Wang Thesis 2018

Copyright
by
Denning Wang
2018
The Thesis Committee for Denning Wang
Certifies that this is the approved version of the following Thesis
Surfactant Retention in Limestones
APPROVED BY
SUPERVISING COMMITTEE:
Gary A. Pope, Supervisor
Kishore Mohanty
by
Denning Wang
Thesis
Presented to the Faculty of the Graduate School of
The University of Texas at Austin
in Partial Fulfillment
of the Requirements
for the Degree of
Master of Science in Engineering
The University of Texas at Austin

May 2018
Dedication
To my Family and my Friends

Acknowledgements
Over the past two years, I have both enjoyed my time and learned a great deal at
the University of Texas at Austin. A great part was due to my supervisor Dr. Gary A.
Pope. Without his continuous mentorship, I would not be where I am today. He was
always available to work with me. He taught me valuable lessons as a graduate student
and gave me advice to grow as an individual. I would like to thank Dr. Kishore Mohanty
for being on my thesis committee.
Without the laboratory staff’s support, none of my work would have been
feasible. I would like to thank Pathma Liyange for always ensuring my work went
smoothly and offering his expertise and advice. Without Nadeeka Upamali’s knowledge,
I would not have been able to navigate the complexity of optimizing phase behaviors.
Sung Hyun Jang and Mathieu Maubert have been pivotal in lending me their expert
know-how. Arnob Bhuyan and Erin Shook have been both coworkers that lent me their
experience and companions outside of the lab. Zach Quintanilla, Nathan Hsu, and Brain
Kang contributed greatly as undergraduate research assistants who aided in my research.
Himanshu Sharma, though not a laboratory staff, patiently helped me with my research.
The moral support by my friends greatly supported me these past two years.
Leonard Chang always made the office welcome with his shining personality. Miguel
Mejia, Lauren Churchwell, and I shared our common experience working in the lab.
Jenny Ryu always made herself available to talk over sandwiches. My roommates
v
Brandon Tang and Ryan Leung were pivotal. Our camaraderie, discussions, and shared
experiences were invaluable.
I would also like to thank the Chemical EOR project sponsors in the Center for
Petroleum and Geosystems Engineering for funding this work and making this reaseach
possible.
vi
Abstract
Denning Wang, M.S.E.
The University of Texas at Austin, 2018
Supervisor: Gary A. Pope
Chemical enhanced oil recovery processes are used to reduce the IFT between oil
and water and mobilize the residual oil. To utilize this method, a surfactant slug is
injected followed by a polymer drive. For the process to be economic, the surfactant
retention must be low so a small surfactant slug can be injected without compromising
the oil recovery. Much progress has been made in reducing surfactant retention in
sandstones, but typically the retention in carbonates is high. Carbonate oil reservoirs
represent a huge target for chemical EOR. Therefore, improving the efficiency of
chemical floods in carbonate oil reservoirs was the focus of this research.
Understanding the geochemical reactions of the injected fluid, in-situ fluid, and
carbonate rocks is important for the chemical flood design. The waterflood brine
typically contains divalent cations such as calcium and magnesium that will consume
alkali and delay the propagation of the high pH front. A preflood can be used to prevent
or mitigate adverse reactions and scaling. Most reservoir carbonates contain gypsum;
vii
therefore, it is important to use an alkali that does not react with gypsum or to suppress
gypsum dissolution as was done in this study.
Systematic experiments were done to examine the effect of pH on surfactant
retention and the geochemical reactions in limestone by adding ammonia and sodium
hydroxide to the chemical solutions. The addition of alkali significantly reduced the
surfactant retention from 0.30 mg/g-rock without using alkali to 0.20 mg/g-rock using
0.75 wt% ammonia to 0.14 mg/g-rock using 0.3 wt% sodium hydroxide. Using sodium
hydroxide to increase the pH reduced the surfactant retention by more than half, which
directly translates to decreasing the surfactant cost by more than half. Since adding a low
concentration of alkali to the chemical solutions is a minor additional expense, the
chemical cost to produce an incremental barrel of oil is greatly reduced.
viii
Table of Contents
LIST OF TABLES XI
LIST OF FIGURES XIV
CHAPTER 1 INTRODUCTION 1
1.1 Research Objectives ...........................................................................................1

1.2 Description of Chapters .....................................................................................2
CHAPTER 2 LITERATURE REVIEW 3
2.1 Chemicals ...........................................................................................................3

2.1.1 Surfactants..............................................................................................3
2.1.2 Co-solvents ............................................................................................4
2.1.3 Polymers ................................................................................................5
2.1.4 Alkali......................................................................................................7
2.2 Microemulsion Phase Behavior .........................................................................9

2.3 Microemulsion Viscosity .................................................................................13
2.4 Mobility Control ..............................................................................................14
2.5 Salinity Gradient ..............................................................................................16
2.6 Alkali-Surfactant Polymer Flooding ................................................................16
2.7 Zeta Potential ...................................................................................................18
2.8 Surfactant Retention.........................................................................................21
2.9 Geochemistry ...................................................................................................23
CHAPTER 3 MATERIALS AND PROCEDURE 25
3.1 Materials ..........................................................................................................25

3.1.1 Surfactants............................................................................................25
3.1.2 Co-Solvents ..........................................................................................25
3.1.3 Polymers ..............................................................................................25
3.1.4 Brines and Alkali .................................................................................25
3.1.5 Crude Oil ..............................................................................................26
3.1.6 Core ......................................................................................................26
3.2 Procedures ........................................................................................................27

3.2.1 Brines ...................................................................................................27
3.2.2 Polymer Solutions ................................................................................27
3.2.3 Chemical Slug and Polymer Drive Solutions ......................................27
3.2.4 Oil Dilution ..........................................................................................28
3.2.5 Phase behavior .....................................................................................28
3.2.6 Aqueous stability .................................................................................29
3.2.7 Coreflood Setup ...................................................................................29
3.2.8 Refractometer .......................................................................................30
3.2.9 pH Measurement ..................................................................................30
3.2.10 HPLC .................................................................................................31
3.2.11 Hyamine Titration ..............................................................................31
ix
3.2.12 Rheometer ..........................................................................................32
3.2.13 Inductively Coupled Plasma Spectroscopy (ICP) ..............................32
3.2.14 Ion Chromatography (IC) ..................................................................33
CHAPTER 4 EXPERIMENTAL RESULTS 34
4.1 Surfactant-Polymer Experiments .....................................................................34

4.1.1 Phase Behavior.....................................................................................34
4.1.2 Single-Phase Dynamic Adsorption Experiment S-1 ............................37
4.1.3 Oil Recovery Experiment S-2 ..............................................................44
4.2 Alkali-Surfactant-Polymer Experiments with Ammonia.................................55

4.2.1 Phase Behavior.....................................................................................56
4.2.2 Single-Phase Dynamic Adsorption Experiment A-1 ...........................58
4.2.3 Oil Recovery Experiment A-2 .............................................................66
4.2.4 Oil Recovery Experiment A-3 .............................................................78
4.3 Alkali Surfactant Polymer Experiments with Sodium Hydroxide ...................91

4.3.1 Phase Behavior.....................................................................................92
4.3.2 Single-Phase Dynamic Adsorption Experiment A-4 ...........................93
4.3.3 Oil Recovery Experiment A-5 ...........................................................100
4.3.6 Oil Recovery Hard Brine Experiment A-8 ........................................134
4.4 Effluent Ion Analysis and Geochemical Interpretation .................................158

4.5 Discussion of Experiments ............................................................................164
CHAPTER 5 SUMMARY AND CONCLUSIONS 169
5.1 Geochemistry .................................................................................................169

