Thesis Title

(Research Project)

THE IMPACT OF ASSOCIATE POLYMER AND ELECTROLYTE

ON RHEOLOGICAL PROPERTIES FOR ENHANCED OIL
RECOVERY

B.Sc. Chemical Engineering

SUPERVISOR

DR. TANVEER IQBAL

CO-SUPERVISOR

HAFIZ MUDASER AHMAD

Group Members

Name Registration No.

Shah Muhammad 2016-CH-207
Zubair Khalid 2016-CH-227
Naeem Akhtar 2016-CH-289

DEPARTMENT OF CHEMICAL, POLYMER, AND COMPOSITE

MATERIALS ENGINEERING
University of Engineering and Technology Lahore, New
Campus
June 2020

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 UNIVERSITY OF ENGINEERING AND TECHNOLOGY
LAHORE, NEW CAMPUS-54890, PAKISTAN
DEPARTMENT OF CHEMICAL, POLYMER AND COMPOSITE MATERIALS
ENGINEERING

This thesis is written by

1) Shah Muhammad

2) Zubair Khalid

3) Naeem Akhtar

Under the direction of their thesis advisor, has been presented and accepted, in partial

fulfillment of the requirements of the degree of Bachelor of Science in Chemical

Engineering.

__________________________ __________________________
Dr. Tanveer Iqbal Dr. Sikander Rafiq
Department Chairman (Supervisor)

__________________________
Dr.
(Internal Examiner)

Date: _____________________

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© Mr. Haris

© Mr. Aslam

© Ms. Alina

© Mr. Akbar

2020

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 Dedication
“This work is dedicated

To our beloved parents and

Our kind teachers”

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 ACKNOWLEDGMENTS

Thanks to Allah Almighty for all the countless gifts you have offered me and thanks to my

family for their love and support.

Foremost, I would like to express my sincere gratitude to my supervisors Dr. Tanveer Iqbal

and Hafiz Mudaser Ahmad and for their never-ending support during Bachelor’s thesis and

research, for his patience, motivation, enthusiasm, and immense knowledge. Guidance of

both advisors helped me in all the time of research and writing this thesis. I could not have

imagined having better advisors and mentors for my project. Most of all, I am fully

indebted to Dr. Tanveer Iqbal and Hafiz Mudaser Ahmad, my supervisors, for their

wisdom, passion, encouragement, and for pushing me farther than I thought I could go. it

is a great honor to work under your supervision. And I would also like to thank my team

members and friends for letting me give up both and on and off the water.

And also, I would like to thank our department for providing us every facility during

research and the staff members for their continuous support throughout this period. This

thesis become reality with kind support and help of many individuals. I would like to extend

my sincere thanks to all of them.

My thanks and appreciations also go to my people who have willingly helped me out with

their abilities. I also place on record, my sense of gratitude to one and all who, directly or

indirectly, have lent their helping hand in this venture.

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 ABSTRACT

The world energy requirements are escalating day by day as a result of an increase in

population. To fulfill those requirements crude oil is the most essential source of energy

and other than crude oil not to sufficiently integrating energy sources to replace it. So, there

is a need to improve the oil extraction underneath the surface by improving technologies

of Enhanced Oil Recovery (EOR). These technologies are strictly depending on different

parameters such as viscosity, shear rate, shear stress, storage modulus, and loss modulus,

etc. of flooding fluid in the original reservoir and all these parameters can be affected by

temperature, pressure, the concentration of polymer used for this purpose, concentration of

salt (effect of salinity) and most important residence time in the original reservoir.

Rheology is most important and suitable to check and measure all these earlier explained

parameters and either the fluid or polymer can be used or not for EOR. Often conventional

polymers (HPAM, PAM, HEC) are used for EOR flooding which can’t maintain the

rheological properties such as viscosity, shear rate, and biodegradability for long required

time and cannot bear high salinity under the harsh condition real reservoirs.

The objective of this study is to reveal the rheological properties of associate polymer that’s

why conventional polymer is replaced by an associate polymer which can bear high

salinity, maintain viscosity, and resist degrading at high temperature. To make a successful

application of that polymer rheology is performed to study the effect of concentration of

polymer (associated), the concentration of salt (CaCl₂), and time at a different temperature

as 20°C, 40°C and 60°. The polymer is used in solution form with distilled water, the first

rheology is performed for only polymer solution for different concentrations as 0.01wt%,

0.1wt%, and 0.15% at three constant temperatures as 20°C, 40°C and 60°. The result is
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plotted as viscosity Vs shear rate. It shows shear thickening behavior which favorable for

EOR. Then the same experimentation is performed polymer with different concentrations

of salt as 0.05M, o.1M, and 0.15M at the same temperatures and the resulting graph shows

that the trend remains unchanged by adding salinity which indicates that associate polymer

can bear high salinity and it is favorable to salinity reservoirs. After that effect of time is

observed for 120 minutes by keeping 200 1/s shear rate constant of both solutions polymer

and polymer with salt at the same temperatures and resultant viscosity vs time shows that

there is no major effect of time on viscosity. Hence all rheological properties resulting in

experimentation are satisfied and associate polymer more preferable on conventional

polymer for EOR.

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 CONTENTS
Acknowledgments............................................................................................................................ 6

Abstract ............................................................................................................................................ 7

List of Figures ................................................................................................................................ 14

Abbreviations ................................................................................................................................. 15

1 Introduction and objective ..................................................................................................... 16

1.1 Overview ........................................................................................................................ 16

1.2 Background .................................................................................................................... 17

1.2.1 Primary recovery .................................................................................................... 17

1.2.2 Secondary recovery ................................................................................................ 18

1.2.3 Tertiary recovery .................................................................................................... 18

1.3 Objectives and problem statement ................................................................................. 23

2 Literature review .................................................................................................................... 25

2.1 Overview ........................................................................................................................ 25

2.2 Sweep Efficiency ........................................................................................................... 26

2.3 Interfacial Tension ......................................................................................................... 27

2.4 Wettability alteration ..................................................................................................... 28

2.5 Viscous fingering ........................................................................................................... 28

2.6 Mobility control ............................................................................................................. 29

2.7 Polymer flooding ........................................................................................................... 30

2.7.1 Bio-polymers.......................................................................................................... 30

2.7.2 Surfactant ............................................................................................................... 31

2.8 Alkaline flooding ........................................................................................................... 32

2.9 Foam flooding ................................................................................................................ 32

2.10 Nano-technology ............................................................................................................ 33

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2.11 Types of nanofluids flooding ......................................................................................... 34

2.11.1 Polymeric Nanofluids ............................................................................................ 34

2.11.2 Smart nanofluid Flooding ...................................................................................... 34

2.12 Alkaline Surfactant Polymer Flooding .......................................................................... 35

2.13 Polymers ........................................................................................................................ 38

2.13.1 Monomers .............................................................................................................. 38

2.14 On source Basis.............................................................................................................. 38

2.14.1 Naturally occurring ................................................................................................ 38

2.14.2 Man Made or synthetic monomers......................................................................... 39

2.15 On the Basis of Structure ............................................................................................... 39

2.15.1 Linear Monomers ................................................................................................... 39

2.15.2 Cyclic Monomers ................................................................................................... 39

2.16 Polar and Non-Polar Monomers .................................................................................... 39

2.17 Polymers ........................................................................................................................ 39

2.18 Classification of polymers ............................................................................................. 40

2.19 Based on Source............................................................................................................. 40

2.19.1 Natural Polymers ................................................................................................... 40

2.19.2 Semi-Synthetic polymers ....................................................................................... 40

2.19.3 Synthetic Polymer .................................................................................................. 40

2.20 Based on structure .......................................................................................................... 41

2.20.1 Linear Polymer....................................................................................................... 41

2.20.2 Cyclic Polymers ..................................................................................................... 41

2.21 Based on their formation phenomena ............................................................................ 41

2.21.1 Condensation Polymers.......................................................................................... 41

2.21.2 Addition Polymers ................................................................................................. 42

2.22 High Temperature Polymer............................................................................................ 42

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 2.23 Properties of Polymers ................................................................................................... 42

2.24 Uses of polymers............................................................................................................ 42

2.25 Salts and their Classification .......................................................................................... 43

2.25.1 Alkaline Salts ......................................................................................................... 43

2.25.2 Acidic Salts ............................................................................................................ 43

2.25.3 Neutral Salts ........................................................................................................... 43

3 Materials and Methodology ................................................................................................... 44

3.1 Materials ........................................................................................................................ 44

3.1.1 Salt ......................................................................................................................... 44

3.2 Associative Polymer ...................................................................................................... 45

3.3 Distilled water ................................................................................................................ 45

3.4 Methodology .................................................................................................................. 46

3.5 Rheology ........................................................................................................................ 46

3.6 Types of Rheology and properties ................................................................................. 46

3.6.1 Steady state Rheology ............................................................................................ 47

3.6.2 Dynamic Rheology ................................................................................................ 47

3.7 Properties ....................................................................................................................... 47

3.7.1 Shear rate ............................................................................................................... 47

3.7.2 Shear stress............................................................................................................. 48

3.7.3 Viscosity ................................................................................................................ 48

3.7.4 Torque .................................................................................................................... 49

3.7.5 Rheometry .............................................................................................................. 49

3.8 Rheometer ...................................................................................................................... 49

3.9 Working Principle .......................................................................................................... 50

3.9.1 Parts of Rheometer ................................................................................................. 50

3.10 Types of Rheometer: ...................................................................................................... 51

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 3.10.1 Shear Rheometer .................................................................................................... 52

3.10.2 Extensional Rheometer .......................................................................................... 52

4 Experimentation ..................................................................................................................... 54

4.1 Overview ........................................................................................................................ 54

4.2 Chemicals....................................................................................................................... 54

4.2.1 Polymer .................................................................................................................. 54

4.2.2 Salt ......................................................................................................................... 55

4.3 Apparatus ....................................................................................................................... 55

4.3.1 Weight balance....................................................................................................... 55

4.3.2 Magnetic stirrer ...................................................................................................... 56

4.3.3 Beakers along with aluminum file ......................................................................... 57

4.4 Preparation of solutions ................................................................................................. 57

