THE EFFECT OF pH ON INTERFACIAL PROPERTIES OF HEAVY OIL/BRINE AND

SURFACTANT ADSORPTION DURING SURFACTANT ENHANCED ALKALINE

FLOODING

By

OLATUNJI ADENIYI KEHINDE

Submitted in partial fulfillment of the requirements

for the degree of Master of Engineering

Major Subject: Petroleum Engineering

at

Dalhousie University

Halifax, Nova Scotia

September, 2012.

1
 DALHOUSIE UNIVERSITY

Faculty of Engineering,

Petroleum Engineering Program

The undersigned hereby certify that they have read and recommend to the Faculty of Graduate
Studies for acceptance a thesis entitled “THE EFFECT OF pH ON INTERFACIAL
PROPERTIES OF HEAVY OIL / BRINE AND SURFACTANT ADSORPTION DURING
SURFACTANT ENHANCED ALKALINE FLOODING” by Olatunji Adeniyi Kehinde in
partial fulfillment of the requirements for the degree of Master of Engineering.

Dated: 15th September 2012

Supervisor: _________________________________

Reader: _________________________________

Departmental Representative: ___________________________

2
 DALHOUSIE UNIVERSITY

DATE: 15th September 2012

AUTHOR: Olatunji Adeniyi Kehinde

TITLE: The effect of pH on interfacial properties of heavy oil/brine and adsorption

of surfactant during surfactant enhanced alkaline flooding.

DEPARTMENT OR SCHOOL: Faculty of Engineering, Petroleum Engineering

Program

DEGREE: M.Eng. CONVOCATION: October YEAR: 2012

Permission is herewith granted to Dalhousie University to circulate and to have copied for non-
commercial purposes, at its discretion, the above title upon the request of individuals or
institutions. I understand that my thesis will be electronically available to the public.
The author reserves other publication rights, and neither the thesis nor extensive extracts from it
may be printed or otherwise reproduced without the author’s written permission.
The author attests that permission has been obtained for the use of any copyrighted material
appearing in the thesis (other than the brief excerpts requiring only proper acknowledgement in
scholarly writing), and that all such use is clearly acknowledged.

_______________________
Signature of Author

3
 DEDICATION

I dedicate this work to almighty God, the source of my knowledge and inspiration.

4
 ACKNOWLEDGEMENTS
I am extremely grateful to my parents who spared no dime in getting me to where I am today. I

also thank them for their moral support and advice throughout the course of this programme.

Special thanks to my supervisor Dr. Michael Pegg for his continuous support and guidance

throughout this project work.

I am immensely grateful to all the faculty members especially Mr. Mumuni Amadu and Mr. Ray

Dube for making sure all I needed for this work was available at the right time.

I say thank you to Dr. Jan Haelssig for taking time out of his busy schedule to read this work and

for his constructive criticism.

Finally, to my ever ready friends, I say God bless you all for your contribution in making this

project a success.

5
 Table of Contents
List of Tables ................................................................................................................................................ ix
List of Figures .............................................................................................................................................. x
Abstract…………………………………………………………………………………………………………………………………………….……xi

List of symbols………………………………………………………………………………………………………………………………….……xii

List of Abbreviations …………………………………………………………………………………………………………………………..xiii

1.0 INTRODUCTION ............................................................................................................................... ………1

1.1 Background.........................................................................................................................................1
1.2 Objectives: .......................................................................................................................................... 7
1.3 Research outline ................................................................................................................................. 8
2.0 LITERATURE REVIEW ............................................................................................................................... 9
2.1 Crude Oil ............................................................................................................................................. 9
2.1.1 Heavy crude oil formation and Characteristics. ......................................................................... 10
2.1.2 World Distribution of Heavy Oil ................................................................................................. 11
2.1.3 Heavy oil Basin (The Foreland Basin) ......................................................................................... 12
2.2 Heavy oil Recovery ............................................................................................................................ 13
2.2.1 Chemical Recovery ..................................................................................................................... 14
2.2.2 Principle of Mobility ................................................................................................................... 15
2.2.3 Alkaline Flooding ........................................................................................................................ 16
2.2.3.1 Principle of Interfacial Tension ……………………………………………………………………………………....16

2.2.4 Surfactant Flooding .................................................................................................................... 19

2.2.5 Surfactant enhanced alkaline flooding. ..................................................................................... 19
3.0 MATERIALS AND EXPERIMENT. ............................................................................................................. 21
3.1 MATERIALS ........................................................................................................................................ 21
3.1.1 Heavy Oil .................................................................................................................................... 21
3.1.2 Brine Solution............................................................................................................................. 21
3.1.3 Surfactant. .................................................................................................................................. 22
3.1.4 Alkali ........................................................................................................................................... 22
3.1.4 Toluene and its Effect on Heavy Oil ........................................................................................... 23

6
 3.2 EQUIPMENTS..................................................................................................................................... 24
3.2.1 Kruss Spinning Drop Tensiometer Site 100 ................................................................................ 24
3.2.2 Measurement Principle of the Spinning Drop Tensiometer. ..................................................... 25
3.3 Experimental Procedure: .................................................................................................................. 27
3.3.1 Heavy Oil Preparation ................................................................................................................ 27
3.3.2 Preparation of Brine, Alkaline and Surfactant solution. ............................................................ 28
3.3.3 Sand Stones ................................................................................................................................ 29
3.3.4 Spinning Drop Tensiometer site-100 Measurement. ................................................................ 29
4.0 RESULTS AND DISCUSSION.................................................................................................................... 31
4.1 Experimental Results......................................................................................................................... 31
4.2 Discussion of Results ......................................................................................................................... 31
4.2.1 Effect of Temperature on IFT…………………………………………………………………………………………………31

4.2.2 Effect of pH Optimization on Interfacial Tension and Surfactant Adsorption. .......................... 32

5.0 CONCLUSION AND RECOMMENDATION .............................................................................................. 35
5.1 Conclusion ........................................................................................................................................ 35
5.2 Recommendation.............................................................................................................................. 37
REFERENCES ........................................................................................................................................... 38
APPENDICES ............................................................................................................................................ 42
Appendix A: Table of IFT measurements vs. Temperature ........................................................................ 42
Appendix B: Table of IFT vs pH . .............................................................................................................. 49

7
 LIST OF TABLES

Table 3-1: Physical properties of salts …………………………………………….. 21

Table 3-2: Physical properties of Sodium dodecyl sulphate………………………………..22

Table 3-3: Physical properties of Sodium Hydroxide ……………………………………..22

Table 3-4: Physical Properties of Toluene solvent……………………………………...… 23

Table 3-5: Salt, Alkaline and Surfactant composition ………………………………….…28

Table 3-6: Calibration test experiment results..............................................................30

8
 LIST OF FIGURES

Figure 1-1: International Energy Agency chart (IEA Chart, 2012)……………………………... 2

Figure 1-2: Enhance Oil Recovery methods (Petrsas, 2011)...…………………………………...4

Figure 2-1: Unconventional sources of crude oil double Conventional sources …......................10
(Image from Wikipedia 2012).

Figure 2-2: Heavy oil distribution (Extracted from Petroleum Equities Inc. 2004)...…………...11

Figure 2-3: Formation of the Foreland Basin and Heavy oil, A: Pre Foreland Basin, .………....12
B: Foreland Basin (Extracted from Head et al)
Figure 2-4: Enhanced oil Recovery methods (Extracted from Speight, 2009)……….…………14

Figure 2-5: Residual oil saturation as a function of Capillary…………………………………..17

(Retrieved from Farouq – Ali and Thomas, 1994).
Figure 3-1: Schematic of spinning drop tensiometer showing the measuring cell………………24
(From Leicket al.2010).
Figure 3-2: Schematic of the spinning drop method (Retrieved from Drelich et al. 2002)….…..25

Figure 3-3: Viscous Heavy oil …………………………………………………………...……...27

Figure 3-4: Spinning Drop Tensiometer Site-100…………………………………………….....29

Figure 4-1: IFT against pH at varying pH ………………………...……………..……………...31

Figure 4-2: IFT against pH at varying temperature ……………………………………………..32

9
 ABSTRACT
Stable mixtures of water in oil emulsions create several problems in oil recovery and usually
increase the cost of production by over fifty percent especially when the field becomes older and
older. These oil emulsions are formed when water dispersed in oil is agitated by flowing through
rock pores and stabilized in the presence of naturally occurring emulsifiers such as asphaltenes
and resins containing organic acids and bases. These emulsifiers create high interfacial tension
between brine and oil by forming films hence making oil recovery difficult and expensive.