5.2 Surfactant Retention and pH ..........................................................................170
5.3 Recommendations for Future Work...............................................................171
BIBLIOGRAPHY 173
x
List of Tables
Table 2.1 Brine Compositions for Simulation. Source: Sanaei et al., 2018 ....................... 9
Table 3.1 Mineralogy of Indiana Limestone by XRD ...................................................... 27
Table 4.1 Core Properties for Experiment S-1.................................................................. 37
Table 4.2 Brine Permeability at 24oC and 78oC for Experimnet S-1................................ 39
Table 4.3 Surfactant Slug and Polymer Drive Properties for Experiment S-1 ................. 39
Table 4.4 Ionic composition of waterflood brine, SP Slug, and polymer drives for
Experiment S-1 ................................................................................................................. 40
Table 4.5 Core Properties for Experiment S-2.................................................................. 45
Table 4.6 Brine Permeability at 24oC and 78oC for Experiment S-2................................ 46
Table 4.7 Sectional Oil Permeability and Oil Relative Permeability for Experiment S-2
........................................................................................................................................... 47
Table 4.8 Oil Flood and Waterflood Summary for Experiment S-2................................. 48
Table 4.9 Total Relative Mobility Curve Parameters for Experiment S-2 ....................... 49
Table 4.10 Surfactant Slug and Polymer Drive Properties for Experiment S-2 ............... 50
Experiment S-2 ................................................................................................................. 50
Table 4.12 Core Properties for Experiment A-1 ............................................................... 58
Table 4.13 Brine Permeability at 24oC and 78oC for Experiment A-1 ............................. 60
Table 4.14 Surfactant Slug and Polymer Drive Properties for Experiment A-1 .............. 60
Table 4.15 Ionic composition of waterflood brine, ASP Slug, and polymer drives for
Experiment A-1 ................................................................................................................. 61
Table 4.18 Sectional Oil Permeability and Oil Relative Permeability for Experiment A-2
........................................................................................................................................... 69
Table 4.19 Water Permeability and Water Relative Permeability for Experiment A-2 ... 69
Table 4.20 Summary of Oil Flood and Waterflood for Experiment A-2.......................... 69
Table 4.21 Total Relative Mobility Curve Parameters for Experiment A-2..................... 70
Table 4.23 Ionic Composition of Waterflood, ASP Slug, and Polymer Drive for
Experiment A-2 ................................................................................................................. 72
Table 4.24 Dilution Test with ASP Slug and Polymer Drive for Experiment A-3 .......... 79
........................................................................................................................................... 82
Table 4.28 Water Permeability and Water Relative Permeability for Experiment A-3 ... 82
Table 4.29 Summary of Oil Flood and Waterflood for Experiment A-3.......................... 82
Table 4.30 Total Relative Mobility Curve Parameters for A-3 ........................................ 83
Experiment A-3 ................................................................................................................. 85
xi
Experiment A-4 ................................................................................................................. 96
Table 4.37 Core Properties for Experiment A-5 ............................................................. 101
Table 4.38 Brine Permeability at 24oC and 78oC for Experiment A-5 ........................... 102
......................................................................................................................................... 103
Table 4.40 Water Permeability and Water Relative Permeability for Experiment A-5 . 103
Table 4.41 Summary of Oil Flood and Waterflood for Experiment A-5........................ 103
Table 4.42 Total Relative Mobility Curve Parameters for Experiment A-5................... 104
Table 4.43 Surfactant Slug and Polymer Drive Properties for Experiment A-5 ............ 106
Experiment A-5 ............................................................................................................... 106
......................................................................................................................................... 114
Experiment A-6 ............................................................................................................... 117
Table 4.55 Sectional Oil Permeability and Oil Relative Permeability for A-7 .............. 125
Table 4.56 Water Permeability and Water Relative Permeability for A-7 ..................... 125
Table 4.57 Summary of Oil Flood and Waterflood for A-7 ........................................... 125
Experiment A-7 ............................................................................................................... 128
......................................................................................................................................... 137
Experiment A-8 ............................................................................................................... 140
xii
Table 4.71 Sectional Oil Permeability and Oil Relative Permeability for A-9 .............. 149
Table 4.74 Total Relative Mobility Curve Parameters for A-9 ...................................... 150
Table 4.76 Ionic Composition of Preflood Brine, ASP Slug, and Polymer Drive for
Experiment A-9 ............................................................................................................... 152
Table 4.77 Chemical Formulations used in Experiments ............................................... 164
Table 4.78 Coreflood Summary for Experiments S-1 to A-3 ......................................... 166
Table 4.79 Coreflood Summary for Experiments A-4 to A-9 ........................................ 167
xiii
List of Figures
Figure 2.2.1 Possible Structure of C15-18 IOS. Source: Levitt et al., 2006 .......................... 4
Figure 2.2 Comparison of Carreau and Power Law Models. Source: Sorbie, 1991. .......... 7
Figure 2.3 Precipitation using Sodium Hydroxide with Various Brines. Source: Sanaei et
al., 2018 ............................................................................................................................... 9
Figure 2.4 Salinity Scan for Microemulsion Phase Behavior ........................................... 11
Figure 2.5 Microemulsion Viscosity as a Function of Oil Fraction. Source: Tagavifar et
al., 2016 ............................................................................................................................. 14
Figure 2.6 Total Relative Mobility Curve......................................................................... 15
Figure 2.7 Relationship of pH and pCa or pMg. Source: Al Mahrouqi et al., 2017 ......... 18
Figure 2.8 Effect of pH on Zeta Potential. Source Tagavifar et al., 2018 ........................ 19
Figure 2.9 Effect of Constant pCa on Zeta Potential. Source: Al Mahrouqi et al., 2017 . 20
Figure 2.10 Sulfate and Calcium Concentration to Zeta Potential. Source: Zhang and
Austad, 2006 ..................................................................................................................... 20
Figure 4.1 Activity Diagram for Formulation SP-1 .......................................................... 35
Figure 4.2 Salinity Scan with 30 Vol% Oil for Formulation SP-1 ................................... 36
Figure 4.3 Tracer Test for Experiment S-1 ....................................................................... 38
Figure 4.4 Effluent Surfactant Concentration for Experiment S-1 ................................... 40
Figure 4.5 Pressure Drop for Experiment S-1 .................................................................. 41
Figure 4.6 Effluent pH for Experiment S-1 ...................................................................... 42
Figure 4.7 Chemical Flood Effluent Salinity for Experiment S-1 .................................... 43
Figure 4.8 Effluent Viscosity for Experiment S-1 ............................................................ 44
Figure 4.9 Tracer Test for Experiment S-2 ....................................................................... 46
Figure 4.10 Total Relative Mobility Curve for Experiment S-2 ....................................... 48
Figure 4.11 Viscosities for SP and PD at 78oC for Experiment S-2 ................................. 49
Figure 4.12 Oil Recovery for Experiment S-2 .................................................................. 51
Figure 4.13 Pressure Drop for Experiment S-2 ................................................................ 52
Figure 4.14 Effluent pH for Experiment S-2 .................................................................... 53
Figure 4.15 Effluent Salinity for Experiment S-2 ............................................................. 54
Figure 4.16 Effluent Viscosity for Experiment S-2 .......................................................... 55
Figure 4.17 Activity Diagram for Formulation ASP-1 ..................................................... 56
Figure 4.18 Salinity Scan with 30 Vol% Oil for Formulation ASP-1 .............................. 57
Figure 4.19 Tracer Test Profile for Experiment A-1 ........................................................ 59
Figure 4.20 Effluent Surfactant Concentration for Experiment A-1 ................................ 62
Figure 4.21 Chemical Flood Pressure Drop for Experiment A-1 ..................................... 63
Figure 4.22 Effluent pH for Experiment A-1.................................................................... 64
Figure 4.23 Chemical Flood Effluent Salinity for Experiment A-1 ................................. 65
Figure 4.24 Effluent Viscosity for Experiment A-1 ......................................................... 66
Figure 4.25 Normalized Salinity Tracer for Experiment A-2 ........................................... 68
Figure 4.26 Total Relative Mobility Curve for Experiment A-2 ...................................... 70
Figure 4.27 Viscosities of ASP Slug and PD at 78oC for Experiment A-2 ...................... 71
Figure 4.28 Oil recovery for Experiment A-2 .................................................................. 73
xiv
Figure 4.30 Pressure Drop for Experiment A-2 ................................................................ 75
Figure 4.34 Normalized Tracer Profile for Experiment A-3 ............................................ 81
Figure 4.35 Total Relative Mobility Curve for Experiment A-3 ...................................... 83
Figure 4.36 Viscosities of ASP Slug and PD at 78oC for Experiment A-3 ...................... 84
Figure 4.37 Oil recovery for Experiment A-3 .................................................................. 86
Figure 4.39 Pressure Drop for Experiment A-3 ................................................................ 88
Figure 4.43 Activity Diagram for Formulation ASP-2 ..................................................... 92
Figure 4.44 Solubilization Ratios for 30% Oil Vol for Formulation ASP-2 .................... 93
Figure 4.45 Normalized Tracer Test for Experiment A-4 ................................................ 95
Figure 4.46 Chemical Flood Effluent Surfactant Concentration for Experiment A-4 ...... 97
Figure 4.49 Effluent Viscosity for Experiment A-4 ....................................................... 100
Figure 4.50 Normalized Tracer Profile for Experiment A-5 .......................................... 102
Figure 4.51 Total Relative Mobility Curve for Experiment A-5 .................................... 104
Figure 4.52 Viscosities for ASP slug and PD at 78oC for Experiment A-5.................... 105
Figure 4.53 Oil recovery for Experiment A-5 ................................................................ 107
Figure 4.54 Effluent Surfactant Concentration for Experiment A-5 .............................. 108
Figure 4.55 Pressure Drop for Experiment A-5 at 2 ft/D ............................................... 109
Figure 4.56 Effluent pH for Experiment A-5.................................................................. 110
Figure 4.57 Chemical Flood Effluent Salinity for Experiment A-5 ............................... 111
Figure 4.60 Viscosities for ASP Slug and PD at 78oC for Experiment A-6 ................... 116
Figure 4.63 Pressure Drop for Experiment A-6 .............................................................. 120
xv
Figure 4.85 Total Relative Mobility for Experiment A-9 ............................................... 150
Figure 4.86 Viscosities of ASP Slug and PD at 78oC for Experiment A-9 .................... 151
Figure 4.93 Effluent Calcium Concentration vs pH ....................................................... 160
Figure 4.94 Effluent Magnesium Concentration vs pH .................................................. 161
Figure 4.95 Effluent Iron Concentration vs pH .............................................................. 161
Figure 4.96 Effluent Aluminum Concentration vs pH.................................................... 162
Figure 4.97 Effluent Ion Concentration for Experiment A-2 ......................................... 162
Figure 4.100 Effluent Ion Concentration for Experiment A-7 ....................................... 164
Figure 4.101 Surfactant Retention vs pH (using data from Maubert et al., 2018).......... 168
xvi
Chapter 1 Introduction
This chapter discusses the primary focus of the thesis and a brief description of
what each chapter entails.
1.1 Research Objectives
As the world’s energy consumption continually increases and the amount of
easily recoverable oil diminishes, the need for additional recovery methods increases to
satisfy energy demands. Surfactants are used in chemical flooding to improve oil
recovery by reducing interfacial tension which reduces the residual oil saturation. Ideally,
a minimum amount of surfactant would be injected to recover the oil. Surfactant retention
is the amount of surfactant lost to the reservoir and directly correlates to the cost of
producing an incremental barrel of oil. When alkali is used to increase the pH and
polymer used to increase the solution viscosity, the chemical flooding process is called
alkali-surfactant-polymer (ASP) flooding. The alkali changes the surface charges from
positive to negative thus repelling the anionic surfactants, leading to a reduction in
surfactant retention. The ASP process and the effect of pH on surfactant retention in
sandstones have been extensively studied for many years and are well understood;
however, the same cannot be said for carbonates. With much of the world’s oil reserves
being in carbonates, this thesis focuses on surfactant retention in limestones. Limestones
and other carbonate rocks are more complex and generally more heterogeneous than
sandstones. The objective of this research was to conduct coreflood experiments to better
1
understand the effect of pH on the adsorption and retention of anionic surfactants using
Indiana limestone.
1.2 Description of Chapters