4.4.1 Polymer solution preparation ................................................................................. 58

4.4.2 Preparation of salt solution .................................................................................... 58

4.5 Experimental Sequence .................................................................................................. 59

5 Results and Discussion .......................................................................................................... 60

5.1 Overview ........................................................................................................................ 60

5.2 Effect of polymer concentration: ................................................................................... 61

5.3 Effects of salt ................................................................................................................. 66

5.4 effect of time .................................................................................................................. 69

5.5 Effect of temperature ..................................................................................................... 71

6 Socio and Economic considerations ...................................................................................... 72

6.1 Social Impacts of Enhanced Oil Recovery (EOR) ......................................................... 72

6.1.1 Social Impacts ........................................................................................................ 72

6.1.2 Land disturbances .................................................................................................. 73

6.1.3 Effect on water ....................................................................................................... 73

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 6.1.4 Deterioration of Surface water ............................................................................... 73

6.1.5 Ground water contamination:................................................................................. 74

6.1.6 Air Pollution: ......................................................................................................... 74

6.2 Economic impact: .......................................................................................................... 74

7 Conclusion and Recommendations ........................................................................................ 76

7.1 Conclusion ..................................................................................................................... 76

7.2 Recommendations .......................................................................................................... 78

8 References .............................................................................................................................. 81

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 LIST OF FIGURES

Figure 1 Secondary Oil Recovery(Miklos et al., 1973) ................................................................. 18

Figure 2 Enhanced Oil Recovery(Rodriguez et al., 2016) ............................................................. 19
Figure 3 Molecular Structure of HPAM (Abidin et al., 2012) ....................................................... 21
Figure 4 Molecular structure of Xanthan gum(Abidin et al., 2012) .............................................. 22
Figure 5 Association among polymer chains(Wever et al., 2011b) ............................................... 23
Figure 6 Effect of surfactant on interfacial tension(Sangroniz et al., 2019) .................................. 27
Figure 7 Wettability alteration(Bila et al., 2019) ........................................................................... 28
Figure 8 Viscous fingering(Gao, 2014) ......................................................................................... 29
Figure 9 Shear rate demonstration ................................................................................................. 48
Figure 10 Rheometer...................................................................................................................... 49
Figure 11 Geometry of Rheometer ................................................................................................ 51
Figure 12 Weight balance .............................................................................................................. 56
Figure 13 Magnetic Stirrer ............................................................................................................. 56
Figure 14 Experimental sequence .................................................................................................. 59
Figure 15 viscosity profile of 0.05 wt.% polymer at different temperatures ................................. 64
Figure 16 viscosity profile of 0.1 wt.% polymer at different temperatures ................................... 64
Figure 17 viscosity profile of 0.05 wt.% polymer at different temperature ................................... 64
Figure 18 viscosity profile 0.15 wt.% polymer at different temperatures...................................... 65
Figure 19 flow curves of 0.15 wt.% polymer at different temperatures ........................................ 65
Figure 20 Effect of salts on steady shear viscosity of polymer (0.15wt%) at 20°C....................... 67
Figure 21 Effect of salts on steady shear viscosity of polymer (0.15wt%) at 40°C....................... 68
Figure 22 Effect of salts on steady shear viscosity of polymer (0.15wt%) at 600°C..................... 68
Figure 23 Flow curves of polymer in salted water at different temperature .................................. 69
Figure 24 Effect of residence time on steady shear viscosity of polymer (0.15wt%) at different
temperature .................................................................................................................................... 70

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 ABBREVIATIONS
EOR Enhanced Oil Recovery

HPAM Hydrolyzed Polyacrylamide

OOIP Original Oil in place

PAM Polyacrylamide

HEC Hydroxyethyl cellulose

IFT Interfacial Tension

ASP Alkaline surfactant polymer

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 Chapter 1

1 INTRODUCTION AND OBJECTIVE

1.1 OVERVIEW
Oil demand is increasing day by day and according to some surveys it is increasing 1% a

year and oil demand was 85 million barrel a day but according to future assessments it will

goes up to 110 million barrels in 2030 (Gbadamosi et al., 2019). And this demand of oil

cannot be meet with conventional recovery method, therefore application of enhanced

recovery become significant. As conventional method recovers only 40% of OOIP and

after enhanced oil recovery (EOR) it goes up to 80-90% OOIP. The average recovery of

oil from reservoir is estimated up to 42%. According to the Norway petroleum world have

85.5 billion of barrels of oils(Kokal & Al-Kaabi, 2010).

Major consumption of oil is in transport industry and it controlled the oil demand and oil

market and half of oil is used in transportation industry. Although, in the presence of other

renewable energy resource like Bio-fuels, electricity they have gained the required

potential to meet the oil demand in the upcoming years(Barman et al., 2001). So Enhanced

oil recovery become a purposeful way to meet the required demand in market. So, by using

multiple EOR methods in which addition of chemicals or agents that increases the viscosity

of injection water which increases the viscosity of injectants fluid and creates high pressure

differences and in results higher recovery of oil(Sangroniz et al., 2019).

The mostly used polymers is HPAM and its derivatives and it is frequently used due to low

prices and another type which is commonly used is Xanthan gum which is known as bio-

polymer but due to higher cost it is not economically suitable(Needham et al., 1987).
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Hydrophobically modified polymers also known as associative polymer which shows

promising results in many EOR application because of their stability at higher shear rate

encountered in heterogenous reservoir and instant viscosity increase. Lower concentration

usually prefers due to cost and in associative polymers which are very robust and have

shear thickening ability are mostly required in EOR process(Kv, 2013).

1.2 BACKGROUND

1.2.1 Primary recovery

Primary recovery is defined as first stage of recovering oil underneath earth surface and

comes naturally to earth surface due to pressure difference between earth surface and

reservoir pressure(Wever et al., 2011b). Gases that are present in the reservoir when

expands exerts force on the oil and causes the movement of oil towards lower pressure

region. Primary recovery can also be done by mechanical means like pumps or suction lift

devices which are normally uses when we encountered with the reservoir having high

depth. Mostly, rod pump is used which is actually reciprocating pump which creates high

pressure difference and more than two pumps are uses in series to recover oil efficiently.

In this initial recovery stage only up to 15% oil recovers by OOIP. Due to high quantity of

oil remained after primary recovery we have to move towards secondary recovery.

Approximately, 2*10^12 barrels of light oil and 5*10^12 barrels of heavy oil remains

unrecovered after conventional method, like the natural rise of hydrocarbons to earth

surface(Gbadamosi et al., 2019). To meet the supply-demand balance it became very clear

that to meet the required demand of oil escalate the recovery of oil from not sufficiently

utilized reservoir become significant.

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1.2.2 Secondary recovery
Secondary recovery is defined in terms of injection of water into the reservoir due to

reduction in pressure of reservoir after primary recovery. In water injection water sweeps

the oil and causes a high pressure in production well.

Figure 1 Secondary Oil Recovery(Miklos et al., 1973)

But a major drawback of water injection is that water have lower viscosity as compared to

oil and it leaves a huge amount of oil that is trapped by capillary forces between the rocks

or bypassed in thief zones. It recovers up to 40% of OOIP.

1.2.3 Tertiary recovery

Tertiary recovery is also known as enhanced oil recovery and it is done by injecting

different chemicals like polymers, surfactants, alkali and nanoparticles and energy(heat)

into reservoir. Steam injection is not preferred to due to high depth of reservoir and

economically not suitable. As tertiary recovery becomes a purposeful way to meet demand-

supply balance of fuel. It recovers up to the 80-90% of OOIP(Kokal & Al-Kaabi, 2010).

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Efficiency of EOR process can be evaluated on the basis of many factors like sweep

efficiency and mobility ratio etc.

Figure 2 Enhanced Oil Recovery(Rodriguez et al., 2016)

Ultimate goal is to enhance Overall oil displacement efficiency which is defined as the

combination of both macroscopic displacement efficiency and microscopic displacement

efficiency. Microscopic efficiency defined in terms of the ability of injecting fluid to

contact oil zone volumetrically and microscopic efficiency is the capability of injectant is

to mobilize the oil trapped in thief zones or bypassed(Urbissinova et al., 2010). Polymer

flooding has acquired great attention both in academic and field applications. Water-

soluble polymers shows higher success factor for multiple EOR application, mainly in

China(Han et al., 1999). In polymer flooding, one of most challenging tasks for Researcher

is to maintain polymer viscosity in Harsh reservoir condition. Polymer viscosity relies on

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chemical Structure of polymer, molecular weight, concentration of Polymer used,

temperature, salinity, pH(Wilton & Torabi, 2013)(Wever et al., 2011a)(Buchgraber et al.,

2009).

Hydrolyzed polyacrylamide (HPAM) is most commonly used polymer in many EOR

applications due to suitable chemical and physical properties and by taking in economic

aspects it has low price in market as compared to the other polymers. HPAM can bear the

temperature of up to 100⁰C and but found to be sensitive in the presence of metal ions and

salts like Ca2+ and Mg2+ which decreases the efficiency(Zhu et al., 2013). HPAM is

extensively used as oil displacement agent but notorious congenital drawback is failing in

hostile environment, high temperature, high concentration of salts like Calcium Chloride

and Magnesium Chloride etc. and unfavorable permeability of reservoir(Wang et al.,

2011). Metal ions in oil field brine interact and largely surrounds the repulsion occurring

from Carboxylic group along the structure of Hydrolyzed polyacrylamide resulting coils

of polymer to caved in, reduction in hydrodynamic volume and finally the overall effect

resulting lowering solution viscosity(Zaitoun & Potie, 1983). Effectiveness of HPAM

aqueous solution becomes genuine concern at elevated temperature resulting into extensive

hydrolysis causes conversion of amino group to carboxylic groups and, which triggers the

formation of hydrolyzed product when comes in contact with Calcium and magnesium

ions, which are commonly present in reservoir. More robust, efficient and cost- effective

thickeners are needed(Environments et al., n.d.). Molecular Structure of HPAM is give

below:

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 Figure 3 Molecular Structure of HPAM (Abidin et al., 2012)

Bio-polymers are used in many EOR application and a step towards the green chemistry

and to protect the environment. Xanthan gum is mostly used as biopolymer and one of the

most prominent factor of Xanthan gum is that it can bear high salinity and can be used with

other injectant like surfactants and alkali for recovery of oil(SANDVIK & MAERKER,

1977). Molecular structure of Xanthan gum is given below:

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 Figure 4 Molecular structure of Xanthan gum(Abidin et al., 2012)

An associative water-soluble polymer shows encouraging results as compared to

conventional polymers (HPAM, Xanthan gum etc.)(Pancharoen et al., 2010). Polymer

structure consists of hydrophilic group, which is usually comprises long chain molecules

(Backbone) and hydrophobic group present in small number may be present on chain ends

or along chain. Hydrophobic group construct intermolecular and intramolecular association

resulting into strong three-dimensional network(Buchgraber et al., 2009). This stance

increases the viscosity even at low concentration of polymer and one of the prominent

factors of these newly developed polymers is that their functional group can bear high

salinity as compared to traditional polymers used(Lara-ceniceros et al., 2007). Associative

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polymer forms inter and intra molecular associations which gives the strength to the

structure and causes the shear thickening behavior(Bautista & Puig, 2006).