Adding inorganic acids or bases changes the physical properties such as IFT between the oil and
brine and the stabilizing properties of the emulsifier and hence improves oil recovery.

This work is aimed at investigating the effect of pH on IFT of the oil-brine system and surfactant
adsorption on rock surfaces during Surfactant Enhanced Alkaline flooding.

This experimental work was carried out using the Kruss Spinning drop Tensiometer site-100.
Different solutions of brine, surfactant and alkaline at different pH were prepared and dispensed
in the capillary of the tensiometer. A drop of oil is also dispensed at a particular speed after
which measurement are taken when the drop length is at least four times the drop diameter along
the axis of rotation.

The result of this experiment showed that IFT goes through a deep minimum in surfactant
enhanced alkaline flooding than each alone. Also the alkaline reduces the adsorption of anionic
surfactant on rock surfaces when the alkaline is prepared within the intermediate range of pH
(9- 12) by impacting a negative charge on the rock surface when an anionic surfactant is used
such as the sodium dodecyl sulphate (SDS).When surfactant adsorption is reduced it helps to
maintain the wettability properties of the reservoir rocks which is desired.

10
 LIST OF SYMBOLS
Symbols

λD Mobility of the displacing fluid

λd Mobility of the displaced fluid
γ Interfacial tension (dynes/cm)
θ Contact angle (degrees)
µ Viscosity (cp)
υ Velocity (cm/s)
∆p Pressure difference (dynes)
Δρ Density difference (g/cm3)
ω Angular velocity (rpm)
bbl Barrel
E1 Vertical Sweep Efficiency
EA Areal Displacement Efficiency (ft2/ft2)
Ev Volumetric Displacement Efficiency (bbl/bbl)
ft feet
k Permeability (m2 or mD)
M Mobility ratio (m3.s/kg / m3.s/kg)
Md Mobility of the displaced fluid
MD Mobility of the displacing fluid
Nc Capillary number
Pc Capillary pressure (dynes/cm3)
po Pressure in the oil phase (dynes)
R Radius of the oil bubble (cm)
Rm Radius of the bubble at the equator (cm)
Sor Residual oil saturation (%)
Sw Water saturation (%)

11
 LIST OF ABBREVIATIONS

API American Petroleum Institute

ASP Alkaline Surfactant Polymer flooding

CCD Charge-Coupled Device

CSS Cyclic Steam Stimulation

CHOPS Cold Heavy Oil Production with Sand

CDC Capillary Desaturation Curve

EOR Enhanced Oil Recovery

EIA Energy Information Administration

HC Hydrocarbon gases

IFT Interfacial Tension

JCPT Journal of Canadian Petroleum Technology

LED Light-Emitting Diode

MP Micellar-Polymer flooding

NEB National Energy Board

OOIP Original Oil in Place

PV Porous Volume

ROS Residual Oil Saturation

SAGD Steam Assisted Gravity Drainage

VAPEX Vapour Extraction

WAG Water Alternating Gas

12
1.0 INTRODUCTION

1.1 Background

According to the United Nations, the world population is estimated to rise to 9.1 billion by

2050.Technically, this means the world demand for energy is expected to double by 2050 and

sources of energy will also have to double to meet the growing demand for energy. According to

the IEA (International Energy Agency), with the conventional sources of oil peaking in 2006 and

now in the final stages of depletion in most mature oil fields, there is a need to implement

advanced methods of oil recovery to maximize the production and to extend the economic life of

the oil fields.

Conventional oils are recovered using natural forces of the reservoir. According to the Canadian

Association of Petroleum Producers, many of the world’s sources of conventional oil are in

decline, and Canada is no exception. The conventional oil reservoirs that were abundant and easy

to find 30 years ago are harder to locate and more costly to develop (CAPP, 2012). With the

growing demand of energy across the world and the depletion in most of conventional oils in

most oil fields, the conventional oil alone will be insufficient to meet the world energy demand

over the next three decades. According to the IEA, there is no shortage of oil and gas in the

ground, but quenching the world thirst for them will require investment in modern technology.

Since it is likely for oil and gas to remain the major sources of energy in the world, rapid

technological development would be the solution to supplying the desired quantities at prices

that do not hinder worldwide economic growth, while ensuring diversity of the origin of

supply (IEA 2005).

13
Unconventional oils are produced using techniques other than the conventional techniques. This

technique requires the use of advanced methods to recover oil in commercial quantity and has

proven to be successful except for the huge challenges associated with it such as the expenses.

However with the decrease in availability and rise of prices of conventional oil, there arises the

incentive to develop methods of producing the unconventional oil (Selley, 1998).

Figure 1-1 is an International Energy Agency Chart which shows that Convectional sources of

oil peak and declined.

Figure 1-1: International Energy Agency chart (IEA Chart, 2012)

This chart shows that by year 2035 conventional oil will decline to less than 20 million barrels

per day which is roughly what the United States currently consumes per day (IEA 2012). Also,

according to Figure 1-1, unconventional oil will be on the increase by the year 2035 and

probably continue increasing. This shows why unconventional technologies need to be focused

on if the increasing energy demand is to be met.

14
Unconventional resources include heavy oil, extra heavy oil and bitumen which are characterized

by high viscosities (i.e. resistance to flow) and high densities compared to conventional oil

(NPC, 2007). Heavy oils are formed at shallow depths, this shallow depth allows for condition

favourable for their formation such as bacteria degradation and weathering. Because of their

resistance to flow and high density they require enhanced oil recovery method to produce them

and additional upgrading before processing. The fact that most heavy oil reservoirs are shallow

(up to 1000 meters below the surface line) therefore present low reservoir temperatures (between

40 and 60oC) (Speight, 2010).

Enhanced oil recovery also known as tertiary recovery involves the introduction of heat,

chemicals, microbes or gases which are not present in the formation into it to reduce viscosity or

density of the formation fluid so as to improve the fluid ability to flow into the well bore.

Tertiary recovery (EOR) enables producers to extract up to over half of a reservoir’s original oil

content, depending on the reservoir and the EOR process applied (Teledyne Isco, 2007). The

volumetric displacement is largely represented as a function of mobility ratio (Farouq–Ali and

Thomas, 1994). A mobility ratio greater than unity is unfavourable because water is more mobile

than oil. Water will finger through the oil zone and reduce oil recovery efficiency (Donaldson et

al, 1989). Hence for a high oil recovery efficiency mobility ratio must be unity or less than unity.

15
 Figure 1-2: Enhance Oil Recovery methods (Petrosas, 2011)

The choice of method depends on how much oil will be extracted and how profitable the oil

extracted is in the market. According to Sarma (1999), EOR can be classified into two broad

groups known as non-thermal and the thermal methods of recovery .The non- thermal methods

do not involve heat and this is subdivided into Gas drives, microbial and chemical flooding.

Chemical flooding involves the injection of chemicals or additives into the reservoir for the

purpose of reducing interfacial tension or viscosity of the displaced fluid. Such chemicals include

surfactant, alkaline or polymer or combination.

16
Chemical flooding is particularly effective in recovering a large fraction of the oil left in the

reservoir after water flooding. This method of EOR could produce as much as 60 percent of the

original oil in place (Farouq–Ali and Thomas, 1994). This method aims at adjusting the mobility

ratio between the displacing fluid and the displaced phase less than or equal to unity. This is

achieved by making the mobility of the displacing fluid equal or less than the mobility of the

displaced fluid mainly by lowering the interfacial tension (IFT) between the displaced phases as

much as possible.

Interfacial tension can be lowered in a stable mixture of brine-oil emulsion by alkaline flooding

or surfactant alone. However, with the addition of surfactant to the alkaline solution, a low

interfacial tension can be obtained rather than using either alkaline or surfactant alone (Schuler et

al.1986.).According to Rudin et al (1993), IFT can go through a deep minimum by optimizing

the pH of the alkaline solution.