The thesis is comprised of five chapters. Chapter 2 introduces the background and
literature review on various components involved in chemical EOR. Chapter 3 discusses
the experimental procedures and equipment used in the experiments. Chapter 4 discuss
the experimental results using surfactant-polymer, alkali-surfactant-polymer using

ammonia, alkali-surfactant-polymer using sodium hydroxide, and alkali-surfactant-
polymer using ammonia and sodium hydroxide corefloods and the effluent ion analysis
with geochemical interpretation. The last chapter discusses the conclusions drawn from
the experiments.
2
Chapter 2 Literature Review
The following chapter describes the screening process done to select the optimal
formulations for chemical enhanced oil recovery as well as the current literature for
alkali-surfactant polymer processes.
2.1 Chemicals
This section describes the chemicals used in chemical EOR.
2.1.1 Surfactants
Surfactants are used in the chemical EOR processes to lower the interfacial
tension between oil and water (Lake et al., 2014; Green and Willhite, 2018). Surfactants
or surface-active agents consist of a hydrophilic head group and a hydrophobic tail. EOR
surfactants are selected to interact with both polar and non-polar elements equally and
strongly (Bourrel and Schechter, 1988). Surfactants can be classified into four groups:
cationic, anionic, non-ionic, and zwitterionic. Anionic surfactants were used in this
research study. Anionic surfactants possess negative head charge which is beneficial in
the reduction of surfactant adsorption when the surface charges are negative.
Guerbet alkoxy sulfate surfactants have high performance and low-cost (Adkins et
al. 2012, Lu, et al., 2014, Yan et al., 2017, Pinnawala et al. 2018). These surfactants can
be made with a varying number of propylene oxide (PO) and ethylene oxide (EO) groups
to optimize their performance with the oil and brine. Increasing the number of EO
groups makes the surfactant more hydrophilic. This in turn causes the optimum salinity to
increase. The reverse occurs when increasing the number of PO groups (Bourrel &
Schechter, 1988).
Internal olefin sulfonates (IOS) with carbon numbers of C15-18 and C19-23 are high
performing surfactants (Flaaten et al., 2009; Levitt et al., 2009). IOS are synthesized by
3
sulfonating an olefin at a random internal double bonded position within its aliphatic
carbon chain. The IOS’s twin-tailed characteristic improves the surfactant performance.
The figure below presents an image of what C15-18 could look like (Levitt et al., 2009).
Branching reduces microemulsion viscosity, reduces equilibration time, and promotes
microemulsion formation with fewer tendencies to form undesirable phases such as
viscous macroemulsions (Levitt et al., 2009, Hirasaki et al., 2011, Walker et al., 2012,
Karasinghe et al., 2016).
Figure 2.2.1 Possible Structure of C15-18 IOS. Source: Levitt et al., 2009
2.1.2 Co-solvents
Co-solvents are light alcohols with hydrophobic tails up to C6. Co-solvents differ
from surfactants as surfactants have hydrophobic tails greater than C7, and co-solvents
increase the IFT rather than decrease it. Despite this negative property, co-solvents offer
many other advantages, prompting its use in chemical EOR.
Co-solvents possess many benefits. They lower microemulsion viscosity, increase
aqueous stability, and change the slope of the activity diagram to a more favorable
inclination (Sahni et al., 2010; Lake et al., 2014, Fortenberry et al., 2015, Chang et al.,
4
2016, Tagavifar et al., 2016). Some activity maps show a positive slope where the
optimal salinity increases with oil volume fraction. This is disadvantageous when using a
salinity gradient for the chemical flood as the salinity gradient would need to be steep to
achieve ideal behavior of Type I at the end of the flood. Addition of co-solvents can
flatten the slope, making it more favorable (Fortenberry et al., 2015). Co-solvents reduce
lamellar structures to bicontinuous ones with a high degree of disorder. This prevents the
formations of viscous macroemulsions. Co-solvents also reduce the microemulsion
viscosity (Tagavifar et al., 2016). Hydrophilic co-solvents increase the aqueous solubility
of the surfactants (Sahni et al., 2010).
2.1.3 Polymers
Polymers are used to increase the viscosity of chemical solutions. An efficient
chemical flood requires a stable displacement of the oil bank. The mobility of the
chemical solution must be less than the mobility of the oil bank for a stable displacement.
The surfactant increases the relative permeability and thus mobility by decreasing the
IFT. The viscosity of the displacing phase must be increased to counteract this increase in
mobility. The mobility ratio between the surfactant solution and the oil bank must be less
than one for a stable displacement. The minimum viscosity required for a stable
displacement is equal to the inverse of the minimum total relative mobility of the oil
bank. Higher viscosity also increases the sweep efficiency.
A commonly used polymer is hydrolyzed polyacrylamide (HPAM) (Sorbie,
1991). At typical HPAM used in EOR is hydrolyzed to about 25 to 30% anionic groups.
HPAM viscosity decreases with an increase in salinity until the viscosity is similar to that
of unhydrolyzed polyacrylamide (PAM) at high salinities on the order of 40,000 ppm
TDS. At a high pH or high temperature, additional hydrolysis of the polymer occurs and
increases the sensitivity of the HPAM to divalent cations such as calcium (Levitt et al.,
5
2008) and eventually the HPAM will precipitate at high concentrations of divalent
cations. Therefore, for applications at high temperature in hard brine, alternative
polymers must be used (Levitt and Pope., 2008; Levitt et al., 2011; Quadri, et al., 2015;
Sheng et al., 2015).
Polymer solutions typically exhibit non-Newtonian behavior. At low shear rates,
polymer displays a Newtonian plateau. A non-Newtonian behavior occurs at intermediate

shear rates, which can be fitted to a power-law model, given by the equation below. 𝜇𝑎𝑝𝑝
is the apparent viscosity, and 𝑦̇ is the shear rate in the porous media. K and n are
constants. At high shear rates, polymer rheology is Newtonian.

(1) 𝜇𝑎𝑝𝑝 = 𝐾𝑦̇ (𝑛−1)
. The Carreau model can capture both the Newtonian and non-Newtonian
behavior where 𝜇0 is the viscosity at low shear rates, 𝜇∞ is the viscosity at high shear
rates, and 𝜆 is a time constant.