Figure 5 Association among polymer chains(Wever et al., 2011b)

In this work, aqueous solution of associative polymer of various concentration were

analyzed and found stable at high temperature and high saline environment. The effect of

temperature, polymer concentration, electrolytes and residence time of polymer on steady

state rheology is discussed.

1.3 OBJECTIVES AND PROBLEM STATEMENT

Problem Statement

Because conventional polymers like HPAM degrades at high temperature and cannot

maintain their viscosity in hostile environment and degrades which results in the reduction

of viscosity. As reduction in viscosity causes the loss in viscosity and causes poor

efficiency of EOR process.

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Objectives

Major objectives of this project were to analyze rheological properties of associative

polymer solution of different concentration and mixed with salt to predict the behavior of

polymer under constant shear rate to study the effect of temperature, concentration salts

and residence time on steady state rheology. As during flooding of injectant there are

different beds of materials like injectant has to counter with the shale bed, the slats bed and

as polymer remained in the reservoir for 10-12 month so it is important that to study the

effect of residence time on polymer viscosity

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 Chapter 2

2 LITERATURE REVIEW

2.1 OVERVIEW
Oil and gas remain major contribution to world energy even though in the presence of other

renewable energy resources(Udeagbara, 2017). Enhanced oil recovery is the technique,

which recovers one third of the oil that remains trapped in reservoir or by pass in other

way, is classified as Tertiary recovery of oil. Efficiency of any EOR method is determined

by overall displacement oil efficiency which is further classified into two domains one is

macroscopic which defines effectiveness of injecting fluid volumetrically and other is

microscopic which also known as pore scale is the property of injecting fluid to extract oil

from the rocks(Rodrigue & Romero-zero, 2013). Basically, EOR is classified into two

types

• Thermal

• Non-thermal

Thermal method which is not abundantly used because of high depth of reservoir and not

suitable economically, and other is non-thermal which mostly used in recovery

methods(Jackson et al., 2019).

Non-thermal method which is further sub-categorized into different domains namely as

• Polymer flooding

• Surfactants flooding

• Alkaline flooding

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 • Nano-particles flooding

• Foam flooding

And binary mixture of these chemicals increases the stability of injecting fluid and

increases the efficiency of overall process. And after doing several experiments on pilot

and lab scale have given promising results by using combination of these chemicals for

example Polymer + Surfactants or nano-particles + polymer.

Combination of polymer and nanofluids has high efficiency due to nanofluids governed by

nano-technology. There are limitations for non-thermal (Chemical) process as polymer loss

its viscosity in presence of reservoirs brine and at elevated temperature and surfactant

which adsorb in the pores of rock(Rellegadla et al., 2017). Nano-technology helps solving

problem like drilling operations and recovery of oil were improved by introduction of

properties such as structural disjoining pressure, to make rock oil wet to water wet and

interfacial tension reduction(Gbadamosi et al., 2019). The main objective of the overall

process is to alter some properties in the reservoir as a result of injection:

• Sweep Efficiency

• Interfacial Tension

• Wettability alteration

• Viscous fingering

• Mobility Control

2.2 SWEEP EFFICIENCY

Sweep efficiency is the ability of injectant fluid to sweep oil trapped or bypassed in

Heterogenous reservoir. Sweep efficiency is calculated as sum of microscopic

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displacement efficiency and macroscopic displacement efficiency. Microscopic efficiency

is defined in terms of ability of fluid contacting oil zones in reservoir as a bulk and on the

other hand macroscopic displacement efficiency is the ability of the injecting fluid to move

oil in the zones that is not driven by traditional water flooding(Rodrigue & Romero-zero,

2013). Sweep efficiency depends upon multiple factors like density difference between

displacing fluid and displaced fluid, Selection of injection pattern, permeability of the

reservoir.

2.3 INTERFACIAL TENSION

Surfactants are usually known as the surface-active agent because during surfactants

flooding the molecules adsorb and form emulsion on the water/oil and oil/rock interface

which causes the trapped oil to move from thief zones in heterogenous fractured

reservoir(Nilsson et al., 2013). Formation of emulsion at interface is due to fact that

elevation in the length of structural hydrophobic chain the adhesion between two phases

and length of structural hydrophobic

Figure 6 Effect of surfactant on interfacial tension(Sangroniz et al., 2019)

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chain is directly related and resulted increase in the recovery of oil. Interfacial tension can

be measured by various method like measurement of concentration at interface electrically

(Conductivity)(Saha et al., 2019).

2.4 WETTABILITY ALTERATION

Production of oil reduced by capillary forces in well-bore zone and rupture reservoir which

offer lower recovery of oil as result of primary and secondary recovery due to lower

Figure 7 Wettability alteration(Bila et al., 2019)

viscosity of water. Wettability alteration means changing reservoir wettability from oil wet

to water wet by injection of chemicals into reservoir. The change in wettability of oil wet

and those reservoirs which are not strongly water wet enhances the recovery of oil(Xia et

al., 2004).

2.5 VISCOUS FINGERING

Viscous fingering is the phenomenon in which injectant fluid bypass the oil trapped in

reservoir by capillary forces as result of lower viscosity as compared to displaced fluid.

This is the major drawback encountered in secondary recovery where water bypass the oil

due to lower viscosity creating non-uniform pattern(Gao, 2014). As a result of viscous

fingering it will decrease the sweep efficiency which in turns reduces the recovery of oil.

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 Figure 8 Viscous fingering(Gao, 2014)

2.6 MOBILITY CONTROL

Mobility control is related to viscous fingering and is defined as a ratio of viscosity of

displaced fluid to the viscosity of displacing fluid and mathematically can be written as:

M=Kwµo/Koµw

Where,

µo= Oil viscosity (cP)

µw= Water viscosity(cP)

Ko= Permeability to Oil

Kw= Permeability to water

Mobility ratio can be used to evaluate the recovery whether it is stable or not. Value of M

should be less than 1 because if M>1 then it means that injectant has higher mobility than

the oil which in turns bypass the oil and viscous fingering occurs and causes in lower oil

recovery. If M<1 it means that injectant have greater viscosity as compared to oil which

swept oil efficiently and as result higher recovery of oil(Rellegadla et al., 2017)(Druetta &

Picchioni, 2019).
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2.7 POLYMER FLOODING
Polymer flooding is required when water flooding is not efficient due to effect of formation

of viscous fingers mainly caused by early water injection and to increase the efficiency of

flooding polymers, which are usually soluble in water added to water to form a solution

which injected into reservoir to enhance oil recovery(Rodrigue & Romero-zero, 2013).

Injection of polymers enhances the recovery of oil recovery through this combined

mechanism of mobility control, Permeability and during the deformation process they have

shown great viscous and elastic property. There are two basic types of polymer, synthetic

and Biopolymer(Rellegadla et al., 2017). Mostly used synthetic polymer is partially

hydrolyzed Polyacrylamide (HPAM) and it has shown high tolerance against bacterial

decay, high solubility, and low cost and it’s has overall negative charge due to hydrolysis

during flooding in which some amide groups (-CONH2) changes it properties into (-COO-

). And it has disadvantages that it is sensitive to pH, temperature, salinity and hardness(Al-

Shakry et al., 2019).

2.7.1 Bio-polymers
And other type is biopolymer like Xanthan gum, lignin, Welan gum and Guar gum etc.

Bio-polymers have some merits and demerits like they are highly tolerant against too high

salt concentration, temperature, stability, friendly to environment, good solubility in water

and excellent hydration properties(Rellegadla et al., 2017). Major drawbacks of Bio-

polymers that they are high susceptible to degradation through biological process and

oxidation, biopolymers can be trapped into reservoir, decomposition through oxidation and

degradation through thermal process, insoluble in water and performance dependent on

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presence of cations in reservoir. Formaldehyde is used to minimize the degradation of

Xanthan gum(Han et al., 1999).

2.7.2 Surfactant
Surfactants are those materials which reduced the interfacial tension, which enhanced

fluid/fluid interaction and through wettability alteration and it is also known as surface

active agent(Shen et al., 2010). Basically, it consists of two functional group one is

hydrophilic (quaternary ammonium salts, carboxylates, alcohols and sulfonates etc.) which

is usually water-soluble and other one is hydrophobic (Long chain hydrocarbon,

fluorocarbon and short-term polymer etc.). Reduction in IFT is measured through capillary

number and more the value of capillary number more reduction in IFT(Sharma et al., 2016).

Carbonate reservoirs are flooded with cationic surfactant while sandstone reservoirs are

flooded with anionic due likeness of charge which makes process more efficient. Basically,

there are three types of surfactants cationic, non-ionic, anionic and zwitterionic surfactants,

and due to low efficiency of these surfactants there are more surfactants being developed

like bio-surfactant, viscoelastic surfactants, Gemini surfactants and polymer surfactants.