Gas drives involve the introduction of gases such as CO2 to sweep the reservoir fluids into the

well bore. EOR through the injection of CO2 is one mechanism through which more oil recovery,

oil field extension and increase in profitability can be obtained (Trondheim and Stavanger,

2003).

Enhanced oil recovery by microbes was first suggested by Beckman in 1926 after which

experimental work by Claude Zobell in 1947 showed that sulphate reducing bacteria could

potentially release oil by a number of mechanism .This bacteria utilizes hydrocarbons in crude

oil and produces acids and carbon dioxide. The acid reacts with rock carbonates thereby

increasing rock permeability and producing more carbon dioxide which helps to increase

17
reservoir pressure. The carbon dioxide dissolves in the crude oil thereby reducing viscosity and

aiding displacement of oil into the well bore.

Thermal methods of EOR involves the injection of high temperature fluids into the reservoir

aimed at reducing viscosity of displaced fluid and increasing the mobility of the displaced fluid

into the well bore. This includes steam assisted gravity drainage (SAGD), cyclic steam

stimulation (CSS). This method of oil recovery depends on the thickness of the pay zone. If the

pay zone is thin there is tendency that heat could be lost from the injected steam to the colder

environment. The application of this process depends on the characteristics of the formation such

as thickness of the pay zone, depth, pressure and permeability (Green et al., 1998).

18
1.2 Objectives:

The experimental and analytical objectives of this research were:

1. Investigate the effect of pH on interfacial properties of heavy oil/brine and surfactant

adsorption using an anionic surfactant (Sodium dodecyl Sulphate).

2. Determine the pH range at which ultra-low interfacial tension is obtained during surfactant

enhanced alkaline flooding.

3. Measure IFT between heavy oil and surfactant enhanced alkaline-brine system as a function

of pH and temperature.

4. The feasibility of surfactant enhanced alkaline flooding over alkaline or surfactant flooding

alone.

19
1.3 Research outline

This report starts with a review of literature relevant to crude oil production with special

consideration on heavy oil such as the world heavy oil distributions, formation, characteristics

and location of heavy oil such as the Foreland basin in Western Canadian. Methods of Enhanced

oil recovery were reviewed with more attention paid to the chemical methods of recovering oil

such as alkaline flooding, Surfactant flooding and the combination of both.

Chapter three describes the method and materials used for this experimental works and

equipment such as the spinning drop tensiometer used for this experiment. The experimental

procedure was also included in this chapter.

Chapter four starts with the results of the experimental work and analysis of the results. This

chapter also contain graphical representation of the experimental results.

A summary of discoveries and conclusions were presented in chapter 5 alongside

recommendations for future research work on this topic.

20
2.0 LITERATURE REVIEW

2.1 Crude Oil

Crude oil is a naturally occurring liquid formed from accumulation of large remains of organic

matter under anaerobic conditions, high temperature and pressure. Generally, crude oil consists

of long chain hydrocarbons of various molecular weight and other organic liquids found beneath

the earth crust. It is classified based on API (American Petroleum Institute) gravity which is a

function of specific gravity. API is a measure of how heavy or light crude oil is compared to

water. The API gravity is inversely proportional to specific gravity of a crude oil according to

Equation (2-1). This equation shows that crude oil with a low specific gravity will have a high

API gravity and the higher the API gravity the lighter the crude and vice versa.

…………… [2- 1]

Based on the API gravity, crude oil is classified as heavy, medium or light. Crude oil with API

gravity less than 20° is considered to be heavy with most heavy oil falling within the range of

10° to 15° API (Speight, 2009). According to Boardman Energy (2012), heavy crude oil has an

API gravity below 22.3°, medium crude oil has API gravity between 22.3 ° and 31.1°, and API

gravity above 31.1° is regarded as light crude oil.

Heavy crude oil is classified by high viscosity and density and is formed as a result of bacterial

activities and weathering on conventional oil that migrate to shallow depth from deep

formations. This oil is difficult to exploit economically, but with the continuous decline in

conventional oil as projected by the international Energy Agency (IEA), there is a need to focus

on economical methods of heavy oil production if the world is to depend on crude oil as the main

source of energy in the future.

21
According to Speight (2009), heavy crude oil accounts for double the quantity of conventional

oil in the world. Figure 2-1 shows the world conventional oil and unconventional oil in

percentage..

Figure 2-1: Unconventional sources of crude oil double Conventional sources

(Wikipedia 2012)

Unconventional oil is further divided into heavy, extra heavy oil (API < 10 °) and oil sands with

Canada, Venezuela and USA leading producers of these unconventional oils.

2.1.1 Heavy crude oil formation and Characteristics.

Crude oil with API gravity less than 22.3° is regarded as been heavy while oil with API gravity

less than 10° is termed extra heavy. Heavy crude oils are formed when conventional oil migrates

from deep formation to shallow depth where it is been degraded by bacteria and weathering.

Heavy oil is found at shallow depth because these degrading bacteria cannot withstand the high

temperature at deep formation and therefore only degrade crude oil at shallow depth where they

can survive. Heavy oils are deficient in hydrogen because the degrading bacteria feed on the

hydrogen content of the oil and produced the denser, more viscous heavy oil and

22
bitumen (NPC, 2007). Because heavy oils are deficient in hydrogen, upgrading is needed (hydro

processing) or coking to remove carbon before it can be processed in a conventional refinery.

Generally, heavy oil contains high carbon, sulfur, and heavy metal and deficient in hydrogen. Also

heavy oil contains organic acids such as naphthenic acid and others which are responsible for the

formation of surfactants in situ.

2.1.2 World Distribution of Heavy Oil

Heavy oil deposits are well known and abundant, which implies that little cost of exploration will

be required. According to IEA, 6 trillion barrels of heavy oil is available worldwide with 2

trillion barrels recoverable. Figure (2-2) shows the world distribution of heavy oil with Canada

estimated to hold the largest heavy oil deposit.

Figure 2-2: Heavy oil distribution (Herron et al., 2004).

Canada is estimated to hold about 2.5 trillion barrels with current reserves at 175 billion barrels

Venezuela is estimated to hold 1.5 trillion barrels, with current reserves of 270 billion barrels,

Russia holds in excess of 1 trillion barrels of heavy oil while the United States, is estimated to

have current reserve of 100 to 180 billion barrels (NPC, 2007).

23
2.1.3 Heavy oil Basin (The Foreland Basin)

A Foreland basin is a system where heavy oil is mostly found. It consists of an elongated region

of potential sediment accumulation that forms on the continental shelf between a contraction

organic belt and the adjacent craton, as a result of tectonic forces (Decelles, 1996). A foreland

petroleum system consist of source rock, sandstone and a regionally extensive seal on the

continental shelf. It is formed during the period of active erosion which subsequently buries the

source rock formed in the pre foreland basin. Figure 2-3 shows the formation of Foreland Basin

and how heavy oil is been trapped.

Figure 2-3: Formation of the Foreland Basin and Heavy oil, A: Pre Foreland Basin,

B: Foreland Basin (Head et al., 2003)

24
As the source rock gets to the oil window, oil is formed and migrates to the shallow cool basin

flank where degradation bacteria can survive. At this shallow depth biodegradation of oil occurs

which increases the viscosity (resistance to flow) there by trapping the degraded oil. Figure 2-3

shows the formation of the Foreland basin and heavy oil. This basin can be found in Alberta and

Saskatchewan provinces in Canada, in California, in Northern Mexico, and in Venezuela.

These heavy oil deposits contain brine which mixes with the heavy oil to form emulsions in the

presence of natural stabilizers such as bacterial refuse and resins which hinders oil recovery.

Hence it is important to reduce the interfacial tension between these stable mixtures so as to

enhance oil recovery.

2.2 Heavy oil Recovery

Since the locations of large deposits of heavy oil are well known, exploration should not be very

difficult but the technology to optimize heavy oil production remains a huge challenge. The

technology used in recovery of heavy oil in a case may not work in another because the

properties of the resource might vary. Hence each production method must be tailored to the

resource and fluid properties such as oil composition, gas content, density and viscosity (NPC

2007). Other essential properties that must be addressed before a method is selected include the

depth, area extent, geological setting and thickness of the resource. However, these technologies

recover about 30% of the available heavy oil. Hence, if the growing demand of energy is to be

met, there is need to improve on this recovery factor. Figure 2-4 shows the methods of enhancing

oil recovery.