(𝑛−1)
𝜇−𝜇∞
(2) = (1 + (𝜆𝑦̇ )2 ) 𝑛
𝜇0 −𝜇∞
6
Figure 2.2 Comparison of Carreau and Power Law Models. Source: Sorbie, 1991.
The shear thinning behavior is favorable in reservoirs since at near wellbore
conditions the viscosity will be low, allowing for higher injectivity, while further from
the reservoir, the viscosity increases providing mobility control.
2.1.4 Alkali
Various alkalis have been used for chemical EOR purposes. The main purpose of
using alkali is to increase the pH of the injected fluids. Increasing the pH has many
benefits including the generation of soap from active crude oils and changing the surface
charges of the rock from positive to negative. With the generation of soaps, less
surfactant needs to be injected; however, not all soaps help in lowering the IFT. Some
soaps can hurt the IFT; therefore, it is important to test the effect of pH on the chemical
formulation.
Sodium hydroxide has been used for chemical floods in sandstone reservoirs;
however, it was found that sodium hydroxide reacts with the sandstones (McAuley, 1977;
7
Southwick, 1985). These reactions result in scale formation and a loss in alkalinity.
Surprisingly, the use of sodium hydroxide in ASP floods of carbonates was never
investigated until recently despite it not reacting with calcite (Ehrlich and Wygal 1977;
Mohnot and Bae 1989). Recent studies have shown that sodium hydroxide decreases
surfactant retention (Wang et al., 2017; Maubert et al., 2018). Sodium carbonate is a less
reactive alkali than sodium hydroxide (Burk, 1987; Bataweel et al., 2011; Sheng, 2013;
Kalwar et al., 2014, Sanaei et al., 2018). However, many carbonate reservoirs contain
gypsum or anhydrite which react with sodium carbonate to form a precipitate of calcium
carbonate. Ammonia is an alternative alkali that doesn’t react with calcite (Sharma et al.,
2014; Sharma, 2016; Southwick et al., 2016; Southwick et al., 2018).
Sodium carbonate and ammonia work well as alkalis in sandstones as they buffer
at a sufficient pH above the pHiep of sandstones; however, the same cannot be said for
calcite. Calcite has a higher pHiep than sandstones, so the pH from sodium carbonate and
ammonia may not be adequate to reduce the zeta potential sufficiently to observe the
same benefits in sandstones (Kosmulski, 2010) whereas the pH of sodium hydroxide is
greater than the pHiep of limestone. The lower molecular weight of sodium hydroxide is
another advantage since less mass is needed compared to sodium carbonate.
A concern of using alkali is the reaction with divalent ions. In the presence of
gypsum or anhydrite, calcium carbonate forms with sodium carbonate and calcium
hydroxide forms with hydroxyl ions. To prevent precipitation and loss of alkalinity, a soft
bine preflood can mitigate scale issues. Metal complexing agents and scale inhibitors can
prevent scaling in hard brine (Karazincir et al., 2011).
A simulation done using the coupled UTCHEM-IPREEQC chemical flooding
simulator showed that there was no precipitation using sodium hydroxide in a carbonate
reservoir using a softened seawater preflood (Sanaei et al., 2018). Table 2.1 lists the brine
8
compositions that were used to study scaling. Figure 2.3 shows the results of this scaling
study for the different brines.
Table 2.1 Brine Compositions for Simulation. Source: Sanaei et al., 2018
Figure 2.3 Precipitation using Sodium Hydroxide with Various Brines. Source: Sanaei et
al., 2018
2.2 Microemulsion Phase Behavior

Microemulsion phase behavior samples are prepared by adding brine, surfactants
and oil to a pipette or test tube. It is the first step in a series of laboratory tests needed to
9
develop and optimize a chemical formulation. The rapid formation of a microemulsion
with low viscosity is one of the desirable characteristics of a good formulation.
A microemulsion is a thermodynamically stable fluid consisting of oil, water, and
amphiphile (Bourrel and Schechter, 1988). Microemulsions are classified as Type I, Type
II, or Type III (Winsor 1954). Winsor Type I describes a mixture with an excess oil phase
and a microemulsion phase. Winsor Type II describes a mixture with an excess brine
phase and a microemulsion phase. Winsor Type III describes a three-phase mixture with
an excess brine phase, an excess oil phase, and a microemulsion phase. A Winsor Type
III microemulsion has bicontinuous layers of water and oil and ultra-low interfacial
tension between the microemulsion and the excess phases. The phase behavior shifts
from Type I to Type III to Type II with an increase in salinity or hardness, so
microemulsion phase behavior experiments are done using a salinity scan over a broad
range to capture all three behaviors (Adkins et al., 2012). Figure 2.4 shows an example of
a salinity scan. The phase behavior shifts from a Type I to a Type III to a Type II with
increasing salinity. Keeping the salinity constant, the phase behavior can shift from Type
I to Type II with an increase of propylene oxide (PO) or decrease of ethylene oxide (EO)
in the surfactant molecule.
10
Increasing Salinity
Type I Type III Type II
Figure 2.4 Salinity Scan for Microemulsion Phase Behavior
Once the phase behavior solutions are made, they are mixed several times for the
next few days or weeks. A visual test called an emulsion test is helpful to quickly identify
mixtures with both low IFT and viscosity even before the fluids have equilibrated. The
solubilization ratios are recorded at different times until the mixtures reach equilibrium.
The water solubilization ratio (σw) is the ratio of the volume of brine to the volume of
surfactant in the microemulsion. The oil solubilization ratio (σo) is the ratio of the volume
of oil to the volume of surfactant in the microemulsion. Huh (1979) derived an equation
relating the interfacial tension as a function of the solubilization ratios.
𝐶
(3) 𝛾 = 𝜎2
Where C is a constant typically taken as 0.3 and 𝜎 is the solubilization ratio. A
solubilization ratio of 10 leads to an interfacial tension of 0.003 dynes/cm which is often
sufficient for high tertiary oil recovery in corefloods. The typical IFT for crude oil and
water is 20 dynes/cm, so with a good formulation, the IFT can be reduced by four orders
of magnitude. The optimal salinity is defined as the salinity where the oil and water
11
solubilization ratios are equal. A good surfactant formulation has a low equilibration time
and a high solubilization ratio at the optimal salinity.
Dilution tests are done to observe the behavior between the waterflood brine and
oil (simulated oil bank) and the surfactant slug and between the surfactant slug and
polymer drive. As the mixtures of slug and polymer drive approach the polymer drive
composition, the phase behavior should be Type I to avoid phase trapping and thus high
surfactant retention. Co-solvents can be added to the polymer drive to help with
achieving Type I behavior. If the dilution tests do not present ideal behavior, a change in
co-solvent or co-solvent concentration is applied until the results are satisfactory. Ideally
mixtures of the slug and oil bank should not form viscous macroemulsions or other
undesirable behavior such as precipitation and should initially exhibit low IFT with small
dilutions of the slug. If necessary, the type of concentration of co-solvent in the slug can
be optimized to avoid such undesirable behavior.
Activity maps depict the Type III window as a function of oil volume fraction and
salinity. Soap is formed when alkali is used with active crude oils. The soap typically
shifts the Type III region since it has a different hydrophilic-lipophilic balance (HLB)
than the synthetic surfactant. HLB describes a surfactant’s degree of being hydrophilic or
lipophilic. Co-solvents and hardness also shift the Type III region. If the soaps are more
lipophilic or hydrophobic than the synthetic surfactants in the formulation, the optimal
salinity decreases as the oil volume fraction increases. Co-solvents can be added to
adjust the activity diagram to a more desirable behavior. By knowing how the Type III
boundary shifts with oil concentration, the chemical flood designed can be further
optimized by using a robust salinity gradient.
Chemical mixtures are injected as aqueous solutions, so it is imperative that the
chemicals are soluble or “stable” in the injected brine. Aqueous stability tests are done by
12
conducting a salinity scan. The solutions are clear, single-phase solutions until at salinity
where phase separation occurs. This is an important factor when developing the chemical
formulation (Levitt et al., 2009, Flaaten et al., 2009; Pinnawala et al., 2018). Addition of
hydrophilic co-solvents can increase the aqueous stability (Sanz and Pope, 1995). In most
cases, the aqueous stability salinity must be equal to or greater than the optimum salinity.
2.3 Microemulsion Viscosity

Low IFT is not sufficient for an efficient chemical flood. Microemulsions with
high viscosities or a non-Newtonian behavior result in high surfactant retention and
reduced sweep efficiency (Walker et al., 2012). As the microemulsion viscosity
increases, an increase in polymer concentration of the slug and drive is required to
maintain a stable displacement. The microemulsion viscosity varies as a function of oil
volume fraction (𝜙) as shown in Figure 2.5. Optimal formulations typically yield
microemulsion viscosity 5-6 times greater than the oil viscosity; however, co-solvents
can decrease the viscosity to roughly 2 times greater than the oil. To decrease the
microemulsion viscosity and promote Newtonian behavior, co-solvents are added
(Tagavifar et. al, 2016). The addition of co-solvents also helps to decrease surfactant
retention by decreasing phase trapping.
13
Figure 2.5 Microemulsion Viscosity as a Function of Oil Fraction. Source: Tagavifar et
al., 2016
2.4 Mobility Control

