeability of 70% at Swi is caused by emulsion formation.

Relative permeability curves at 500 ppm surfactant concentration indicate water-

wet/intermediate-wet characteristics (S wi=45\%>25\% Sw.c-o=56%> 50\% Krw=2.6%<30%)
The end-point oil relative permeability of 56% at S_{wi} is once again attributed to emulsion
formation. Similar trends are observed in the characteristics of relative permeability curves at
all other surfactant concentrations.
Table 10.2.1 Comparison between the effect of various concentrations of surfactant

Case Recovery Swi Sor Ko Kw Kro krw

(%OOIP)
Brine 48 0.400 0.320 0.6834 0.08241 0.6999 0.0844
Water
500 ppm 45 0.450 0.332 0.5435 0.0887 0.5566 0.0911
1500 47 0.365 0.362 0.4170 0.0933 0.4271 0.0955
ppm
3500 54 0.300 0.365 0.2197 0.08830 0.2250 0.09044
ppm
5000 54 0.285 0.375 0.2040 0.06377 0.2089 0.06531
ppm

53
Table 10.2.2 Core Flood Simulated Results at Various Non-ionic Surfactant Concentrations
with Kro/ Krw

Figure 10.2.1 Effect of surfactant concentration fw

54
Table 10.2.3 Core Flood Simulated Results at Various Ionic Surfactant Concentrations with
fw10

Figure 10.2.2 Effect of surfactant concentration on Kro/Krw

55
 Anionic Surfactant (Ethoxy Sulphate)
The formation of oil/water emulsion was observed during the core floods in this system
also, which has a strong impact on relative permeability curves. Therefore, the wettability
shifts inferred from the characteristics of relative permeability curves are considered to be
doubtful for this system. These emulsions at surfactant concentrations of 500 ppm and above
caused serious difficulties in the core-flooding experiments resulting in no-flow situations or
very high-pressure drops, as in the case considered in section . The summary of experimental
and simulated results for waterflood at various concentrations of the anionic surfactant,
ethoxy sulphate . The resulting relative permeability curves obtained from the simulating for
this system for different anionic surfactant concentrations of the effect of anionic surfactant
concentration on relative permeability ratio and fractional water flow.

From Table 10.3.1, it is evident that only minor adjustments are needed in end-point water
relative permeabilities in the simulator to obtain an acceptable history match of oil recovery
and pressure drop at all anionic surfactant concentrations used in this study Relative
permeability curves at 0 ppm surfactant concentration indicate water-wet / intermediate-wet
characteristics (Swi = 40% > 25%, Sw,c-o = 50%, K20% <30%). The end-point oil relative
permeability of 76% at Swi is caused by emulsion formation. Relative permeability curves at
500 ppm surfactant concentration indicate weakly water-wet / intermediate-wet
characteristics (Swi = 36% > 25%, Sw.c-o = 48% <50%, Krw = 25% <30%). The end-point
oil relative permeability of 67% at Swi is once again attributed to emulsion formation.
Similar trends are observed in the characteristics of relative permeability curves at other
surfactant concentrations.

Table 10.3.1 Comparison between effects of various concentrations of surfactant.

Case Recovery Swi Sor Ko Kw Kro krw
(%OOIP)
Brine 40 0.400 0.374 0.7390 0.1383 0.757 0.1417
500 ppm 42 0.355 0.390 0.6511 0.1400 0.667 0.1434
1500 ppm 45 0.310 0.400 0.2059 0.1606 0.211 0.1645
3500 ppm 49 0.230 0.410 0.0370 0.0314 0.038 0.0322
5000 ppm 49 0.310 0.360 0.0185 0.0146 0.019 0.0150

56
Table 10.3.2 Core Flood Simulated Results at Various Ionic Surfactant Concentrations with
Kro/Krw

Figure 10.3.1 Effect of surfactant concentration on Fw

57
Table 10.3.3 Core Flood Simulated Results at various Ionic Surfactant Concentrations with fw

Figure 10.3.2 Effect of surfactant concentration on kro/krw,

58
 CONCLUSION

➤ The oil recovery gradually increases from 45% to 54% as the non-ionic surfactant
concentration is increased from 0 ppm to 5000 ppm. These enhanced oil recoveries are
attributed to the reduction in oil-water interfacial tension and not to wettability alteration as
discussed below.

➤ The relative permeability ratio curves are gradually shifting to the left as the non- ionic
surfactant concentration is increased. This shift appears to indicate a shift from water-wet to
less water-wet or intermediate-wet conditions. However, this shift is attributed to the
formation of oil/water emulsion observed at all surfactant concentrations as noted earlier,
and not to wettability alteration.

➤ The recoveries for the non-ionic surfactant (ethoxy alcohol) concentrations are higher
than the recoveries at the same concentrations of the anionic surfactant (ethoxy sulfate).

➤ Optimum oil recovery is obtained at a surfactant concentration of 3500 ppm for both non-
ionic and anionic surfactants. Anionic surfactant caused flow problems due to the formation
of strong emulsion. These observations suggest that the non- ionic surfactant, ethoxy alcohol
as the preferred surfactant and 3500 ppm is the optimum surfactant concentration.

59
 RECOMMENDATIONS FOR FUTURE WORKS
• Completing the remaining experimental part and obtaining the results from the built-up rig
to study the effect of added chemicals on the injection process in EOR instead of using a
simulator.

• Studying the effect of water saturation and salinity of water on the wettability and overall
recovery has been recommended.

• Using sandstone core samples, since sandstone has greater permeability than carbonate core
samples and it is predicted that results will be clearer more than in carbonates.

60
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