25
 Figure 2-4: Enhanced oil Recovery methods (Speight, 2009).

The chemical methods of oil recovery would be emphasized being the background of this work

even as others have been discussed in the previous chapter.

2.2.1 Chemical Recovery

This involves the injection of additives which are not originally present in the reservoir into the

reservoir for the purpose of altering properties of the fluid in the reservoir and aid displacement

of fluid into the wellbore either by mobility control or lowering interfacial tension between

oil/brine. Though EOR by chemical flooding has not been very successful due to economic

reasons, it is the key to the future because of advancement in technology and science. The major

chemical flooding processes include polymer flooding, surfactant flooding, alkaline flooding,

micellar flooding and surfactant enhanced alkaline flooding.

26
2.2.2 Principle of Mobility

Mobility is the ratio of permeability to viscosity. It is defined as any activity that tends to alter

the relative rates at which injected and displaced fluids move through the reservoir by Green and

Willhite (1998).

Mobility = .......................................................... [2-2]

Where, k = Permeability (m2 or mD)

µ = Viscosity (kg/m.s or cp).

Chemical recovery is a mobility control process which is aimed at keeping mobility ratio

between the displacing fluid and the displaced fluid less than or equal to unity. The ratio of the

displacing fluid to the displaced fluid is known as the mobility ratio.

Mobility ratio (M) = .......................................... [2-3]

It is necessary to keep the mobility ratio (M) less than or equal to unity in order not to allow the

displacing fluid flow past much of the displaced fluid. Therefore the mobility determines the

sweep efficiency (Farouq – Ali and Thomas, 1994). According to Farouq Ali and Thomas

(1994), mobility ratio can be improved by increasing the viscosity of the displacing fluid to at

least greater than that of the displaced fluid. According to equation 2-2, mobility is inversely

proportional to viscosity; hence, a displacing fluid with a high viscosity gives a low mobility

which in turn provides a low mobility ratio and a better sweep efficiency.

27
2.2.3 Alkaline Flooding

This process involves the injection of alkaline into a reservoir. The alkaline reacts with organic

acid present in the fluid to form surfactant in-situ by a process known as saponification. The

surfactants formed in-situ release oil by lowering interfacial tension between oil/brine and

therefore more fluid is displaced into the well bore. This process is only effective in enhancing

oil recovery if the oil contains efficient organic acid for the formation of the surfactant. Also in

carbonate reservoirs alkaline flooding is not recommended because of the abundance of calcium:

the mixture between the alkaline chemical and the calcium ions can produce hydroxide

precipitation that may damage the formation.

2.2.3.1 Principle of Interfacial Tension.

Interfacial tension (IFT) is the property of the interface between two immiscible liquid such as

oil/brine. In Chemical recovery such as alkaline flooding, the surfactant formed in-situ in an

oil/brine system lowers the interfacial tension between oil and brine, hence enhancing oil

recovery. Ultra low interfacial tension can be obtained by pH and ionic strength optimization

even though alkaline flooding and surfactant enhanced alkaline flooding are classically

interpreted on the basis of ionic strength alone, neglecting the effect of pH which causes

confusion in designing meaningful formulations to be injected into the reservoir (Rudin, 2004).

IFT influences capillary pressure, capillary number and adhesion tension and its value is time

dependent in an oil/aqueous solution (Jill, 2005). Capillary number (Nc) is the effect of viscous

forces to interfacial tension acting across the interface between two immiscible liquids. Oil

recovery can be improved if the capillary number is increased. According to Farouq – Ali and

Thomas, (1994), increasing the capillary number lowers residual oil saturation which in turn

28
enhances oil recovery. Figure 2-5 below shows the relationship between increasing capillary

number and residual oil saturation.

Figure 2-5: Residual oil saturation as a function of Capillary

(Farouq – Ali and Thomas, 1994).

Figure 2-5 above shows that increasing Nc lowers residual oil saturation. According to equation

2-4 interfacial tension is inversely proportional to Nc, hence lowering interfacial tension

increases Capillary number (Nc) which lowers residual oil saturation and hence improve oil

recovery.

29
 Capillary number (Nc) = = ..................................................... [2-4]

Where;

k is effective permeability (mD).

∆p/L is pressure gradient (Pa/m).

γ is interfacial tension between oil and brine (N/m)

µ is viscosity (cp).

v is velocity (m/s).

Ø is porosity.

Capillary pressure is the pressure generated between the interfaces between two immiscible

liquid in the pores of a reservoir rock. To enhance oil production this pressure must be lowered

by lowering interfacial tension between the immiscible fluids such as oil and water. Capillary

pressure is given by equation 2-5:

Capillary pressure (Pc) = ................................................... [2-5]

Where:

Pc is capillary pressure (N/m2).

θ is contact angle (degree).

γ is interfacial tension (N/m)

r is pore radius (m).

Since it is difficult to alter the pore radius and contact angle, lowering interfacial tension alone

would be the only way to lower capillary forces thereby increasing oil recovery

30
2.2.4 Surfactant Flooding

Surfactants are compounds which lower surface or interfacial tension in a medium. Schramm

(2000) defined surfactants as compounds that have one part that has affinity for non-polar media

and one part that has affinity for polar solvents. A surfactant molecule consists of a hydrophilic

group (water soluble head) and a hydrophobic group (oil soluble-tail).When surfactant

compounds are added to immiscible medium, they form micelles between molecules of the

immiscible fluids there by lowering interfacial tension.

Surfactant flooding has been used successfully to enhance oil recovery in the petroleum industry

but because of its high cost and excessive loss to the porous medium, its use alone has been

limited but now mostly used in combination with other methods such as surfactant-alkaline and

surfactant-polymer flooding.

2.2.5 Surfactant enhanced alkaline flooding.

Alkaline flooding is a chemical method of lowering interfacial tension in an oil-brine system by

forming surfactant in situ when alkaline is injected into the system. This process relies on

chemical reaction between an alkaline and organic acid in the acidic heavy oil to form surfactant

in situ by a process known as saponification.

Alkali + Organic acid → Soaps.

The saponification reaction generates soap which lowers capillary forces and increases the

capillary number by lowering interfacial tension between oil/brine thereby improving oil

recovery. However, with the addition of surfactant to the alkaline solution, interfacial tension

becomes lower and certainly improves oil recovery than the alkaline solution alone (Schuler et

al., 1986).It has been shown that small amounts of surfactants, normally less than

31
0.5wt%,together with an alkaline additive can produce an ultra-low interfacial tension against an

acidic crude oil thereby improving oil recovery(Martin et al.,1985; Nelson et al.,1984; French

and Burtchfiel,1990; Schuler et al.,1985). Technically, this means improved oil recovery can be

achieved without using much surfactant which is costly by combination of less surfactant and

alkaline unlike using surfactant alone. The exact role the added surfactant play in lowering

interfacial tension is still unknown. However, surfactant retention on rock surfaces is reduced by

the alkaline by impacting a negative charge on the rock surface thereby providing enough

surfactant for high interfacial activity (Rudin and Wasan, 1993).

Interfacial tension has been shown to be sensitive to the pH of the aqueous alkaline in surfactant

enhance alkaline flooding. According Strassner (1968), interfacial films formed by asphaltenes

arestrongest in acids (low pH) and become progressively weaker as the pH is increased. In

alkalin emedium, the films become very weak or are converted to mobile films. However films

formed by resins are strongest in base and become progressively weak in low pH (acid). Falcone

et al. (1982), showed that for interfacial films formed by asphaltenes, interfacial tension is lowest

between the pH range of 9-12 because at this range surfactant adsorption is minimal. Hence,

surfactant retention on rock is minimised providing enough surfactant for interfacial activity and

improving oil recovery.

32
 3.0 MATERIALS AND EXPERIMENT
3.1 MATERIALS

3.1.1 Heavy Oil

Heavy oil from the Western Canadian Sedimentary basin was used in this experiment. At room

temperature, the density and viscosity of the heavy oil were 0.971g/cm3 and 1300cp respectively.