Mobility control is very important for chemical EOR processes. Unless the
viscosity of the injected aqueous solution is greater than a certain value no oil bank will
be formed, or the displacement of the oil bank will be unstable and only a small fraction
of the oil will be produced as oil without chemicals. The total mobility of the oil bank is
the sum of the oil and water mobilities:
(4) 𝜆𝑡𝑜𝑡𝑎𝑙 = 𝜆𝑜𝑖𝑙 + 𝜆𝑤𝑎𝑡𝑒𝑟
The mobility of each fluid is its relative permeability divided by its viscosity. The
apparent viscosity of the oil bank can be calculated from the following equation:
1
(5) 𝜇𝑜𝑖𝑙 𝑏𝑎𝑛𝑘 = 𝑘𝑟𝑜 𝑘
+ 𝑟𝑤
𝜇𝑜 𝜇𝑤
The relative permeabilities are evaluated at the saturations in the oil bank. Figure
2.6 is a plot of the total relative mobility and its inverse. The apparent viscosity of the oil
bank is often close to the maximum in the inverse curve and is typically used to estimate
the required viscosity of the chemical slug. The viscosity of the injected chemical
14
solution must be equal to or greater than the apparent viscosity of the oil bank for stable
displacement to occur.
25 0.4
20
lrtot (1/cP)
15
1/lrtot (cP)
0.2
10
0 0.0
0 0.2 0.4 0.6 0.8 1
Sw
Figure 2.6 Total Relative Mobility Curve
SP and ASP slugs are typically non-Newtonian so the viscosity must be estimated
as a function of shear rate. The equivalent shear rate of a power-law fluid in a porous
medium can be determined by using the following equation.
𝑛
3𝑛+1 𝑛−1 4𝑢
(6) 𝛾𝑒𝑞̇ = 𝐶 ( )
4𝑛 √8𝑘𝑘𝑟𝑤 𝜙𝑆𝑤
Where
𝛾𝑒𝑞̇ represents the equivalent shear rate
C represents the shear correction factor
n represents the power law exponent
u represents the Darcy velocity (Q/A)
k represents the brine permeability
15
krw represents the water relative permeability
𝜙 represents the porosity
Sw represents the water saturation
2.5 Salinity Gradient

A salinity gradient is used to increase the robustness and efficiency of a chemical
flood. Ideally the chemical slug has a salinity less than the waterflood salinity and the
polymer drive has a salinity less than the slug. A relatively low salinity (Type I) in the
polymer drive is required for a low surfactant retention. The slug is usually injected at
optimum salinity to achieve the lowest IFT. Mixing with a higher salinity in the oil bank
increases the robustness of the design because of variations of the optimum salinity for
various reasons such as dilution effects and the uncertainty of the optimum salinity in the
reservoir for various reasons such as uncertainty in the oil composition and changes in the
effective salinity caused by cation exchange (Pope et al., 1979; Lake et al., 2014; Green
and Willhite, 2018). A normal salinity gradient is defined as a waterflood salinity that is
Type II, followed by a slug salinity that is Type III followed by a polymer drive salinity
that is Type I.
A reverse salinity gradient occurs when the waterflood brine is at a lower salinity
than the optimal salinity. This design is less robust than a normal salinity gradient. The
surfactant slug may be injected at a higher than optimal salinity (provided it is still
aqueous stable) so Type III behavior will still occur when it is diluted. Alternatively, a
high salinity preflood can be done to increase the salinity to above optimum, allowing for
a negative salinity gradient.
2.6 Alkali-Surfactant Polymer Flooding

Adding alkali to the surfactant slug has numerous benefits but it also increases the
complexity of the chemical flood. Alkali provides in-situ soap generation with active oils
16
and decreases surfactant adsorption (Nelson et al. 1984, Lake et al. 2014). Alkali by itself
without any synthetic surfactant can produce low IFT when soap forms; however, the
lowest IFT typically occurs at very low alkali concentration. This is a problem for pH
propagation since at a low concentration the alkali will be consumed by the reservoir
(Lieu et al. 1982). Adding surfactants remedies this problem (Nelson et al. 1984).
Surfactants aide in obtaining low IFT with the soaps produced from the alkali being the
primary surfactant and a higher alkali concentration can be used to allow for better pH
propagation (Yang et al. 2010). Co-solvents can also be used to remedy the problem
(Fortenberry et al., 2015), which is the basis for the new ACP flooding process.
The in-situ soap comes from the interaction of naphthenic acid in crude oils with
alkali. The resulting naphthenic soaps are often but not always hydrophobic surfactants.
More soap is generated with sodium hydroxide compared to sodium carbonate (Ding et
al. 2016). The resulting soap causes a shift in the Type III window. This variation can be
captured with an activity map. The salinity gradient would then be designed to account
for the varying Type III window and be in the Type I region when the oil volume fraction
is small and the salinity low relative to optimum salinity.
Surfactant adsorption is reduced as the alkali changes the surface charges of the
minerals in the formation from positive to negative. The zeta potential describes the
electrostatic interactions between the mineral surface and charged species in the aqueous
solution (Al Mahrouqi et al., 2017). The surface charge of calcite is positive at neutral
pH. Increasing the pH above the isoelectric point (pHiep), the point at which the surface
charge is zero, changes the surface charge to negative. This is greatly beneficial in
reducing the adsorption of anionic surfactants. The greater the negative charge, the lesser
the surfactant adsorption for anionic surfactants. Stronger alkali such as sodium
17
hydroxide can provide a higher pH than conventional alkali such as sodium carbonate,
allowing for a more negative surface charge.
2.7 Zeta Potential

Zeta potential is the electric potential between the mineral surface and aqueous
phase, described with a magnitude and sign. A negative zeta potential or negative surface
charge reduces anionic surfactant adsorption, thereby lowering surfactant retention. The
main potential determining ions for zeta potential on carbonates are calcium, magnesium,
and sulfate (Al Mahrouqi et al., 2017). pH indirectly changes the calcium and magnesium
concentration, thereby influencing the surface charges.
Figure 2.7 Relationship of pH and pCa or pMg. Source: Al Mahrouqi et al., 2017
The surface charge consists of negatively and positively charged surface sites.
The amount of each site depends on the relative concentrations of H+ and OH-. If the
number of negatively charged sites is the same as the number of positively charged sites,
the net surface charge is zero. This state is commonly referred to as the point of zero
charge or the isoelectric point (Sondi et al., 2009). The in-situ minerals affect zeta
18
potential. Figure 2.8 illustrates the zeta potential versus pH for calcite and calcite with
iron bearing minerals (hydrous ferric oxides). The zeta potential for calcite with HFO is
greater than that of pure calcite. In reservoirs with iron bearing minerals, a higher pH is
needed to further decrease the zeta potential. Once the pH is greater than the isoelectric
point, the zeta potential becomes negative and increases in magnitude with a further
increase in pH. This indicates that the surface charges become more negative with an
increasingly higher pH can thus further reduce the surfactant adsorption.
Figure 2.8 Effect of pH on Zeta Potential. Source Tagavifar et al., 2018
Studies have shown that changing pH affects pCa, and if pCa is kept constant
while pH is varied, the zeta potential does not change. As the amount of calcium ions
decrease, the zeta potential becomes more negative (Thompson and Pownall, 1988). This
suggests that pH indirectly affects the surface charges by influencing the calcium and
magnesium concentration.
19
Figure 2.9 Effect of Constant pCa on Zeta Potential. Source: Al Mahrouqi et al., 2017
Sulfate has been discussed as a potential determining ion. An increase in sulfate
concentration decreases the zeta potential (Zhang and Austad, 2006). When the amount
of sulfate is in excess of the amount of calcium, the zeta potential becomes negative.
Figure 2.10 Sulfate and Calcium Concentration to Zeta Potential. Source: Zhang and
Austad, 2006
Zeta potential is also affected by salinity. Most brine contains a variety of ions,
including Na+, K+, and Cl-. Since these ions are not potential determining ions, they are
referred to as indifferent ions. As salinity increases, the zeta potential becomes more
20
positive due to the non-potential determining ions interfering with the potential
determining ions’ ability to interact with the calcite surface (Vinogradov et al., 2010). In
order to decrease the zeta potential sufficiently, a higher pCa is required. This can be
achieved with a high pH (Al Mahrouqi et al., 2017).
In reservoirs possessing a formation brine of high salinity, the zeta potential may
be positive. To change the zeta potential from positive to negative, the in-situ calcium
and magnesium concentration must be decreased. This can be done by injecting a brine
with less calcium or magnesium than the in-situ brine, injecting a brine with higher
sulfate concentration, and/or injecting a high pH solution using alkali.
The effect of pH on surfactant retention in limestone using different alkalis is the
main subject of this thesis. Extensive measurements of the ionic composition of effluent
brine samples from corefloods were done to help understand and interpret the results of
the SP/ASP floods.
2.8 Surfactant Retention