Anionic surfactants (COO-, SO42-, SO3-) mostly used for sandstone reservoir and sulfonates

surfactants shows high stability in high temperature but shows less stability to high salinity

and sulfates are stable in high salinity and decomposes at high temperature(Abdel-Azeim

& Kanj, 2018). Cationic surfactants are those which bear positive charge, used for

carbonate reservoirs, through combination of with halide group. They are more efficient to

remove abundant hydrocarbons from carbonate reservoir and hydrogenation mechanism at

high pressure required during their formation(Olajire, 2014).

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2.8 Alkaline flooding
Alkaline flooding is another method to enhance oil recovery by flooding alkali which reacts

with acidic component of organic compound (raw oil) to form emulsion which acts as

surfactants and lowers IFT. Depending upon the composition of rock alkali comes in

contact with rock in different ways like hydrolysis and dissolution reaction. Most used

alkali compounds are sodium metaborate, sodium hydroxide, sodium carbonate and

sodium bicarbonate and concerned factors for alkali selection are clay type, minerals

contents and the presence of divalent cations(Olajire, 2014). There are some limitations of

alkali flooding that NaOH is less preferred due interaction with sandstone surface at

elevated temperature and causes sandstone weight loss and further Na2CO3 precipitates due

to presence of divalent cations but is preferred due to its low cost and have high ability of

transport in porous media and NaBO2 is tolerant to divalent cations. Due to presence of

Gypsum and anhydrite alkali flooding is preferred in sandstone reservoir(English et al.,

2002).

2.9 FOAM FLOODING

Foam flooding is another technique in which made by a phenomenon in which gas is

dispersed into liquid in that way liquid phase becomes continuous phase and some portion

of gas phase becomes discontinuous and made film(Gbadamosi et al., 2019). Foam

increases oil recovery by two ways, one is by increasing injectant viscosity and secondly

bubbles in foam passes through porous media. Mostly, foam used are air foams, CO2 foams

and N2 foams and chemicals used are surfactants, polymer, and proteins. Major drawback

of foam flooding is the stability of foam under reservoir at elevated temperature, high

salinity and high pH factors(Gao, 2013).

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2.10 NANO-TECHNOLOGY
The applications of nanotechnology have become a new trend in chemical Enhanced Oil

Recovery e.g. ionic liquid having nano particles use for EOR is a solution of many issues

loss of the, completion of drilling process, flow rate problem and hydraulic

fracturing(Gbadamosi et al., 2019). It shows that nanofluids i.e. mixture of nano particles

and liquids can increase the trapped efficiency because of nano dispersion. nano particles

mixed with aqueous alcohol or brine and nanofluids chemical based i.e. surfactants and

polymer are used to enhance the flooding properties of injected substance called nanofluid

flooding. Recently nano technology applications for Enhanced Oil Recovery are used in

different countries mostly in Colombia for a trial(Druetta & Picchioni, 2019).

In the nanofluids flooding mechanism for EOR purpose they act same kind of quality as

surfactants through the wettability, interfacial tension reduction and emulsion

stabilization(Pellens et al., 2004). Wettability (to make rock oil wet to water wet) by

nanofluids is and the forces between water and rock surface which are not in equilibrium

and thus effect the property of spreading over rock surface. Initially a wedge film is formed

in an ordered way of nanoparticles within the fluid between the solid and oil substrate.

With the increase of film tension or combination of different pressure (Dispersion forces,

electrostatic forces etc.) the ability of nanoparticles to move on wedge tip also increases

thus enhancing the spreading behavior of nanoparticles(Sangroniz et al., 2019). Interfacial

tension is the decrease in frictional force between the oil and the displacing fluid IFT is

measured by capillary number and with the increase in capillary number the oil recovery

also enhances. The adsorption which is irreversible at the interface guard the emulsion

Page | 33
droplets formed against the aggregation and coalesce thus increases stability(Bila et al.,

2019).

2.11 TYPES OF NANOFLUIDS FLOODING

2.11.1 Polymeric Nanofluids

A combination of polymers and nanofluids which presents sterling and fascinating

properties for EOR purposes. This newly discovered material possesses improved thermal

properties, tolerant to high salt concentration behavior, rheological properties ion shielding

effect thermal vibrations of nanoparticles, so PNF are most suitable to perform in high salt

concentration environment and high temperature(Wever et al., 2011a).

Combination of nanoparticles and surfactants studied through experimentation testing for

EOR. The properties modified are wettability change, achievement of ultralow interfacial

tension, and stable emulsion.

2.11.2 Smart nanofluid Flooding

Flooding of nanoparticles solution in water NaCl and alcohol is also known as the smart

nanofluid flooding. This process dependent on large surface area and other built-in

properties of the particles to potentiate oil recovery. Smart fluids can alter IFT reduction at

the interface of oil and water, viscosity decreasing and most of the fluids alters the

wettability to improve oil recovery(Wang et al., 2011).

Due to unfavorable economic condition and environmental drawback, ionic liquids a

molten salt is used to change conductivity reusability and good thermal stability. depending

upon the compositions of anions cations their properties also changes.

Page | 34
Nano fluids are termed as smart fluids and uses with surfactants to reduce the interfacial

tension up to 70-80% than conventional fluids. The main purpose of nanoparticles is the

intensify and improve hereditament at very small volume mass of scattering medium and

the major specification about nanoparticles is that having hereditaments are usually in

dimension of particles and suspension of nanoparticles increases sedimentation stability,

Rheological properties, stress-strain, electrical and optical properties. Dispersed particles

in solution alter the IFT specification of the liquid-liquid system and hence increase the

efficiency of EOR. Nanoparticles presence at the interface layer reduces IFT due

absorption of particles in liquid and concentration larger than 0.4% completely removes

surfactants from an aqueous phase. An experimental setup is prepared in which aqueous

solution of anionic surfactants and nanoparticles which contains a negligible amount of

iron was used to analyze the effect of nanoparticles in EOR. The first setup of experiments

is done for IFT, wettability, and adsorption and equipment used for the measurement of

interfacial tension(Esfandyari Bayat et al., 2014). Following methods are adopted for our

purpose:

❖ Pendant drop technique supported by a mathematical equation which is also known as

the Laplace equation which brings out us the relation between difference in pressure

and surface tension

❖ Sessile drop technique which is based on contact angle wrinkle to measure the

capability of decentralized solid surface

2.12 ALKALINE SURFACTANT POLYMER FLOODING

The future energy demand and high prices of oil have necessitated the demand for EOR

methods. Because of the several drawbacks of other processes like adsorptive surfactant
Page | 35
loss ASP is a highly beneficial and cost-effective method with the significant advance

techniques to reduce IFT, improving the capillary number, potentiate microscopic

efficiency, altering mobility ratio and refine macroscopic sweep efficiency(Xia et al.,

2004). Mobility ratio is also known as the mobility of displacing fluid to the ability of

movement of the displaced fluid. Mobility ratio is kept equal or less than one by improving

relative permeability, increased viscosity of injecting fluid, and vice versa in case of the

displaced fluid. Similarly, capillary forces also influence the oil recovery in fractured and

non-fractured reservoirs differently. The two different number capillary numbers and bond

numbers are used to check the oil displaced in this method.

ASP is the combined injection of surfactant, polymer, and alkali to swept and displacing

purposes in the petroleum industry. A surfactant is used to activate the surface consists of

two functional groups one is hydrophilic which is usually Water Soluble and the other one

is hydrophobic which is oil Soluble(Olajire, 2014). In ASP surfactant plays a role to

decrease the surface tension between raw oil and NaCl solution and contribute to the

formation of oil banks. The selection of surfactant is based upon the ability to thermal

stability brine resistant etc. And polymer injection is the process of injection of polymer to

the water, injected into the reservoir to increase the viscosity of the aqueous phase. The

most commonly used polymers now days are hydrolyzed Polyacrylamide and xanthan a

biopolymer and some of their derivatives which are divided into two classes which consist

of organic and biopolymers as sodium carboxymethyl cellulose and guar gum etc.

respectively. A group of associative polymers recently discovered in the oil fields consists

of a high ratio hydrophilic group, which consists of long-chain structure with backbone

and a low ratio of the hydrophobic group which flocculates to reduce their windage to

Page | 36
water. Another fundamental point of this is that the functional group on this polymer is less

tolerant to high salinity in comparison with ploy acrylamide, their viscosity decreases with

increasing salt concentration(English et al., 2002).

Rheology of polymers is an important area that includes stability, retention, apparent

viscosity and shear rates and resistance, and permeability reduction. Rheology the study of

flowing properties and deformation of materials unprotected to external stress. At high

shear rates, HPAM is susceptible to degrade due to elastic behavior of PAM.PAM is

unstable at 62 degrees centigrade at seawater salinity and which restricts their use for

offshore applications. Polymers and biopolymers are also susceptible for bacterial attack

to deactivate them. Retention is a mechanism of the entrapment of polymers in the pores

of rocks and causes the decreasing in mean velocity of polymers for their breeding. To

estimate the efficiency of polymer flooding it is mandatory to determine the patent value

of viscosity of solution in both shear and extensional flows.

Alkali a basic ionic salt (alkali based) and in a chemical flood supply many advantages and

consists of promoting raw oil emulsification and, maximizing aqueous phase ionic

capability. Alkali can be beneficial in reducing the use surfactant in two ways by reducing

the surfactant adsorption and producing soaps by reacting with acidic component in raw

oil. Alkali picked by the composition clay and presence of divalent cations. Ca and ions

having valency of 2+ can reason of precipitation of sodium carbonate so it is replaced with

sodium boric oxide due to its tolerance for divalent ions. In Alkaline-surfactants-polymer

flooding alkaline and brine solutions are flooded into the reservoirs, the chemicals

component reacts with the natural acidic component present in the oil to form surfactants

in place to reduce IFT between oil and water interface and move considerable amount of

Page | 37
oil into production wells. Alkaline flooding is applied according to oil in API gravity range

of 13-15. Suitable oil formation for alkaline injecting are sandy rocks field than carbon

trioxide and hydrogen carbon trioxide formation that consist of anhydrate or gypsum that

may use very huge quantity of alkali-based chemicals.

2.13 POLYMERS

2.13.1 Monomers
Chemically single molecules which combines to each other to form large chain molecules

are known as monomers. Which are classified on different basis according to their polarity,

structure, source and the type of polymers formed.