3.1.2 Brine Solution

To conform to the salinity of the Western sedimentary basin were the heavy oil was obtained;

Calcium chloride, Sodium chloride, Magnesium chloride and Sodium sulphate were used to

prepare the brine solution used for this experiment being the dominant salts in the Western

Canadian basin. These salts were supplied by Sigma Aldrich-Canada and have the physical

properties as shown in Table 3-1 below.

Table 3-1: Physical properties of salts

Salts Chemical Formula Purity % Density (g/cm3) Molecular weight (g/mol).

Calcium Chloride CaCl2 93 2.150 110.98

Sodium Chloride NaCl 99.5 2.1650 58.44

Magnesium Chloride MgCl2 98 2.32 95.21

Sodium Sulphate Na2So4 99 2.68 142.04

33
3.1.3 Surfactant.

Sodium dodecyl sulphate (SDS) is the choice of surfactant for this experiment. It is a highly

effective surfactant and is used in the petroleum laboratory to lower IFT and any task requiring

the removal of oily stains and residues. The SDS used for this experiment was supplied by Sigma

Aldrich-Canada and have the physical properties as shown on Table 3-2

Table 3-2: Physical properties of Sodium dodecyl sulphate.

Surfactant Chemical Formula Purity % Density (g/cm3) Molecular weight

Sodium dodecyl sulfate C12H25NaO4S 99 1.01 288.38

3.1.4 Alkali

The alkali used for this experiment is sodium hydroxide. This choice was made based on the

success of the alkaline in past studies by Rudin et al., (1993) and Krumrine et al (1982). This

alkali lowers interfacial tension by generating soaps and also reduces surfactant retention on rock

surfaces as explained by Krumrine et al (1982). The sodium hydroxide used for this experiment

was also supplied by Sigma Aldrich-Canada with physical properties as shown on table 3-2

below.

Table 3-3: Physical properties of Sodium Hydroxide

Alkali Formula Purity % Density (g/cm3) Molecular Weight (g/mol)

Sodium Hydroxide NaOH 98 2.1300 40.00

34
3.1.4 Toluene and its Effect on Heavy Oil

Toluene (also called methyl benzene) is a colorless, flammable liquid. It occurs naturally in

petroleum crude oil (OPPT, 1994). Since petroleum crude oil is by far the largest source of

Toluene, adding Toluene to the heavy oil will have no effect on the petro physical properties of

the oil other than its viscosity.

The Toluene used to reduce the viscosity of the heavy oil in this experiment was provided by

Sigma Aldrich with physical properties as shown below:

Table 3-4: Physical Properties of Toluene solvent.

Chemical Formula Purity % Density (g/cm3) Molecular Weight (g/mol)

Toluene C6H5CH3 99.8 0.865 92.14

This step was necessary because it was impossible to get the very viscous heavy oil into the

needle to be dispensed into the capillary of the measuring cell.

35
3.2 EQUIPMENTS

3.2.1 Kruss Spinning Drop Tensiometer Site 100

The spinning drop Tensiometer is equipment used to measure interfacial tension as low as 10-6

mN/m. It is a computer controlled tensiometer equipped with a high-resolution camera and

interchangeable lenses for various measuring ranges. The equipment can preset speeds of up to

20,000 min-1 with accuracy and can measure and control temperature since it is an important

emulsion property. The measuring cells can be thermostatted within a temperature range of 0°C

and 100°C.

It is controlled by the DSA (Drop Shape Analysis) software which is a universal software for

controlling measuring devices and spinning drop measurements. The equipment general view

includes a light phase inlet, heavy phase inlet, measuring cell, camera and a platform inclination.

The measuring cell consist of the capillary which holds the light (capsule) and heavy phase as

shown below in Figure 3-1

Figure 3-1: Schematic of spinning drop tensiometer showing the measuring cell.

(Leick et al.2010).

36
The light phase is dispensed into the capillary through the septum and the heavy phase is inserted

into the capillary which is open to an inlet and an outlet. The measuring cell is illuminated in two

directions; horizontally to get a clear video image of the drop and vertically for visual control of

the filling and dispensing procedure and observed with the camera. The drop diameter is detected

by the DSA software from the drop image

3.2.2 Measurement Principle of the Spinning Drop Tensiometer.

The Spinning Drop Tensiometer relies on the technique that gravitational acceleration has little

or no effect on the shape of a fluid drop suspended in a liquid when the drop and liquid are

contained in a horizontal tube spun along its longitudinal axis (Drelichet al. 2002).

Fig 3-2: Schematic of the spinning drop method (Retrieved from Drelich et al. 2002).

If a light phase (drop) is situated in a heavy phase (bulk), the drop radius vertical to the axis of

rotation depends on the interfacial tension (γ) between the two phases, density difference (Δρ)

between the phases and the rotational velocities (ω). At low rotational speed, the shape of the

light phase becomes ellipsoidal and at high rotational speed the shape becomes cylindrical as

shown above in Figure 3-2. However, given a rotational velocity and densities of the two phases,

37
the interfacial tension can be calculated from the measured drop diameter using equation 3-1

below;

......................................................... [3-1]

where:

γ is the interfacial tension between the two phases (N/m).

r is the radius of the drop (m)

ω is the spinning or rotational velocity (rad/s)

ρH is the density of the heavy phase (kg/m3)

ρL is the density of the light phase (kg/m3)

Equation 3-1 shows that for very low interfacial tension to be obtained, the radius of the drop of

the light phase and rotational velocity must be small.

38
3.3 Experimental Procedure

3.3.1 Heavy Oil Preparation

The heavy oil obtained from the Western Canadian sedimentary basin has a viscosity of 1300cp

and API gravity of 13.8°. Being very viscous to be dispensed into the needle, the heavy oil was

diluted with 10% by volume of Toluene to reduce viscosity. As studies does not show any

significant effect of Toluene on heavy oil apart from changes in the viscosity even as Toluene is

largely produce from Petroleum crude oil (OPPT ,1994); 50ml of Toluene was added to 450ml of

Heavy oil at room temperature and the solution was stirred thoroughly with magnetic stirrer. The

density of the mixture was measured at room temperature to be 0.971g/cm3.

Figure 3-3: Viscous Heavy oil

39
The heavy oil was dispensed into the needle and a drop is dispensed into the capillary containing

solutions of brine, alkaline and surfactant.

3.3.2 Preparation of Brine, Alkaline and Surfactant solution.

The choices of salts for this experiment as discussed earlier are Calcium Chloride (CaCl2),

Sodium Chloride (NaCl), Magnesium Chloride (MgCl2) and Sodium Sulphate (Na2SO4) being

the dominant types of salt in Western Canadian sea water (Castro and Huber,2009).This is to

imitate the salinity of the Western Canadian Sedimentary Basin where the heavy oil was

obtained.

The brine solution was prepared by weighing 40g of NaCl, 25g of CaCl2, 25 g of MgCl2 and 10g

of Na2SO4and pouring into a conical flask containing 400g of distill water. 0.1 wt. percent (0.5g)

of surfactant, sodium dodecyl sulfate (SDS) is added to the brine and stirred thoroughly.

No. Composition of Solution % wt. of salt + SDS and %V NaOH pH Density (g/cm3)

at room temp

1 Brine + SDS + 0% v NaOH 20.5% (salt + SDS) 8.86 1.09

2 Brine + SDS + 4.0% v NaOH 20.5 (salt + SDS) and 4.0%VNaOH 9.12 1.09

3 Brine + SDS + 8.0% v NaOH 20.5 (salt + SDS) and 8.0 %NaOH 10.84 1.09

4 Brine + SDS + 12.0% v NaOH 20.5 (salt + SDS) and 12.0%NaOH 11.03 1.09

5 Brine + SDS + 16.0% v NaOH 20.5 (salt + SDS) and 16.0 %NaOH 11.45 1.09

6 Brine + SDS + 20.0% v NaOH 20.5 (salt + SDS)and 20.0 %NaOH 11.89 1.09

7 Brine + SDS + 24.0% v NaOH 20.5 (salt + SDS) and 24.0 %NaOH 12.56 1.09

Table 3-5: Salt, Alkaline and Surfactant composition

40
The solution of Brine and surfactant is then divided into 7 portions and solution of sodium

hydroxide is added to each portion to control the pH as desired and as shown on the table above.