Surfactant retention is the difference between the amount of surfactant injected
and the amount of surfactant produced. To improve the economics of chemical EOR, it is
vital the surfactant retention is reduced. A lower surfactant retention means that less
surfactant would need to be injected. Surfactant retention consists of the surfactant
adsorbed onto the rock matrix and lost to phase trapping. An effective way to reduce the
retention of anionic surfactants is to increase the pH above the isoelectric point of the
rock. Above the isoelectric point, the rock surface has a net negative charge. Phase
trapping can occur with macroemulsions or microemulsions (Nelson and Pope 1978). Co-
solvents can be used to prevent macroemulsions and a negative salinity gradient
minimizes both surfactant adsorption and phase trapping of microemulsions (Pope et al.,
1979; Hirasaki et., 1983; Jang et al., 2016; Upamali et al, 2016). The microemulsion
21
rheology affects surfactant retention. A shear-thinning behavior results in more phase
trapping and thus higher surfactant retention. As velocity decreases, the microemulsion
viscosity increases and thus will become more difficult to transport, with this behavior
more evident in heterogeneous reservoirs compared to corefloods.
Surfactant retention in sandstones has been significantly reduced to very low
levels in recent studies (Jang et al., 2016); however, the surfactant retention in carbonates
tends to be significantly higher than sandstones (Levitt and Bourrel, 2016). Solairaj et al.
(2012) reported 0.26 mg/g-rock as the surfactant retention for sandstones for experiments
without any alkali. Silica is negatively charged at reservoir conditions; however, clays are
positively charged at reservoir conditions. The isoelectric point for clays occurs at a pH
of 9 (Hirasaki et al., 2011); therefore, sodium carbonate with a pH of 10.5 is sufficient to
convert the charges from positive to negative. ASP corefloods in sandstones that have
been optimized with a formulation containing a high solubilization ratio and low
viscosity microemulsions with Newtonian behavior yielded surfactant retention on
average of 0.061 mg/g-rock with some being as low as 0.007 mg/g-rock with a high clay
content of 8.8 wt% (Jang et al., 2016). Single-phase dynamic adsorption corefloods had
an average surfactant adsorption of 0.078 mg/g-rock. The best corefloods with co-solvent
in the polymer drive had a surfactant retention of zero within experimental error (Jang et
al., 2016). The lack of phase trapping comes from the low viscosity microemulsions with
Newtonian behavior.
A calcite surface is positive at reservoir conditions. Carbonates often possess iron-
bearing minerals which have a high isoelectric point of 9.7. To produce sufficient
negative charges, the pH must exceed the pHiep by at least 2 pH units (Bunn et al. 2002).
Solairaj et al. (2012) reported surfactant retention of 0.34 mg/g rock in Estaillades
limestone. Cottin et al. (2012) reported surfactant retention of 0.30 mg/g rock in an
22
Estaillades limestone core. Estaillades limestone is 99.5 wt% calcite, does not contain
gypsum, and is much less heterogeneous than most reservoir carbonates. Levitt et al.
(2013) reported surfactant retention of greater than 1.38 mg/g rock in a 20 mD reservoir
carbonate core. Levitt and Bourrel (2016) reported average surfactant retention of 0.58
mg/g rock in 40 Estaillades outcrop corefloods. Chevallier et al. (2013) reported
surfactant retention ranging from 0.38 to 1.9 mg/g rock in Lavoux limestone. Few
measurements of retention in reservoir carbonate cores have been reported using alkali
because most of the reservoir carbonates contain gypsum or anhydrite. Recently Wang et
al. (2017) and Maubert et al. (2018) reported surfactant retention of 0.14 mg/g-rock using
sodium hydroxide in Indiana limestone. Most available surfactant retention data on
limestones show high surfactant retention greater than 0.40 mg/g-rock, so decreasing the
surfactant retention is imperative to improve the economics of chemical EOR.
2.9 Geochemistry
Geochemical interactions play an important role in reservoir performance. The
injection fluid cannot negatively interact with the reservoir by precipitating. Many
reservoirs contain gypsum, introducing a large amount of calcium to the aqueous phase.
The presence of divalent ions negatively impacts surfactants and polymers and reacts
with alkali. Sodium carbonate cannot be used due to precipitation of calcium carbonate.
In the presence of gypsum, an alternative alkali must be used. Ammonia has a high
tolerance for reacting with divalent ions (Sharma et al., 2014; Southwick et al., 2016).
This makes it a suitable alkali to be used in reservoirs containing gypsum.
(7) 𝑁𝑎2 𝐶𝑂3 = 2𝑁𝑎2+ + 𝐶𝑂3−2
(8) 𝐶𝑎𝑆𝑂4 = 𝐶𝑎2+ + 𝑆𝑂4−2
(9) 𝐶𝑎2+ + 𝐶𝑂3−2 = 𝐶𝑎𝐶𝑂3
23
When using sodium hydroxide, the main reaction kinetics involves the formation
of calcium hydroxide and magnesium hydroxide. Based on the equilibrium constants,
magnesium hydroxide precipitates the most readily. The primary source of magnesium
comes from dolomite while calcium comes from both calcite and dolomite.
(10) 𝐶𝑎(𝑂𝐻)2 (𝑠) = 𝐶𝑎2+ + 2𝑂𝐻 − log_k = -5.19
(11) 𝑀𝑔(𝑂𝐻)2 (𝑠) = 𝑀𝑔2+ + 2𝑂𝐻 − log_k = -10.88
The dedolomitization process contributes to the magnesium and consumes alkali,
causing a pH delay (Tagavifar et al., 2018).

(12) 𝐶𝑎𝑀𝑔(𝐶𝑂3 )2 + 2𝑁𝑎𝑂𝐻 = 𝐶𝑎𝐶𝑂3(𝑠) + 𝑀𝑔(𝑂𝐻)2(𝑠) + 𝑁𝑎2 𝐶𝑂3
Calcium sulfate has a high equilibrium constant. Sodium sulfate is added to the
injected solution to suppress gypsum dissolution. This in turn decreases the amount of
calcium ions available to interact with the alkali which allows the use of sodium
hydroxide. The addition of sodium sulfate and alkali decreases the amount of calcium
ions present in the aqueous phase. This in turn affects the zeta potential as discussed in
Section 2.10 Zeta Potential. To isolate the effects of alkali on zeta potential and
surfactant retention, sodium sulfate was added to all coreflood experiments using alkali.
Softened seawater contains a significant amount of sulfate, so it may not be necessary to
add sodium sulfate when it is used for the chemical flood.
Increasing the pH has additional effects on the geochemistry. A high pH reduces
the reaction rate of calcite dissolution (Arvidson et al., 2001). High pH dissolves the
clays, causing a release of more aluminum ions. The effect of aluminum and iron
concentrations from clays and iron bearing minerals must be considered when designing
a chemical flood. For example, ferric ions adversely interact with HPAM polymer (Levitt
et al., 2011, Seright and Skjevrak, 2015). The effect of iron minerals depends on the
oxidation state since ferrous ions do not adversely affect HPAM.