2.14 ON SOURCE BASIS

❖ There may be two types of monomers on the basis of their product formed which

are named as,

• Naturally occurring monomers

• Man-made monomers

2.14.1 Naturally occurring

Those monomers which are obtained in their natural form already are known as natural

monomers. They may also be called as biological monomers. The most commonly found

natural monomer is glucose which combines with other chemical molecules to produce and

the product may be cellulose and starch etc.

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2.14.2 Man Made or synthetic monomers
These are the monomers artificially prepared by humans. For examples tetrafluoroethylene,

vinyl chloride are the most common synthetic monomers.

2.15 ON THE BASIS OF STRUCTURE

According to their structures monomer’s may be classified into two following categories:

2.15.1 Linear Monomers

The monomers having straight chain intra molecular bonding are known as Linear

Monomers. e.g. ethylene glycol is a most common linear monomer.

2.15.2 Cyclic Monomers

Monomers having a circular or ring type intra molecular bonding and an opening to connect

with other molecules are classified as cyclic monomers: e.g. styrene is a cyclic monomer.

2.16 POLAR AND NON-POLAR MONOMERS

The molecules of monomers which have double and triple bonds in them are known as

non-polar and with single bonds may be polar e.g. ethylene and vinyl acetate are non-polar

and polar monomers respectively.

2.17 POLYMERS
A chemical combination of monomers to form long chain molecules, those new formed

macromolecules are known as the polymers. e-g DNA is a commonly known polymer in

humane body. There is also polyethylene, poly (vinyl chloride) examples of polymers.

Page | 39
2.18 CLASSIFICATION OF POLYMERS
Different types of polymers are used in our daily routine life which may be categorize

according to their way of formation, origin, structure, types of monomers used or their

functions or behavior. It should be kept noted that as the polymers are formed by

combination of monomers so their classification is also same as of monomers.

2.19 BASED ON SOURCE

Based on the source of polymers they are classified as following;

• Natural occurring,

• Semi synthetic polymers

• Synthetic polymers

2.19.1 Natural Polymers

Those polymers which are found naturally and used without any chemical upgradation are

known as natural polymers e.g. cellulose, starch, and proteins are naturally found polymers

and formed from natural monomers additions to each other. They are found abundantly in

biological resources like plants and animals.

2.19.2 Semi-Synthetic polymers

Semi synthetic polymers are obtained from naturally occurring polymers but they go

through with further chemical additions in them and are known as semi synthetic polymers.

e.g. cellulose nitrate and cellulose acetate are its common examples.

2.19.3 Synthetic Polymer

They are the totally man-made polymers in chemical industry. e.g. nylon 6,6, polyether’s

and plastic which is used for many purposes in our daily routine life.

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2.20 BASED ON STRUCTURE
According to the structure or way of bonding of monomers polymers are divided into two

main following forms;

• Linear Polymers

• Cyclic polymers

2.20.1 Linear Polymer

When monomers are added with each other in a straight chain they from linear polymers.

Poly vinyl chloride and electric pipes are their common examples.

2.20.2 Cyclic Polymers

Those polymers in which cyclic monomers are the subunits are known as cyclic polymers.

e-g cyclic polyethylene.

2.21 BASED ON THEIR FORMATION PHENOMENA

According to the way of formation of polymer they are classified in the following

categories;

• Condensation Polymers

• Addition Polymers

2.21.1 Condensation Polymers

A type of polymers in which subunits of monomers combines to make long chain

molecules with the liberation of some by products like water molecules or methane. e.g.

perylene and polyesters.

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2.21.2 Addition Polymers
In this type of polymers monomers are simply linked to form long chain molecules without

the liberation of any by product.

2.22 HIGH TEMPERATURE POLYMER

These polymers are classified on the basis of their reaction or behavior during their usage.

This is very important type of polymer which are used under high temperature and drastic

condition and they do not degrade with increasing temperature and does their job properly

as at low temperatures.

This is all because of their high molecular weight and structure. Because to rings in these

polymers restrict to break these polymers. Two bonds are required to break in a ring to

break the chain unlike the aliphatic carbon structure.

2.23 PROPERTIES OF POLYMERS

All types of polymers have different properties which may be chemical, and physical

properties. The length of polymers and the linkage of monomers enhances the tensile

strength of polymers. The intermolecular forces give them high strength and hinders the

polymers from melting but they can be converted from crystalline to semi crystalline

structures.

2.24 USES OF POLYMERS

In our daily life polymers are used for many purposes as following;

• Polymers are used in different industries as textile for cloth manufacturing and

plastics industry

• The sewage pipes are also prepared from poly vinyl chloride polymer.
Page | 42
 • A polymer known as Glyptic is used for the manufacturing of coatings and paints.

• Toys, jewelry, insulated containers are also manufactured by using a variety of

polymers e.g. Bakelite.

• High temperature polymers are used in oil industry for crude oil production.

2.25 SALTS AND THEIR CLASSIFICATION

Salt are chemical substances containing cations and anions having positive and negative

charges respectively. They are classified into three mains categorize as following;

• Alkaline Salts

• Acidic Salts

• Neutral Salts

2.25.1 Alkaline Salts

Those salts which produce alkaline solutions when mixed with the water. They are formed

when acid and base react neutrally with each other. Sodium hydroxide is common example

of alkaline salts.

2.25.2 Acidic Salts

When these salts are dissolve in water, they give acidic solution. As a result, they produce

a solution with more ions having more electrical conductivity than other salts.

2.25.3 Neutral Salts

These salts are produced when a strong acid react with a strong base they are completely

neutralize. The salt produced in result of that salt may be acidic alkaline or neutral.

Page | 43
 Chapter 3

3 MATERIALS AND METHODOLOGY

3.1 MATERIALS

3.1.1 Salt
Salt we have used basically is a neutral salt which is a CaCl2 underline is the review of it.

When a strong acid HCl react with a strong base Ca(OH)2 then calcium chloride formed.

It has following properties.

• At room temperature is found in solid form.

• It is a white crystalline solid.

• It has a boiling point of 1600C.

• Highly soluble in water.

• It has ionic bonding because Ca gives 2 electrons and other receive it

• Calcium chloride used for melting ice in winter season.

Calcium Chloride (CaCl2) (Odorless white Powder) having a density of 2.15g/ml with pH

range of 8-9, melting point 782⁰C, hygroscopic in nature and having 99%> purity.

Page | 44
3.2 ASSOCIATIVE POLYMER
Associative polymers are a new type of water-soluble polymer introduced in the modern

EOR process for oil and gas field for flooding. It is a synthetic polymer manufactured by

SNF FLOERGER in France having very high molecular weight ranges from 16-20[4]

million Daltons which comprise of anionic character with bulk density (medium Charge

density) of 0.8 kg/m3 and viscosity measurements are 5g/l(1700cp), 2.5g/l (650cp and) and

1g/l(270cp). It was available in white solid form having nanotubes like shape at room

temperature.

Associative polymers solution generally exhibits two types of behavior shear thickening

and shear thinning by when a shear rate is applied on the solution. In shear thinking solution

the viscosity of solutions gets an increased with the increasing shear rate. But in shear

thinning solution the viscosity gets lower with increasing shear rate. The polymer used in

EOR experiments shows shear thickening behavior after a specific shear until which it may

lower its viscosity because of its initial bonding disturbances.

3.3 DISTILLED WATER

Purified distilled water was taken from the process lab which free of impurities such that

organic and organic compound, heavy metal and biological contaminations such that

bacteria, viruses etc. it was soft water means no carbonates, bicarbonates, sulfates and

chlorides if calcium and magnesium ions were present.

Page | 45
3.4 METHODOLOGY
Enhanced oil recovery is a process of hours to days and days to month, so to use a polymer

or any other material which is undergone flooding process should be capable of bearing

drastic conditions under the reservoir. For this purpose, to check the properties of polymer

and salts used in our EOR project rheological method was used, which is explained

following in detail.

3.5 RHEOLOGY
The word rheology is derived from Greek Language ‘rheo’ meaning flow and ‘logi’

meaning study of. So, the study and analysis of matter in flow, the matter should be in

liquid state or slurries which respond to a shear force applied to them rather than deforming.

The force applied on the materials is referred to as the shear rate. Which gives aid to check

the materials response as follow

Force = (property) (measure of response)

The above equation gives the amount or stress applied on materials per unit area. The

response may be in deformation type as strain.

3.6 TYPES OF RHEOLOGY AND PROPERTIES

Types of rheology are classified on the basis of the way of applied stresses and forces on

the material under consideration. So, two main types of rheology are given as following.

• Steady State Rheology

• Dynamic Rheology

Page | 46
3.6.1 Steady state Rheology
Steady state rheology is referred to as a constant force applied on the solutions with time

and their response is observed. In the solutions response properties like Viscosity, shear

stress, force, torque is observed.

3.6.2 Dynamic Rheology

In this type of rheology, the force or shear rate applied on the solution may be changed

with time and have different values at different time intervals showing odd behaviors of

solution. In this rheology the properties like loss and storage modulus are obtained. Storage

modulus is the ability of a material to store the energy elastically applied on a material.

And loss modulus is the ability of a material to loss stress through heat.

3.7 PROPERTIES
The criteria for the selection of an appropriate material which may be a polymer, a salt, or

a surfactant for EOR flooding is that what is their behavior under the same conditions as

reservoirs. This task is accomplished by checking their properties which are given below.

3.7.1 Shear rate

It is the parallel force applied on a solution between two plates of which one is moving and

other is stationary. The velocity of moving plate is taken in meter per second while the

distance between the plates is taken in meter. So, by definition the units of the shear rate

are the reciprocal of the seconds.

Page | 47
 Figure 9 Shear rate demonstration

The two plates model is helpful and easy way to understand the concept of shear rate. When a

force parallel to the velocity direction is applied on the upper plate then it transfers its stored

energy to the adjacent fluid and the layer to layer this force is transferred to the stationary plate.

3.7.2 Shear stress

It is a vector force and a component of shear force parallel to the materials cross section. It

originates form the force vector component which is perpendicular materials on which it is

acting.