3.3.3 Sandstones

Fine sands that settled at the bottom of the heavy oil container were used as surfaces upon which

surfactants are expected to absorb.

3.3.4 Spinning Drop Tensiometer site-100 Measurement.

Interfacial tension measurements were carried out by following the procedures as stated in the

Kruss User Manual.

Fig 3-4: Kruss Spinning Drop Tensiometer Site-100.

41
The temperature range considered for this experiment is between 20° to 80°C. This is because

reservoirs of heavy oil are found at shallow depth where the temperature is not as high as deep

formations where the oil is formed. This oil formed migrates to shallow depth where degrading

bacteria can survive.

The rate of rotation is increased at intervals until the drop is elongated enough. The length of the

drop (light phase) was at least four times the drop diameter along the axis of rotation before

measurement was taken.

The accuracy of the measurements from the Spinning drop Tensiometer was tested using

Johansen’s work of 1923. He showed that the IFT between distill water and Kerosene is

34.9mN/m. Similar experiment was carried out at 20°C and 3000 rpm for deionised water and

kerosene and the IFT was obtained to be 34.7126 mN/m . With these values being very close, it

was reasonable to conclude that Spinning Drop Tensiometer used for this experiment was at a

perfect condition during this experimental works.Table 3-6 shows the result of this test

Calibration Test
Johansen's work Calibration Experiment
Test fluids Distill water and Kerosene Distill water and Kerosene
Temperature (°C) 20 20
Speed of rotation (rpm) 3000 3000
Measured IFT (mN/m) 34.9 34.7126

Table 3-6: Calibration test experiment results.

42
 4.0 RESULTS AND DISCUSSION

4.1 Experimental Results

The effect of pH on interfacial tension and adsorption of surfactant on sandstones were

investigated at different temperatures and the results are presented in the appendix. A graph of

IFT against pH was also plotted to determine the range of pH at which interfacial tension goes

through a deep minimum during surfactant enhanced alkaline flooding.

4.2 Discussion of Results

4.2.1 Effect of temperature on IFT

As expected IFT decreases as temperature increases as shown in figure 4-1 below .This result

shows that temperature is just as important as the chemicals being used in reducing IFT.

0.6000

0.5000

0.4000
pH of 8.86
IFT in mN/m

pH of 9.12
0.3000
pH of 11.03
pH of 11.45
0.2000
pH OF 11.89
pH of 12.56
0.1000

0.0000
0 20 40 60 80 100
Temperature in degree C

Fig 4-1: IFT against pH at varying pH .

43
At 20°C, IFT was observed to be at its maximum value but gradually decreased as the

temperature of the system increased. This trend is supported by the work of Jennings et al.

(1971). The decrease in IFT as temperature increased can be explained from the angle of

attraction holding molecules of a liquid together. As the temperature of the system increased the

Vander Waal forces holding the liquids together begin to weaken and decrease hence IFT also

decrease as the forces of attraction reduces.

4.2.2 Effect of pH on Interfacial Tension and Surfactant Adsorption.

The result of this experiment shows that pH optimization is just as important as temperature and

ionic strength in lowering IFT in oil-brine system. Ionic strength of a solution is the measure of

the ion concentration in that solution.

Fig 4-2: IFT against pH at varying temperature

44
The higher the ionic strength of an alkali, the better it ionizes in water and the better its ability to

form surfactant in-situ. This has been the basis of interpretation of surfactant enhanced alkaline

flooding neglecting the effect of optimizing pH. Figure 4-2 below shows the graph of IFT as a

function of pH and temperature.

However, IFT is minimum in the intermediate range of 10 -12 according to figure 4-2. This is

also consistent with the works of Rudin and Wasan (1993), Falcone et al (1982), and Krumrine et

al (1982). According to Rudin and Wasan (1993), IFT goes through a deep minimum in an

aqueous buffered alkaline pH of intermediate range (9-12) in surfactant enhanced flooding.

Figure 4-1 shows the curves going through a deep minimum between a pH of 10-12 and began to

rise after this pH range.

This phenomenon was also explained by Krumrine et al (1982). According to this work, the

alkali in the system serves two purposes. First the alkali (NaOH) generates soap which reduces

capillary forces and lowers IFT hence facilitating the displacement of oil. Secondly, the alkali

when prepared within the intermediate range of pH 9-12 helps minimise surfactant adsorption or

retention on rock surfaces by impacting a negative charge on the rock surfaces there by allowing

a larger supply of surfactant for interfacial activities and hence IFT goes through a deep

minimum. When surfactant retention on rock surfaces is minimised, the wettability of the rocks

remains unchanged (water absorbing properties) hence spontaneous imbibitions is more efficient

to recover oil.

The curves were observed to begin to rise after this range of pH range (9-10). The increase in

IFT after this range is as a result of retention of surfactant on rock surfaces which reduces the

amount of surfactant for interfacial activity, hence IFT began to rise after this range.

45
4.3 Statistical Analysis
Standard analysis was done to calculate the standard errors on the graphs above .This step is

necessary so as to reflect the measure of fluctuation from original of the set of datas measured. In

calculating the standard error, the total mean and standard deviation where calculated

respectively using the equations below:

Mean ( ) ∑ …………………………….. [4-1]

……………….. [4-2]

Standard Error = ………………………………………………[4-3]

Where n and xi represents number of data points and individual data points respectively.

46
5.0 CONCLUSION AND RECOMMENDATION

5.1 Conclusion

The result of this experimental works show why surfactant enhanced flooding would improve oil

recovery than either alkaline or surfactant flooding alone. Since alkaline flooding relies on the

quantity of organic acid present in the oil for surfactant in-situ formation. Technically ,this

means alkaline flooding will not be suitable in oils with little or no organic acid .Similarly

alkaline flooding is not recommended in carbonated reservoirs because of the abundance of

calcium which when mixed with alkali produces hydroxide precipitate that damages the

formation.

Also, surfactant flooding will also be a non-economical method of EOR because of its high cost

and excessive loss to the porous medium even though it proved to be a successful method or

EOR .

However, combining small amount of surfactant normally less than 0.5% together with buffered

solution of alkali in an intermediate pH range of (9-12) will certainly increase oil recovery

solving the challenges of using so much expensive surfactant or having oil recovery based on the

quantity of organic acid present in the oil as in the case of alkaline flooding.

Therefore the findings of this experiment can be summarised as follows;

1. pH is as important as temperature and ionic strength in achieving an ultra-low interfacial

tension in surfactant enhanced alkaline flooding.

47
2. Surfactant retention on rocks is minimized and ultra-low interfacial tension is achieved if

the alkali is prepared between buffered pH of 9-12.

3. The alkali react with organic acid in the oil to forms surfactant in-situ and hence lowers

interfacial tension between oil and brine and also lowers the adsorption of surfactant

retention on rocks if the alkali is prepared at a buffered pH between 9-12.

4. Interfacial tension decreases with increase in temperature .This is attributed to the effect

of temperature on Van der Waal forces holding molecules of liquids together.

Van der Waal forces decreases as temperature increases.

48
5.3 Recommendations

1. Adding surfactant to alkaline certainly improves oil recovery than each alone, but the exact

role the surfactant plays in synergism with alkali remains unknown. Therefore further research

on how to take advantage of this combination (type and quantity of surfactant) in designing

floods for maximum oil displacement should be studied in the future. This is because if more

surfactant is added than necessary, more ionized acid is needed to compensate this increase,

resulting in a shift of the minimum IFT to a higher pH.

2. This work has been able to investigate the effect of pH on anionic surfactant adsorption.

Further research should be done on how other surfactant adsorption can be minimised especially

the cationic surfactant such as Laurylamine hydrochloride.

49
REFERENCES

Boardman Energy partners ,”Exploration and production”. Retrieved from

http://benergypartners.com/Facts_About_Crude_Oil.html (visited 2012)

(CAPP) Canadian Association of Petroleum Producers “Canada’s Oil Industry”. Retrieved from
http://www.capp.ca/canadaIndustry/oil/Pages/default.aspx. (visited 2012)

Castro Peter and Michael Huber (Oct 6 2009);”Marine Biology”; McGraw-Hill

Science/Engineering/Math; 8 edition; Publication Date: Oct 6 2009 | ISBN-10: 0073524166

DeCelles PG; Katherine AG.” Foreland basin systems” Department of Geosciences, University
of Arizona, Tucson, AZ 85721, USA .Retrieved from
http://onlinelibrary.wiley.com/doi/10.1046/j.1365-2117.1996.01491.x/pdf (visited 2012).