24
Chapter 3 Materials and Procedure
The materials and experimental procedures used in this research are described in
this chapter.
3.1 Materials
3.1.1 Surfactants
C24 Guerbet alcohols with varying number of propoxy (POx) and ethoxy (EOy)
groups were carboxylated (Adkins et al. 2012). C18 oleyl alcohol with POs and EOs was
sulfated (Adkins et al. 2010) at The University of Texas at Austin and used after diluting
to 10% active solutions. The corresponding alcohol alkoxylates were supplied by Harcros
Chemicals. Internal olefin sulfonates (IOS) with carbon numbers in the range of C15-18
and C19-23 were obtained from Shell Chemical Company and were used after adjusting the
pH to about 8 at 10% activity.
3.1.2 Co-Solvents
Phenol ethoxylates with varying EO groups and IBA-PO1-EO5 were obtained by
Harcros Chemicals and were used at 100% active level as co-solvents.
3.1.3 Polymers
The polymer used in the study was a commercially available polyacrylamide.
Flopaam 3330S (co-polymer of acrylamide and acrylic acid, PAM) polymer was
provided by SNF Floerger (Cedex, France) in powder form.
3.1.4 Brines and Alkali
Brines were made from adding laboratory grade salts. Sodium hydroxide, sodium
chloride, sodium bicarbonate, sodium sulfate, potassium chloride, calcium chloride
dihydrate, and magnesium chloride hexahydrate with purity of at least 99.5% were
25
purchased from Fisher Scientific. Nitric acid solution (70% active) and sodium
hypochlorite solution (5.65% - 6% activity) were obtained from Fisher Chemical.
Ammonia solutions were prepared by adding ACS grade ammonium hydroxide solution
consisting of 30% volume fraction ammonia. All materials were used as received without
any further purification.
3.1.5 Crude Oil
A dead crude oil with an API gravity of 28 was filtered through a 0.45 μm filter at
78oC and diluted with 20 wt% n-hexane to mimic the live crude oil viscosity. The
viscosity of this surrogate oil is about 2.4 cP at 78 °C.
3.1.6 Core
The Indiana limestone was obtained from Kocurek Industries (TX, USA). Powder
X-ray diffraction (XRD) analysis by KT-Geoservices Inc on one core shows that Indiana
limestone consists of mostly calcite with iron bearing dolomite and small amounts of
clay. The effluent samples were analyzed after a residence time of 6 days at 78oC. Ion
chromatography detected about 80 ppm of sulfate. Gypsum is the likely source of the
sulfate despite not being detected by XRD.
26
Table 3.1 Mineralogy of Indiana Limestone by XRD
Mineral Composition (wt%)
Quartz 0.9
Calcite 97.7
Dolomite -
Fe-Dolomite 0.2
Pyrite -
K-Feldspar 0.6
Plagioclase -
Halite 0.6
Illite & Mica 0.6
3.2 Procedures
3.2.1 Brines
Brines were made by mixing the salt with deionized water with a resistivity of 18
mohm-m. After being thoroughly mixed by a magnetic stir bar, the brines were filtered
through a 0.45 µm filter.
3.2.2 Polymer Solutions
Polymers were made in 1 wt% stock solutions. The polymer powder was carefully
added to 0.1 wt% NaCl aqueous solution and stirred at 250 rpm using a 5.5 cm magnetic
stirrer for 24 hours to hydrate and homogenize. The polymer solution was then argon
blanketed and placed in a fridge to preserve the solution.
3.2.3 Chemical Slug and Polymer Drive Solutions
A polymer stock solution was added to an aqueous surfactant solution to make up
chemical slugs. The chemical solutions were mixed at 78 oC in a water bath for 2 hours
using a 5.5 cm magnetic stirrer since the solutions were not stable at room temperature,
The polymer drive was mixed for 2 hours at ambient conditions. Both solutions were
filtered through 1.2 µm filter at a constant pressure of 15 psi using argon. After filtering,
27
the filtration ratio (F.R.) was calculated using the following equation where t is the time
of the filtration it takes to reach the indicated volume.
𝑡200 𝑚𝐿 − 𝑡180 𝑚𝐿
𝐹. 𝑅. =
𝑡80 𝑚𝐿 − 𝑡60 𝑚𝐿
If the filtration ratio was between 1 and 1.2, the solution was deemed acceptable;
however, if the filtration ratio was greater than 1.2, the solution was remade and mixed
longer. After filtering, the chemicals were then argon bubbled for 7 hours to remove
oxygen and transferred to columns under vacuum.
3.2.4 Oil Dilution
Crude oil was filtered through a 0.45 µm filter at 78oC. 600 grams of diluted oil
was added to a 1 L glass jar. 150 grams of n-hexane was carefully added to the jar,
making the oil 20 wt% diluted with n-hexane. A magnetic stir bar was used to thoroughly
mix the diluted oil.
3.2.5 Phase behavior
Phase behavior mixtures were prepared in 5 mL borosilicate pipettes. After
adding the desired volumes of surfactant, and brine solutions, the pipettes were argon
blanketed and sealed using a flame torch. The solutions in the pipettes were mixed every
few hours for several days and left alone to equilibrate at 78oC. The phase volumes were
recorded and used to calculate solubilization ratios for several days until they were
constant indicating equilibrium had been reached. The optimum salinity was determined
by both an emulsion test and by where the solubilization ratio curves crossed. Salinity
scans were done at 10, 30, and 50 vol% oil with a fixed surfactant, co-solvent, and alkali
concentration to obtain an activity map. The activity map was used to design the salinity
gradient.
28
3.2.6 Aqueous stability
Aqueous stability solutions were prepared in 15 mL glass tubes. After making the
solution, the aqueous stability samples were mixed thoroughly and argon blanketed. They
were placed in an oven at 78oC. After 24 hours, they were observed for phase separation
to determine the maximum salinity for aqueous stability.
3.2.7 Coreflood Setup
Cores were placed in a heat shrink wrap to protect the cores from getting
contaminated with mineral oil in case of a leak. Cores were then placed in core holders.
The core is placed inside the rubber sleeve with o-rings and metal end caps on either side
to prevent mineral oil used for confining pressure from coming into contact with the core.
The core holder contains three pressure taps along the length of the core. The pressure
taps, inlet, and outlet were connected to pressure transducers to measure pressure drops
across each section of the core.
After the core was loaded inside the core holder, a confining pressure of 1000 psi
using mineral oil was applied for several hours to observe for any leaks. The core was
then vacuumed for several hours to remove air inside the core. The core was then leak
tested using a vacuum gauge to observe if air was entering the core. Once the core was
vacuumed, a brine solution was imbibed into the core. The same brine solution was then
injected at various flow rates to determine the brine permeability. Tracer brine was
injected to determine the core heterogeneity and pore volume. Once the tracer test was
completed, the core holder was placed in an oven with the temperature set to 78oC After
several hours, brine was injected to measure the brine permeability.
If the experiment was an oil recovery experiment, the core was oil flooded with
the backpressure regulator set at ~30 psi. The core was oil flooded until the water cut was
less than 1%. The oil saturation was determined based on the amount of brine displaced.
29
The endpoint oil relative permeability was determined once the pressure drops reached
steady state. Afterwards, the core was waterflooded until the oil cut was less than 1%.
Residual oil saturation to waterflood was determined by volume balance based on the
volume of oil displaced. The endpoint water relative permeability was determined once
the pressure drops reached steady state. The final step was to inject chemical solutions
(i.e. a chemical slug followed by a polymer drive at the same velocity). The chemical
flood oil recovery results were recorded. Effluent surfactant concentration, viscosity,
salinity, ion concentrations and pH were measured.
If the experiment was a single-phase dynamic adsorption experiment, first brine
was injected and then the chemical solutions were injected in the same way as for the oil
recovery experiments. At the end of the flood, effluent surfactant concentration,
viscosity, salinity, and pH were measured. Several experiments had the effluent ions
analyzed.
3.2.8 Refractometer
Refractometers were obtained from Fisher Scientific and used to determine the
salinity of aqueous solutions. Refractometers were calibrated to NaCl, so measurements
had to be corrected when using solutions with other electrolytes or chemicals.
3.2.9 pH Measurement
pH measurements were done using a pH probe. The samples were left for several
minutes until the measurement stabilized. pH measurements were done at ambient
conditions. Thus, the pH data reported in this thesis are not the values at the experimental
temperature of the corefloods, which tend to be lower than the values at room
temperature.
30
3.2.10 HPLC
The surfactant concentration in the coreflood effluent was measured using a
Dionex Ultimate 3000 HPLC (Thermo Scientific) with an evaporative light scattering
detector (ELSD). For HPLC analysis, the effluent samples were diluted 3-fold with an
aqueous solution of 1 wt% sodium hypochlorite and 10 wt% IPA and mixed for 1 hour at
78 °C to degrade the polymer and to solubilize surfactant in the aqueous phase (i.e. to
extract any surfactant in the oil).
A gradient elution of 0.1 M ammonium acetate solution and acetonitrile was used
to separate the surfactants from the natural soaps. The surfactants partitioned between the
mobile phase and the chromatography column (stationary phase). The stationary phase is
hydrophobic, while the mobile phase is polar. This allows the hydrophilic molecules to
remain in the mobile phase and elute first. The different surfactants had different elution
times. The natural soaps had longer retention times in the HPLC column compared to the
surfactants and did not interfere with the surfactant signal. Surfactant peaks were
obtained at the various elution times and the area under the curve was applied to a
calibration curve to determine the surfactant concentration. The detection limit of the
surfactants was approximately 50 ppm depending on the surfactant types and the
presence of certain cationic species.
3.2.11 Hyamine Titration
Hyamine titration was used to measure the surfactant concentration in the effluent
samples. 500 µL was added to a vial containing 6 ml of high-pH buffer (sodium
tripolyphosphate), 1 ml of bromocresol indicator, and 5 mL of chloroform. A 0.002 M
standard hyamine solution was systematically added to each vial in 100 µL increments
and the vial was then mixed. After 1 minute of equilibration, the vial was observed to see
if the indicator had transferred to the bottom layer of chloroform. More hyamine was
31
added until the indicator transferred to the bottom interface. A calibration curve was used
to determine the effluent surfactant concentrations from the hyamine volumes.
3.2.12 Rheometer
An Ares LS-1 rheometer (TA Instruments) was used to measure solution
viscosity. A double walled cylinder geometry was used to measure the viscosity of the
surfactant-polymer slug and polymer drive. A cone-and-plate geometry was used to
measure the effluent samples’ viscosity as the sample volume was 2 mL, which is a
smaller sample size requirement compared to the double walled cylinder.
3.2.13 Inductively Coupled Plasma Spectroscopy (ICP)
The ICP was used to measure the concentrations of magnesium, calcium,
aluminum, and iron in aqueous solutions. Samples with minimal oil were selected as the
oil interferes with the plasma. 1-2 wt% sodium hypochlorite was added to degrade the
polymer with similar procedures as that for HPLC measurements. The samples were
additionally diluted 3-fold with 10 wt% nitric acid. Nitric acid was added to prevent
precipitation of metal oxides/ hydroxides. Magnesium standards were prepared from 0.25
ppm to 12.5 ppm. Calcium standards were prepared from 2 ppm to 100 ppm. Aluminum
standards were prepared from 0.5 ppm to 25 ppm. Iron standards were prepared from 0.1
ppm to 2.5 ppm. Before analyzing the samples, the ICP was purged with 2 wt% nitric
acid to remove air bubbles and remove any artifacts from previous runs. The samples
were checked to make sure they were free of oil and polymer. The detection limit of the
ICP is approximately 100 ppb.
The prepared samples were transferred from the test tubes to the nebulizer where
they were nebulized into a mist. A torch interacts with supplied argon to form a plasma.
The nebulizer directs the mist into a chamber to allow contact with the plasma and
32
ionizes the chemical elements. Mass spectrometry is used to analyze the signal strength
for each ion. The ion concentration was determined by applying the signal strength to a
calibration curve.
3.2.14 Ion Chromatography (IC)
Ion chromatography (IC) measurements were done using a Dionex ICS 3000 ion
chromatograph. Sulfate concentrations in the aqueous solution were measured. The
chromatograph was purged with DI to remove any air bubbles, and the column was
cleaned of any artifacts from previous runs before every use. The sample’s salinity was
kept at a maximum of 1000 ppm by dilution. The samples were treated with bleach to
degrade polymer and filtered through 0.2 µm filter. Afterwards, the samples were diluted
with DI from 20 to 100-fold. Sulfate standards were done from 5 ppm to 300 ppm. The
standard samples were used to obtain a calibration curve. A characteristic peak was
detected and the area under the curve was used to calculate the ion concentration. The
detection limit of the IC was approximately 1 ppm.
33
Chapter 4 Experimental Results
A series of coreflood experiments were performed to observe the effect of pH on
the surfactant retention in Indiana limestone. First phase behavior experiments using
various anionic surfactants were done to observe the IFT and viscosity of the
microemulsions as a function of salinity using hard brine. Surfactant-polymer
experiments were done using synthetic seawater brine to determine the surfactant
retention where the pH was less than pHiep i.e. for positive surface charge. Alkali-
surfactant-polymer coreflood experiments using ammonia were done to observe the
surfactant retention for a pH of about 11, which is greater than pHiep for Indiana
limestone i.e. for negative surface charge. Alkali-surfactant-polymer coreflood
experiments using sodium hydroxide were done to observe the surfactant retention at a
pH of about 12.6. This systematic study examines the effect of pH on surfactant retention
on limestone.
4.1 Surfactant-Polymer Experiments