3.7.3 Viscosity
Viscosity simply is the resistance of a material to its flow. Which actually explains the

interlayers behavior of a fluid or matter that how strong they are linked with each other. As

honey is thicker than water and also have more strong forces between its molecules, so its

viscosity is more than water.

In rheological measurements the viscosity measurements are analyzed by applied shear

rate for appropriateness of a fluid to use it for flooding purposes in EOR.

Page | 48
3.7.4 Torque
The force applied on a matter in angular way is termed as torque.it gives angular

acceleration to the material under shear stress.

3.7.5 Rheometry
The process of measuring the all above mentioned rheological properties by applying

different techniques on a rheometer is referred to as rheometery. The technique which is to

be used in rheometry depends upon the property which is to be measured. The rheometry

process is considered to be useful in quality control, and many other chemical processes in

industries.

3.8 RHEOMETER
To accomplish all the rheological experiments, the used instrument is called rheometer.

This is an instrument which resembles with simple viscometer which are also used to

measure signal quantity of viscosity.

Figure 10 Rheometer

The dynamic shear rate rheometer was invented in 1993 when solutions and some solid

materials have to be tested for high temperature conditions.

Page | 49
3.9 WORKING PRINCIPLE
A rheometer works based on the principle of controlled shear rate and controlled shear

stress applied on the solution or material under observation.

3.9.1 Parts of Rheometer

A dynamic shear rate rheometer is assembled by combining different parts which are given

below.

• Spindle

• Cup cylinder

• Header

• Drive Shaft

• Base

• Column

• Heat Exchanger

• Software

Rheometers have different shaped parts according to the requirements of properties to be

calculate and the materials to be observe. So, the there are many types of spindles which

are used in a rheometer which are explained in the following figure briefly. A spindle

applies a rotational force on the polymer solution taken in cylinder.

Header is the upper part assembly of rheometer where the drive shaft connects spindle.

And column is the whole section between the header and base. A heat exchanger is also

attached with rheometer to adjust the temperatures of solutions according to requirements.

All methods and jobs are chosen by a rheometer software which is installed in PC.

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 Figure 11 Geometry of Rheometer

The figure 17(left) show the principle of a typical rheometer for rotational tests with

continues rotation and right figure shows rotational oscillation. It is a clear representation

of a fluid moving between the spindle and the outer cylinder wall facing a high shear rate.

Because of this rotational motion of spindle, the torque of the applied force is also

calculated with increasing shear rate.

3.10 Types of Rheometer:

Based on the working principle there a found two most common types of rheometer

which are known as,

• Shear or rotational Rheometer

• Extensional Rheometer

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3.10.1 Shear Rheometer
A type of rheometer which controls the applied shear stress on the liquid or slurry inside

the cylinder.

it further contains on the following types;

• Cyclic Rheometer

Which contains a small tube having constant cross section with known

dimensions to pass the liquid through it and kinematic viscosity is calculated

based on time taking by liquid to pass through aperture of tube’

• Dynamic shear Rheometer

The type of rheometer in which liquid is taken inside a cylinder and a rotating

spindle applies shear stress on it. The spindle speed can be changed according to

the required shear rate to be applied on fluid.

• Cone and plate Rheometer

In this type a liquid is placed on a flat plate and a cone type spindle is adjusted on

the plate to apply the shear rate.

3.10.2 Extensional Rheometer

The extensional rheometer is a type in which shear rate is applied externally of given

fluid. This type of rheometer is not fulfilling the requirements and challenges in the

market for external flow liquids. However, contains on following types;

Page | 52
• Rheotens

This type of rheometer contains on spinning fibers which is appropriate for

polymeric melted fluids, and is used for comparing the extensional properties of

fluids.

• CaBER

It is a capillary breakup rheometer used to measure the extensional shear rate for

low viscosity fluids.

• Sentmanat

A type in which the fluid is subject to a torque or stress between two drums. In

addition to the measurement of extensional viscosity, the SER tool may be used

for solid tensile testing, tear and peer testing, as well as friction testing

Page | 53
 Chapter 4

4 EXPERIMENTATION

4.1 OVERVIEW
This chapter is including chemicals used in experimentation and other apparatus used for
preparation of solutions of different concentrations.

4.2 CHEMICALS
Associate polymer Super pusher D118, Calcium Chloride (CaCl₂) and distilled water are
used for the rheology experimentation.

4.2.1 Polymer
Associative polymers are a new type of water-soluble polymer introduced in the modern

EOR process for oil and gas field for flooding. It is a synthetic polymer manufactured by

SNF FLOERGER in France having very high molecular weight ranges from 16-20[4]

million Daltons which comprise of anionic character with bulk density (medium Charge

density) of 0.8 kg/m3 and viscosity measurements are 5g/l(1700cp), 2.5g/l (650cp and) and

1g/l(270cp). It was available in white solid form having nanotubes like shape at room

temperature.

Associative polymers solution generally exhibits two types of behavior shear thickening

and shear thinning by when a shear rate is applied on the solution. In shear thinking solution

the viscosity of solutions gets an increased with the increasing shear rate. But in shear

thinning solution the viscosity gets lower with increasing shear rate. The polymer used in

EOR experiments shows shear thickening behavior after a specific shear until which it may

lower its viscosity because of its initial bonding disturbances.

Page | 54
4.2.2 Salt
Salt we have used basically is a neutral salt which is a CaCl2 underline is the review of it.

When a strong acid HCl react with a strong base Ca(OH)2 then calcium chloride formed.

It has following properties.

• At room temperature is found in solid form.

• It is a white crystalline solid.

• It has a boiling point of 1600C.

• Highly soluble in water.

• It has ionic bonding because Ca gives 2 electrons and other receive it

• Calcium chloride used for melting ice in winter season.

Calcium Chloride (CaCl2) (Odorless white Powder) having a density of 2.15g/ml with pH

range of 8-9, melting point 782⁰C, hygroscopic in nature and having 99%> purity.

4.3 APPARATUS

In the apparatus electronic weight balance, magnetic stirrer, magnetic plates, beakers of

different volumes and aluminum file were including.

4.3.1 Weight balance

Lab electronic weight balance was used to weight the salt and polymer which sensitive

and having precise calculation up to 0.001g.

Page | 55
 Figure 12 Weight balance

4.3.2 Magnetic stirrer

Magnetic stirrer or magnetic plate with a magnetic stirrer bar is used to prepare a uniform

solution of polymer and salt in the distilled water. Magnetic plate connected to electric

source and magnetic stirrer bar is places in the beaker in which solution of polymer or salt

is to be prepared. It is also used for heating the long with stirring.

Figure 13 Magnetic Stirrer

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4.3.3 Beakers along with aluminum file

Beakers of different volumes are used for the preparation of the solution and for the mixing

on the stirring and heating plate. Aluminum file is used to cover the solution so that it can

be avoid from the evaporation and alter the concentration of the solution.

4.4 PREPARATION OF SOLUTIONS

A required volume of polymers solution is prepared for all experiments of different

temperatures. Polymers solutions of concentrations 0.05wt%, 0.1wt%, and 0.15wt% were

prepared. As 30 ml for every temperature is used so for three temperatures 90ml of each

concentration is prepared. A required amount of polymer is weighed first of all according

the required volume of solution. And beaker was filled up to 90ml with distilled water and

placed on a magnetic stirrer. Then we started to pour polymers slowly to get homogeneity

into water and start the stirrer at medium rpm. After pouring all polymer we covered the

beaker with platinum foil and label the beaker with the concentration and remain it

undisturbed for next 24 hrs.

An electrolyte/polymer solution was prepared for 0.15wt% polymer concentration of three

different molarities 0.05M, 0.1M and 0.15M. Firstly the amount of calcium chloride was

calculated from physiology web according to required molarity. And an already prepared

polymer solution of 0.15wt% is taken in beaker and placed on magnetic stirrer. Then start

to add salt slowly with continues stirring and addition for a homogenize solution. The

procedure of preparing solution is as following;

Page | 57
4.4.1 Polymer solution preparation
First of clean all equipment’s and beakers

• Weight the polymer as for required concentration such that 0.05wt%, 0.1wt%, and

0.15wt%.

• Take 90 ml distilled water in 250 ml beaker and stirrer bar dip in the water and

beaker placed on the magnetic stirrer plate and on the plate adjust the RPM.

• After that put in the water polymer slowly on the side of vortex produce in the

beaker due to stirring.

• Keep on stirring until solution become uniform

Prepared 90 ml solution is divided into three samples for the rheological experimentation

carried out at three different temperatures such that 20°C, 40°C and 60°C. this procedure

is apply for all three concentration of polymer as 0.05wt%, 0.1wt%, and 0.15wt% and in

this nine sample become on which rheology is performed and get the results in table form

as are explained in next chapter.

4.4.2 Preparation of salt solution

For the preparation of salt solution first prepare the polymer solution of required wt.%

separately and solution of salt separately of known molarity. Then by using the formula

M1V1= M2V2 where

M1= molarity of salt solution given

V1= volume of salt solution

M2= molarity of solution required

V2= volume of polymer solution.

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So, that way we can prepare the salt solution in polymer of molarity 0.05m and volume 90

ml then make its three samples and performed rheology at different temperatures. Similarly

prepare solution of 0.1M and 0.15M and in that way nine samples of salt solution becomes

and performed rheology on different temperature

4.5 EXPERIMENTAL SEQUENCE

The sequence of experimentation is given the following and results are explained in the
coming chapter.

start

Preparation of Polymer
solution

Mixing of polymer and salt

Preparation of salt solution
solutions

Rheology measurements

Check the effect of time,

temp. and salinity.

Evaluations and analysis of

results

NO
Results are satisfied

YES

End

Figure 14 Experimental sequence

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 Chapter 5

5 RESULTS AND DISCUSSION

5.1 OVERVIEW
This chapter is based upon all experimental results and different graphs which explain

parameters and dependency according to other parameter. In the section 4.2 effect

concentration on the viscosity and other parameters is explained in detail which shows that

as concentration of polymer is increased the viscosity of flooding fluid also increased. As

shear rate on the flooding fluid is increased the viscosity also increased so shear thickening

behavior is observed. In section 4.3 effect of salt concentration is observed in the polymeric

solution and with increasing of salt concentration the viscosity of fluid decreased but the

trend is also shear thickening which is shown in the Figure 15 ,Figure 16 and Figure 18 at

the concentration of 0.05 wt.%, 0.1 wt.% and 0.15 wt.% of polymer respectively. In section

4.4 effect of on viscosity is observed for 120 minutes at different temperatures by keeping

shear rate constant and there no major effect is observed. Section 4.5 contains effect of

temperature on viscosity, in all graphs 20°C, 40°C and 60°C are used to observed effect on

viscosity.