Donaldson E.C, Chilingarian E.V, Yen T.F (1989) “Enhanced Oil Recovery, II processes and
operations”.2nd ed.Elsevier science Publishing Company Inc. vol. 17B PG 3- 11.

Farouq-Ali,S.M. and Thomas S. (1994). “A Realistic Look at Enhanced Oil Recovery’Scietia

Iranica”, Vol. 1,No.32 ,Sharif University of Technology (October).

Green, D.W, Willhite, G.P (1998), “Enhanced Oil Recovery”.SPE text book series Vol. 6,
Richardson

Head I.M , Martin D.J & Larter S.R (2003),”Biological activity in the deep subsurface and the
origin of heavy oil’ Nature Publishing Group, VOL 426.

Herron E.H; King S.D. (2004) Petroleum Equities Inc. ”Heavy Oil as the Key to U.S. Energy
Security” Retrieved from
http://www.petroleumequities.com/cgibin/site.cgi?p=energysecurity.html&t=5

IEA (2005),” Resources to Reserves—Oil and Gas Technologies for the Energy Markets of the
Future, Available at http://www.iea.org/press/pressdetail.asp?PRESS_REL_ID=159 (visited
2012)

50
IEA (2012)‘IEA Chart Says Conventional Oil Production Peaked in 2006’.Retrieved from
http://www.treehugger.com/corporate-responsibility/iea-chart-says-conventional-oil-production-
peaked-in-2006.html (Visited 2012)

Drelich J., Fang Ch.,. White CL. (2002).”Measurement of Interfacial Tension In Fluid-Fluid
Systems” Michigan Technological University, Houghton, Michigan.

Jennings, H.Y, Newman, G.H, (1971)” The Effect of Temperature and Pressure on the
Interracial Tension of Water Against Methane-Normal Decane Mixtures” Society of petroleum
engineers Journal, Vol.30 No.71

Jill S. Buckley and Tianguang Fan “crude oil/brine interfacial tensions” PRRC, New Mexico
Tech, Socorro, NM, USA. Retrieved from http://www.scaweb.org/assets/papers/2005_papers/1-
SCA2005-01.pdf (visited 2012).

Johansen E.M. (1923); The interfacial tension between Petroleum Products and Water”
Industrial and Engineering Chemistry Vol. 16 pg 2.

Krumrine,P.H.;Falcone,J.S.; Campbell,T.C (1982).” Surfactant Flooding “The effect of alkaline

additives on IFT, Surfactant Adsorption and Recovery Efficiency”.Soc.Pet.Eng.J.1982, Aug, 503
-513.

Martin, F. D.; Oxely, J. C.; Lim, H.(1985); Presented at the 60th Annual Technical Conference
and Exhibition of the Society of Petroleum Engineers Las Vegas, NV, Sept 22-25, 1985; paper
SPE 14293.

Nelson, R. C.; Lawson, J. B.; Thigpen, D. R.; Stegemeier, G. L. (1984) “Cosurfactant-Enhanced

Alkaline Flooding “. Presented at the SPE/ DOE Fourth Symposium on Enhanced Oil Recovery,
Tulsa, OK,April 15-18,1984; paper SPE/DOE 12672.

NPC (July 18, 2007),” Heavy oil ,Extra-Heavy Oil and Bitumen” Retrieved from
http://downloadcenter.connectlive.com/events/npc071807/pdfdownloads/Study_Topic_Papers/22
-TTG-Heavy-Oil.pdf (visited 2012).

OPPT (1994) “Chemical Fact Sheet “Office Of Pollution Prevention And Toxics, U.S.
Environmental Protection Agency; August 1994

51
.

Petrosas Oil and Gas (2011) “upstream” .Extracted from http://petrosas.com/eor.php (visited
2012)

Rudin, J.; Wasan, D. T.; Bernard, C (1994).” Effect of Added Surfactant on Interfacial Tension
and Spontaneous Emulsification in Alkali/Acidic oil system”. Ind. Eng. Chem. Res.1994, 33,
1150- 1158.

Rudin, J.; Wasan, D. T (1993).” Surfactant-Enhanced Alkaline Flooding: Buffering at

Intermediate Alkaline pH”. SPE Reservoir Eng. 1993,November.

Leick S, Stefan H , Patrick D , Dieter Suter and Heinz Rehage (2010).;Deformation of liquid-
filled calcium alginate capsules in a spinning drop apparatus;Department of Physical Chemistry
II, TechnischeUniversität Dortmund,Germany.;Phys. Chem. Chem. Phys., 2010, 12, 2950-2958.

Sarma, H. K. (1999): “Gas Processes: Principles and Field Application,” Japan National Oil
Corporation, Chiba-Shi, Japan.

Schuler, P. J.; Lerner, R. M.; Kuehne, D. L (1985).” Improving Chemical Flood Efficiency with
Micellar/ Alkaline/Polymer Processes”. Presented at the Fifth Symposium on Enhanced Oil
Recovery,

Selley, R.C. (1998),” Elements of Petroleum Geology”, 2nd ed. Academic Press, San Diego.

Speight J.G (2009) “Enhanced Recovery methods for Heavy oil and Tar sands”;Gulf publishing
company.

Speight, J.G. (2010), ”Enhanced Recovery Methods for Heavy Oil and Tar Sands”. Gulf
Publishing Company, Houston.

Strassner, J.E (March 1968); “Effect of pH on Interfacial Films and Stability of Crude Oil-Water
Emulsions,”JPT 303.

Teledyne Isco, Inc. (2007) “Enhanced Oil Recovery pg. 1”.Retrieved from
http://www.isco.com/WebProductFiles/Applications/105/Application_Notes/Enhanced_Oil_Rec

52
overy.pdf (visited 2012)

Trondheim and Stavanger (2003), ‘CO2 as injection Gas for Enhanced Oil Recovery and
Estimation of the potential on the Norwegian continental shelf. NTNU-Norwegian University of
Science and Technology, Department of Petroleum Engineering and Applied Geophysics Tulsa,
OK, April 2&23,1986; paper SPE/DOE 14934

Unconventional Oil (2007). ”Working Document of the NPC Global Oil and Gas Study” ’pages
4-47.Retrieved from http://www.npc.org/study_topic_papers/29-ttg-unconventional-gas.pdf.
(Visited 2012)

Wikipedia (2012), the free encyclopedia, ” Peak oil”. Retrieved from

http://en.wikipedia.org/wiki/Peak_oil

Zobelle 1947 “Bacterial release of oil from oil bearing material I and II world oil” 126 36 44 ad
127 35 40

53
APPENDICES

Appendix A:

Table of IFT measurements vs. Temperature

Run 1: pH of 8.86 INTERFACIAL TENSION (ϒ) 0 % NaOH

Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.94 0.00047 0.5419
30 1084 968 116 418.879 0.76 0.00038 0.2792
40 1076 963 113 418.879 0.58 0.00029 0.1209
50 1071 960 111 418.879 0.51 0.00026 0.0856
60 1068 959 109 418.879 0.5 0.00025 0.0747
70 1059 955 104 418.879 0.49 0.00025 0.0713
80 1052 950 102 418.879 0.48 0.00024 0.0619

Run 2: pH of 8.86 INTERFACIAL TENSION (ϒ) 0 % NaOH

Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.91 0.000455 0.4917
30 1084 968 116 418.879 0.78 0.00039 0.3018
40 1076 963 113 418.879 0.57 0.00029 0.1209
50 1071 960 111 418.879 0.51 0.00026 0.0856
60 1068 959 109 418.879 0.51 0.00025 0.0747
70 1059 955 104 418.879 0.49 0.00025 0.0713
80 1052 950 102 418.879 0.49 0.00025 0.0699