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5.2 EFFECT OF POLYMER CONCENTRATION:
To investigate the rheological behavior of polymer solutions three different concentrations

0.05ml, 0.1ml 0.15ml solutions were examined at three different temperatures 20ºC, 40ºC,

60ºC one by one. The properties like shear stress, viscosity, force, and torque of polymer

solutions were obtained in table for a steady shear rate. All the polymer solutions showed

shear thickening behavior for each concentration and temperature. The steady shear

viscosity of solution distinct based on the polymer concentration of solution. In fig1 the

polymer solution showed change in viscosity for a steady shear rate for 0.05 ml polymer

concentration. A 30ml solution is taken in Rheometer cylinder and a shear rate ranging

from 50-1050 S-1 is applied for a constant time. In Figure 15 polymer solution for 0.05ml

and 20 ºC showed that viscosity starts from 0.0032pa.s at 50s-1 and increased highly to

0.006pa.s for 150s-1 shear rate and then viscosity remains constant till 350s-1.And then from

350s-1 to 450s-1 shear rate viscosity increased from 0.006pa.s to 0.0075pa.s and then

continuously increased to 0.009pa.s until 1000s-1.In Figure 16 when concentration of

polymer is increased the viscosity for a steady shear rate gets start from a higher value of

0.007pa.s and increased to 0.009pa.s and then remains same up to 200s-1.After this an odd

trend were observed that viscosity of solution gets lower from 0.009pa.s to 0.007pa.s

showing the shear thinning behavior of solution. After 250s-1 to 1000s-1 shear rate solution

viscosity gets a constant increase to 0.011pa.s.In Figure 18 for changed polymer

concentration 0.15ml at same temperature 20 ºC the initial solution viscosity starts from

0.01pa.s and increased to 0.011pa.s for shear rate 150s-1 and then decreased to 0.008pa.s

until a shear rate of 400s-1.And after that solution viscosity gets start to increase

continuously to 0.012pa.s until a steady shear rate of 1000s-1.By comparing all three graphs

at three concentrations and constant temperature it was observed that with the increase of
Page | 61
polymer concentration solution viscosity also increases due to high number of

intermolecular bonds between long chain polymer and distilled water.

For all these three concentrations rheological behavior of polymer solutions was also

analyzed for 40 ºC and 60 ºC. In fig1 for 0.05ml polymer solution and 40 ºC the viscosity

of solution gets start from 0.001pa.s and increased in the form of slop to 0..005pa.s for a

steady shear rate 50-150s-1 and then a small decrease occurred to 0.004pa.s due to

rearrangement of bonds to a shear rate 400S-1 and after this viscosity increases slightly to

0.005pa.s for a shear rate of 1000S-1.In fig2 for 0.1ml and 40 ºC of solution viscosity

initiates from 0.005pa.s which is evidently more than 0.05ml solution concentration and it

increases randomly at lower shear rates up to 50-150s-1 and then decreases to 0.005pa.s for

350s-1 and after getting continues increased shear rate it gets smoothly increased to a value

of 0.008 for 1000s-1.In Figure 18 for a solution concentration of 0.15ml and 40 ºC viscosity

of the solution starts from 0.0075pa.s at initial shear rate of 50s-1.This viscosity is more

than both from 0.05ml polymer concentration and 0.1ml concentration showing the effect

of shear thickening behavior of polymer. After applying continues shear rate viscosity of

solution gets more viscous to 0. 0085pa.s for a shear rate of 100-150s-1. And then gets

lower to a shear rate 350s-1 and again starts to increase and a maximum value of viscosity

0. 09pa.s was achieved for 1000s-1 shear rate.

Similarly, the rheological behavior of prepared polymer solution ware also examined again

at constant temperature of 60 ºC for all varying concentrations. In Figure 15 for 0.05ml of

polymer concentration and 60 ºC of temperature it was studied that the shear viscosity starts

from 0.0025 and gets lower for initial shear rate of 50-100s-1. After this with s small

increase in shear rate of 100-150s-1, the viscosity of solution abruptly increases in the form

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of slope to 0. 004pa.s. And then viscosity increases slightly to 0. 05pa.s until maximum

shear rate of 1000s-1. In Figure 16 at 0.1ml polymer concentration and 60 ºC the starting

viscosity is 0.005pa.s which is significantly more than that of solution of 0.05ml but the

initial changing pattern is similar to previous concentration. At the start of operation

viscosity of solution decreases from 0. 005pa.s to 0. 003pa.s and then suddenly increases

to 0. 006pa.s and after this slowly increased to a maximum value 0. 07pa.s for increased

shear rate of 1000s-1. And Figure 18 for 0.15ml of polymer concentration and 60 ºC the

viscosity starts from 0. 006pa.s at 50s-1 and then decreases to 0. 0055pa.s and again

increases slowly to 0. 007pa.s for increased shear rate of 1000s-1.

All figures patterns showed the increasing viscosity behavior of polymer solutions with

increased polymer concentration for each temperature due to strong and more

intermolecular chain formations of monomers of polymer and distilled water molecules.

The figure3 for 0.15ml represents a little different pattern of graphs in which initially

viscosity gets lower and then starts to increase, from other figures and it is attributed to

high concentration of polymer used.

Increasing the temperature causes reduction in viscosity and from the figure it is clear that

at 20ºC temperature possess high shear rate and moving towards the higher temperature

shear stress starts decreasing. At lower shear rate region, change in shear stress is not so

much prominent due to intermingling of coils of polymer and in higher shear rate region

difference become significant and at high temperature shear stress decreases due to

enhancement of mobility of polymer and lesser molecular forces among them.

Page | 63
Figure 17 viscosity profile of 0.05 wt.% polymer at different temperature

Figure 15 viscosity profile of 0.05 wt.% polymer at different temperatures

Figure 16 viscosity profile of 0.1 wt.% polymer at different temperatures

Page | 64
Figure 18 viscosity profile 0.15 wt.% polymer at different temperatures

Figure 19 flow curves of 0.15 wt.% polymer at different temperatures

Page | 65
5.3 EFFECTS OF SALT
Elevated temperature and salts of high molarity or concentration caused reduction in

viscosity and it is the major issue faced in many EOR applications. As mentioned earlier

that associative polymers show very much acceptable results in different oil fields and

shear thickening behavior and in oil fields most demanding thing low concentration of

polymer and high salinity which is rarely available. In this section effect of salts (CaCl2)

on steady shear viscosity is discussed by varying salt concentration at fixed polymer

concentration and constant temperature. To study the salts effect on viscosity of polymer,

steady shear viscosity is plotted against shear rate ranging from (2001/s-10001/s) by

changing salts molarity at three different temperatures (20ºC,40ºC,60ºC).

All the polymer solution of different concentration behaves like Newtonian behavior and

the presence of slats/electrolyte effects its viscosity. From figure at 20ºC 1 it is clear that

polymer exhibits shear thickening and by increasing salts concentration thickening ability

of associative polymers increases and moving towards the lower concentration of

electrolyte, effect of salt on polymer viscosity becomes negligible because of fact that there

is term which is known as critical salinity above which salt can alter the viscosity of

polymer in reservoir. This is due to the fact that polymer chains(structure), in the presence

cations (Ca2+) which produces electrostatic shielding, turned into curled form. In low shear

rate region viscosity increases abruptly and in higher shear rate region when applied shear

rate got required tendency to disturb the polymer structure, polymer coils align themselves

along to way shear rate applied which is that why viscosity increases. Further, association

in polymer elevates which causes increase in viscosity.

Page | 66
At 40°C curves shows, abnormal behavior as overlap each other and in the low shear rate

region trend is obvious as explained earlier that curve having high salinity having

maximum viscosity but moving towards the higher shear rate region viscosity starts

decreasing and further in that region curve having low salinity shows maximum viscosity.

At 60°C, moving towards the higher temperature, in lower shear rate region trend is

abnormal and in higher shear rate region all the curves show almost same viscosity.

From figure it clear that at lower shear rate region, as polymer exhibits shear thickening

behavior, shear stress is not so prominent due to intermixing of chains of polymer and

moving forward in higher shear rate region shear stress becomes prominent and it is evident

from the figure it is clear that higher temperature exerts lower shear stress

Figure 20 Effect of salts on steady shear viscosity of polymer (0.15wt%) at 20°C

Page | 67
Figure 21 Effect of salts on steady shear viscosity of polymer (0.15wt%) at 40°C

Figure 22 Effect of salts on steady shear viscosity of polymer (0.15wt%) at 600°C

Page | 68
 Figure 23 Flow curves of polymer in salted water at different temperature

5.4 EFFECT OF TIME

In this section effect of time on viscosity of polymer having fixed concentration (0.15wt%)

at different temperature to check stability under constant shear rate countered in reservoir.

As in drilling application polymer is injected in the reservoir and remains in the reservoir

for minimum 10-12 months roughly to enhance sweeping efficiency and polymer tackles

with constant shear stress present due to heterogeneity of the reservoir For that purpose,

polymer solution is prepared and kept for almost 3-4hrs for complete dissolution to get the

desired results and at 2001/s constant shear rate performed for 2h to study the effect of

residence time of polymer injected in the reservoir. Temperature relates directly with shear

viscosity as viscosity is the effect of friction between the layers and molecular forces

among the molecules and by increasing temperature which weakens the molecular forces

Page | 69
 which turns in reduces the viscosity. As mentioned earlier polymer shows shear thickening

behavior and from figure 1it is clear that, polymer shows promising results as polymer

present great stability at higher temperature and at high residence time. At 20°C polymer

shows higher viscosity and as temperature goes higher viscosity decreases at 60ºC and as

time goes higher a slight increase in viscosity is observed and moving from lower shear

rate to higher shear rate region a slight increase in viscosity is observed. At 60°C viscosity

up to 50 min there is no change in viscosity but moving forward viscosity shifts towards

the lower region due to elevated temperature.

Figure 24 Effect of residence time on steady shear viscosity of polymer (0.15wt%) at different temperature

Page | 70
5.5 EFFECT OF TEMPERATURE
As shown in Figure 15 when experiment is carried out at temperature 20ºC, the highest

viscosity is observed after that when other sample is performed at 40ºC having same

concentration viscosity decreased as compare to at 20ºC. associate polymer has large

number of monomers and form a cluster with water having strong intermolecular forces.

Due to strong intermolecular forces it formed like a gel ton and bridge between water and

polymer and has high viscosity. When temperature is increased intermolecular forces

become weak and bridge start to break down results lower in viscosity as shown in Figure

15 with the green line. Similarly, when temperature further increased up to 60ºC the

viscosity is decreased that’s why third black line in the Figure 15 is shown lowest viscosity.

This trend is also observed when different concentrations of salt are added to polymer

solution and experiment is performed at different temperatures likewise 20ºC, 40ºC and

60ºC as shown in Figure 20.

Page | 71
 Chapter 6

6 SOCIO AND ECONOMIC CONSIDERATIONS

6.1 SOCIAL IMPACTS OF ENHANCED OIL RECOVERY (EOR)

With the high demand of oil word wide Enhanced oil recovery process is used more

frequently to fulfill the demands. All techniques of EOR as thermal, Gas, and chemical

techniques can extract as much oil as extracted by conventional techniques. The chemicals

used in Enhanced oil recovery like polymers, alkaline solution may have effect on

environment and social life of human beings, plants and animals. As the EOR process used

in a particular situation depends on geological factors and physical properties of the

reservoir oil, so the temperature pressure and type of the solution is selected by keeping in

consideration their effects on environment. So socially and environmentally it may affect

humans social and environmentally in the ways such that Oil prices may vary, Land

disturbances, Daily life activities and Environmental pollution (Water, Soil, Air) which can

be explain as following;

6.1.1 Social Impacts

EOR process in practical way may affect social life by different ways as prices of oil, land

disturbances. Prices of oil may vary according to the techniques used for recovery and how

much costly chemicals such as polymers surfactant or alkaline solution are used in process.

Page | 72
6.1.2 Land disturbances
Land disturbances is related to piping installation, well pet’s construction, roads

construction, waste disposal pits, sediment ponds, and plant facilities like offices, parking

areas and storage tanks are sources of land disturbances. After the years of working the

leakage may occur in old pipes used in well construction for injecting and extracting the

fluids and chemicals which causes the toxic chemicals to get absorbed into land soil to

large distances and effects the soil fertility and affects the human life indirectly. The land

near the well where EOR is carried out cannot be used for the agriculture because due the

oil spillage the nutrients are badly affected.

6.1.3 Effect on water

Accidental oil and chemicals spillage can result in contamination of soil and water with

results loss of productivity. It also becomes the great cause of water pollution because of

during the flooding water chemicals are used and after this polluted water is disposal to the

open land which cause the land pollution as well as water pollution. It also greatly effects

the marine life when EOR is done in the ocean area.

6.1.4 Deterioration of Surface water

Surface disturbances and stream crossings by pipelines may cause significant increase in

stream sedimentation and turbidity with detrimental effects on aquatic habitats. Other

potential problems include seepage of pollutants, such as drilling mud’s and brine, and

sledges from stream generators, from waste disposal pits, and accidental spills of oil, brine

and other chemicals.

Page | 73
6.1.5 Ground water contamination:
Enhanced oil recovery process uses water soluble chemicals which may be toxic to

organisms and carcinogenic to human if transported in sufficient quantities to ground or

surface water. These chemicals although not absorbed by intestine they irritate the mucosa

and by their detergent action they produce the nausea, vomiting and diarrhea. Ground water

contamination may also occur from broken or corroded well casings in both active and well

abounded wells, through the annular space around the casing where well is improperly

completed.

6.1.6 Air Pollution:

Steam generators are used in steam injection process could produce significant emissions

of sulfur dioxide, oxides of nature and suspended particulates, therefore periodic

sampling of the stack gases may be needed to monitor air quality. More data are needed

on the characterization of hydrocarbon emissions generated during steam displacement.

6.2 ECONOMIC IMPACT:

As the future of any EOR process depends upon the many factors like preparing a proper

study of literature and experimentation at the pilot scale-like simulation in software like

Tranvigator but most importantly economic analysis of the EOR process. By optimizing

the economy including many factors like capital cost, cost on operations, and financial

analysis. So, we have to develop an economic model of the EOR process, and the purpose

of any EOR process is to simulate and to modify the operation of an ongoing project.

In this we have to input some variable like properties of the reservoir and as result oil

produced as output and it gives an estimation of the quantity of oil production and

economic analysis of the profit gained and then by observing these factors we can further

Page | 74
predict the amount of oil will be recovered daily and overall recovery of the process. And

another factor is the risk evaluation before going towards the process and build a sample

plant to predict and calculate the risk by following formulae:

(Expenditure of pilot plant) x (Pilot enclosure) x (Chances of failure) (1)

(Expenditure per acre) x (EOR project area) x (1-Chances of failure) (2)

The company uses a particular model by taking suitable assumptions avail on self of

demanding techniques for tax chopping and following principles may apply.

• Incorporeal cost is 70% cost of the drilling and execution cost of production well

• Tactical cost is 30% of drilling and finalization cost of production well

Page | 75
 Chapter 7

7 CONCLUSION AND RECOMMENDATIONS

7.1 CONCLUSION

In this work rheological experimental study is carried out of associated polymer and

polymer (associated) with salt (CaCl₂) by preparing its solution in distilled water for EOR.

Rheology is most important to check the necessarily applications of polymer for EOR.

Commonly conventional polymer is used for EOR but it can’t maintain its viscosity, shear

rate, easily degrade ant can’t bear high salinity under harsh condition reservoir which is

unfavorable. So, conventional polymer is replaced by associate polymer and study the

effect of concentration of polymer by changing as 0.05wt%, 0.1wt% and 0.15wt% at

different temperatures used as 20°C, 40°C and 60°C at range of shear rate from 50 1/s to

1050 1/s for time 300s. And then check the salinity effect by adding salt (CaCl₂) varying

concentrations as 0.05M, 0.1M and 0.15M with 0.15wt% of polymer solution at same

conditions. Also studied the effect of time on viscosity for 2 hrs. at constant shear rate

2001/s. The results are plotted as viscosity vs. shear rate and viscosity vs. time as shown in

figures. It shows shear thickening behavior i.e. viscosity increases by increasing shear rate

because of cross linkage interior structure of associate polymer having greater

solvophobicability than conventional polymer HPAM and solvophilic groups increase the

property of bio compatibility and intermolecular forces with electrolytes ( salts), improves

the properties depending upon the viscosity and external parameters stability such as

temperature and PH. Associate polymers also can form a thickened solution with water or

ionic gel liquid which can able to maintain its viscosity behavior ( shear thickening as
Page | 76
shown in Figure 20) and tress has same trend of shear viscosity due to formation of cluster

in the D118 associate polymer solution either salinity in the solution is low or high as

shown in fig 4 and its behavior maintains for required time under harsh condition original

reservoir.

When increasing the concentration of polymer viscosity increases (as shown in Figure 15,

Figure 16 and Figure 18) because associate polymer contains associate groups which form

inter linkage between different network such as multiplets and transient. That’s why it has

ability to bear high salinity which makes preferable to conventional polymer and its trend

remained unchanged as shown in Figure 21, but it can also observed that as solvophobicity

is increased the viscosity of the solution decreased and there will be greater chance to

produce viscous fingering phenomena which is unfavorable. HPAM, PAM has larger

ability to produced higher degree of hydrophobicity as compare to associate D118 polymer,

so when conventional polymer is used for EOR there will be greater chance of viscous

fingering in the high salinity reservoir.

The strength of bridge or gel is so high which decrease the hydrophobic attraction forces

in associate polymer D118 but by increasing salinity hydrophobic attractions also

increased interior the structure of the gel , hence it shows high level of hydrophobicity

and relative lower level in hydrolysis due to which it is less effected by the ions of

electrolytes. It is also economical beneficial because a very small amount of associate

polymer formed a very strong cluster and increase in viscosity due to having a large number

of monomers.

Page | 77
7.2 RECOMMENDATIONS

Unfortunately, due to COVID-19 there was too short time span and could not performed

the rheological experimentation for nanoparticles. So, for the continuation of this work

there can be many directions such that;

• First all experimentation study which have done in this piece work can be repeat

for the polymer (associate D118) combined with the nanoparticles and study all

rheological properties, effect of temperature, shear rate and most important effect

of time on viscosity of the solution. This is modified and modern research area in

rheology for EOR. The fluids combined with nanoparticles are nano fluids or smart

fluids due to nanoparticles surface area increases and check that how it impacts on

all parameters.

• Secondly salinity effect is most important because under the surface of earth there

are large number of salts are presents and during the flooding these salts easily can

alter the properties of flooding fluid and cause lower in viscosity which has worse

impact on EOR. So that’s why will be important to carried out all experiment action

of associate polymer and nanoparticles combined with salt e.g. Calcium Chloride

(CaCl₂), sodium Chloride (NaCl), Nitrates and sulfates etc. And check how salt and

nanoparticles have combine effect on the rheological properties and real parameters

of the original reservoir.

• Dynamic rheology is another direction to continue this study of all three

classifications such as Associate polymer with salt, Associate polymer with

nanoparticles and then Associate polymer combined with salt and nanoparticles.

Dynamic rheology can be performed for these and study the Storage Modulus and

Page | 78
 Loss Modulus. And check that how modulus’s change by changing the

concentration as effect of concentration, time and temperature etc. and effect on

parameters when we transfer from steady state rheology to dynamic rheology and

how it is important for chemical EOR (cEOR).

• The world is moving toward the Bio materials in every field. So, it can be a good

step is Bio polymers are used in rheology for cEOR because bio materials are

environmentally friendly.

Page | 79
Page | 80
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