54
Run 1: pH of 9.12 INTERFACIAL TENSION (ϒ) 4 % NaOH
Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.89 0.000445 0.4600
30 1084 968 116 418.879 0.75 0.000375 0.2683
40 1076 963 113 418.879 0.58 0.00029 0.1209
50 1071 960 111 418.879 0.51 0.000255 0.0807
60 1068 959 109 418.879 0.49 0.000245 0.0703
70 1059 955 104 418.879 0.48 0.00024 0.0631
80 1052 950 102 418.879 0.47 0.000235 0.0581

Run 2: pH of 9.12 INTERFACIAL TENSION (ϒ) 4 % NaOH

Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.88 0.00044 0.4447
30 1084 968 116 418.879 0.73 0.000365 0.2474
40 1076 963 113 418.879 0.56 0.00028 0.1088
50 1071 960 111 418.879 0.51 0.000255 0.0807
60 1068 959 109 418.879 0.49 0.000245 0.0703
70 1059 955 104 418.879 0.48 0.00024 0.0631
80 1052 950 102 418.879 0.47 0.000235 0.0581

55
Run 1: pH of 10.84 INTERFACIAL TENSION (ϒ) 8 % NaOH
Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.68 0.00034 0.2052
30 1084 968 116 418.879 0.58 0.00029 0.1241
40 1076 963 113 418.879 0.54 0.00027 0.0976
50 1071 960 111 418.879 0.48 0.00024 0.0673
60 1068 959 109 418.879 0.47 0.000235 0.0621
70 1059 955 104 418.879 0.47 0.000235 0.0592
80 1052 950 102 418.879 0.44 0.00022 0.0476

Run 2: pH of 10.84 INTERFACIAL TENSION (ϒ) 8 % NaOH

Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.71 0.000355 0.2335
30 1084 968 116 418.879 0.58 0.00029 0.1241
40 1076 963 113 418.879 0.52 0.00026 0.0871
50 1071 960 111 418.879 0.48 0.00024 0.0673
60 1068 959 109 418.879 0.48 0.00024 0.0661
70 1059 955 104 418.879 0.47 0.000235 0.0592
80 1052 950 102 418.879 0.44 0.00022 0.0476

56
Run 1: pH of 11.03 INTERFACIAL TENSION (ϒ) 12 % NaOH
Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.61 0.000305 0.1481
30 1084 968 116 418.879 0.54 0.00027 0.1002
40 1076 963 113 418.879 0.49 0.000245 0.0729
50 1071 960 111 418.879 0.47 0.000235 0.0632
60 1068 959 109 418.879 0.46 0.00023 0.0582
70 1059 955 104 418.879 0.45 0.000225 0.0520
80 1052 950 102 418.879 0.45 0.000225 0.0510

Run 2: pH of 11.03 INTERFACIAL TENSION (ϒ) 12 % NaOH

Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.64 0.00032 0.1710
30 1084 968 116 418.879 0.54 0.00027 0.1002
40 1076 963 113 418.879 0.49 0.000245 0.0729
50 1071 960 111 418.879 0.46 0.00023 0.0592
60 1068 959 109 418.879 0.46 0.00023 0.0582
70 1059 955 104 418.879 0.45 0.000225 0.0520
80 1052 950 102 418.879 0.45 0.000225 0.0510

57
 Run 1: pH of 11.45 INTERFACIAL TENSION (ϒ) 16 % NaOH
Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.51 0.000255 0.0866
30 1084 968 116 418.879 0.49 0.000245 0.0748
40 1076 963 113 418.879 0.49 0.000245 0.0729
50 1071 960 111 418.879 0.45 0.000225 0.0555
60 1068 959 109 418.879 0.44 0.00022 0.0509
70 1059 955 104 418.879 0.44 0.00022 0.0486
80 1052 950 102 418.879 0.44 0.00022 0.0476

Run 2: pH of 11.45 INTERFACIAL TENSION (ϒ) 16 % NaOH

Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.49 0.000245 0.0768
30 1084 968 116 418.879 0.49 0.000245 0.0748
40 1076 963 113 418.879 0.46 0.00023 0.0603
50 1071 960 111 418.879 0.45 0.000225 0.0555
60 1068 959 109 418.879 0.44 0.00022 0.0509
70 1059 955 104 418.879 0.44 0.00022 0.0486
80 1052 950 102 418.879 0.43 0.000215 0.0445

58
Run 1: pH of 11.89 INTERFACIAL TENSION (ϒ) 20 % NaOH
Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.56 0.00028 0.1146
30 1084 968 116 418.879 0.55 0.000275 0.1058
40 1076 963 113 418.879 0.51 0.000255 0.0822
50 1071 960 111 418.879 0.48 0.00024 0.0673
60 1068 959 109 418.879 0.46 0.00023 0.0582
70 1059 955 104 418.879 0.45 0.000225 0.0520
80 1052 950 102 418.879 0.45 0.000225 0.0510

Run 2: pH of 11.89 INTERFACIAL TENSION (ϒ) 20 % NaOH

Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.61 0.000305 0.1481
30 1084 968 116 418.879 0.57 0.000285 0.1178
40 1076 963 113 418.879 0.51 0.000255 0.0822
50 1071 960 111 418.879 0.48 0.00024 0.0673
60 1068 959 109 418.879 0.46 0.00023 0.0582
70 1059 955 104 418.879 0.46 0.00023 0.0555
80 1052 950 102 418.879 0.45 0.000225 0.0510

59
Run 1: pH of 12.56 INTERFACIAL TENSION (ϒ) 24 % NaOH
Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.81 0.000405 0.3468
30 1084 968 116 418.879 0.73 0.000365 0.2474
40 1076 963 113 418.879 0.68 0.00034 0.1948
50 1071 960 111 418.879 0.67 0.000335 0.1831
60 1068 959 109 418.879 0.66 0.00033 0.1718
70 1059 955 104 418.879 0.65 0.000325 0.1566
80 1052 950 102 418.879 0.65 0.000325 0.1536

Run 1: pH of 12.56 INTERFACIAL TENSION (ϒ) 24 % NaOH

Temperature ρb ρl ∆ρ ω Dm Rm (Dm/2) ϒ
°C Kg/m3 Kg/m3 Kg/m3 rad/s mm m mN/M
20 1090 971 119 418.879 0.79 0.000395 0.3217
30 1084 968 116 418.879 0.73 0.000365 0.2474
40 1076 963 113 418.879 0.68 0.00034 0.1948
50 1071 960 111 418.879 0.67 0.000335 0.1831
60 1068 959 109 418.879 0.66 0.00033 0.1718
70 1059 955 104 418.879 0.65 0.000325 0.1566
80 1052 950 102 418.879 0.62 0.00031 0.1333

60
Appendix B:

Table of IFT against pH.

pH vs INTERFACIAL TENSION ( ϒ)
20°C 30°C
pH ϒ (mN/M) pH ϒ (mN/M)
8.86 0.5168 8.86 0.2905
9.12 0.4523 9.12 0.2579
10.84 0.2193 10.84 0.1241
11.03 0.1596 11.03 0.1002
11.45 0.0817 11.45 0.0748
11.89 0.1313 11.89 0.1118
12.56 0.3342 12.56 0.2474

61
 pH vs INTERFACIAL TENSION ( ϒ)
40°C 50°C
pH ϒ (mN/M) pH ϒ (mN/M)
8.86 0.1209 8.86 0.0747
9.12 0.1149 9.12 0.0807
10.84 0.0923 10.84 0.06731
11.03 0.0729 11.03 0.0612
11.45 0.0666 11.45 0.0555
11.89 0.0822 11.89 0.06673
12.56 0.1948 12.56 0.1831

62
 pH vs INTERFACIAL TENSION ( ϒ)
60°C 70°C
pH ϒ (mN/M) pH ϒ (mN/M)
8.86 0.0713 8.86 0.0713
9.12 0.0731 9.12 0.0631
10.84 0.0641 10.84 0.0592
11.03 0.0583 11.03 0.052
11.45 0.0509 11.45 0.0486
11.89 0.05817 11.89 0.0537
12.56 0.1718 12.56 0.1566

63
 pH vs ( ϒ)
80 °C
pH ϒ (mN/M)
8.86 0.0659
9.12 0.0581
10.84 0.0476
11.03 0.051
11.45 0.0461
11.89 0.051
12.56 0.1434

64