Surfactant-polymer experiments were done to test the surfactant retention in
Indiana limestone where the pH was below pHiep. The surface charges are positive at the
buffered pH of Indiana limestone, so these coreflood experiments demonstrate the
retention without any alkali in the chemical solutions. Synthetic seawater was used for
the waterflood, surfactant-polymer slug, and polymer drive.
4.1.1 Phase Behavior
Multiple phase behavior experiments were done with various surfactants and co-
solvents. Formulation SP-1 containing 0.50 wt% C18-45PO-45EO-sulfate, 0.30 wt%
Enordet 0332 (C15-18 IOS), 0.20 wt% Enordet 0342 (C19-23 IOS), and 0.50 wt% IBA-1PO-
34
5EO was selected for use in the experiments. The formulation showed ultra-low IFT,
high solubilization ratios, favorable aqueous stability, and a favorable activity diagram.
0.50 wt% C18-45PO-45EO-sulfate, 0.30 wt% Enordet 0332 (C15-18 IOS), 0.20
wt% Enordet 0342 (C19-23 IOS), and 0.50 wt% IBA-1PO-5EO
100000
90000 Type II
TDS (ppm)
80000
Type III
70000
60000
Type I
50000
10 20 30 40 50 60
Oil Concentration
Figure 4.1 Activity Diagram for Formulation SP-1
The activity diagram (Figure 4.1) shows a slight positive slope with the Type III
window shifting to a slightly higher salinity with a greater oil volume fraction. As the
slope was only slightly positive, the formulation was selected. The formulation had a
broad Type III window over 20,000 ppm TDS with a high solubilization ratio at various
oil volume fractions.
35
Aqueous stability = 90,000 ppm TDS
Temp. :78 ºC
After 48 days Optimal: 70,000 ppm TDS
40 30% Oil based on emulsion test done at 48 days
Solubilization Ratio (ml/ml)
30
20
10
0
30000 40000 50000 60000 70000 80000 90000
Salinity (ppm TDS)
Figure 4.2 Salinity Scan with 30 Vol% Oil for Formulation SP-1
The microemulsion phase behavior at 30% oil volume fraction (Figure 4.2)
showed a solubilization ratio of 25 at a salinity of 60,000 ppm TDS, which exceeds the
minimum requirement of 10. Based on an emulsion test, the optimum salinity was 70,000
ppm TDS. The formulation showed favorable fluidity and a short equilibration time. The
aqueous stability was 90,000 ppm TDS with 1500 ppm FP3330S, which is greater than
the optimal salinity. The high solubilization ratio and sufficient aqueous stability justified
the use of this formulation in the surfactant-polymer coreflood experiments.
Dilution tests were done with the oil bank (waterflood brine and oil) and the
surfactant slug. Ultra-low IFT was observed at 50% slug and 50% waterflood brine and
oil. Dilution tests were done with surfactant slug and polymer drive containing 0.50 wt%
36
Phenol-6EO showed low IFT from 10% to 30% polymer drive. Type I behavior occurred
for dilutions greater than 50% polymer drive indicating the surfactant was transferred to
the aqueous phase which minimizes the amount of surfactant lost due to phase trapping.
4.1.2 Single-Phase Dynamic Adsorption Experiment S-1
Coreflood S-1 was a single phase dynamic adsorption experiment (without oil) to
determine the surfactant adsorption in Indiana limestone cores with a positive surface
charge at low pH using formulation SP-1 without any alkali. The core’s dimensions and
mass were recorded (Table 4.1). Afterward, the core was prepared as described in the
3.2.7 Coreflood Setup. The dead-end volume in the core holder was 2 ml. The core was
saturated with 2 wt% KCl.
Table 4.1 Core Properties for Experiment S-1

Rock Type INLS
Diameter 3.81 cm
length 30.56 cm
mass 782.18 g
bulk volume 348.37 cm3
porosity 0.166
area 11.40 cm2
Brine perm (24oC) 219 mD
Pore volume 57.9 mL
Length to Tap 1 7.62 cm
Length to Outlet 30.48 cm
Temperature 78 °C
Brine Flood and Tracer Test at 24oC
2 wt% KCl brine was injected at 2 mL/min and 4 mL/min to establish the brine
permeability at 24oC using Darcy’s equation. The pressure drop at steady state was used
37
to calculate the brine permeability. SW brine with brine composition listed in Table 4.4
was injected as tracer brine at 2 mL/min with a sample taken every 2 minutes for a
samples size of 4 mL. The tracer brine broke through at 0.26 PV and took 2.1 PV for the
effluent salinity to reach the injected salinity (Figure 4.3). The early breakthrough time
and the pore volume injected to reach the influent salinity indicates the core was very
heterogeneous. The pore volume was determined to be 57.9 mL with a porosity of 16.6%.
After the tracer test, the core was placed in an oven and heated to 78oC.
1.0
PV =57.9 ml
0.8
Normalized Salinity
0.6
0.4
0.2
0.0
0 50 100 150
Effluent Volume (ml)
Figure 4.3 Tracer Test for Experiment S-1
Brine Flood at 78oC
Once the core equilibrated at 78oC SW brine was injected at 2 mL/min and 4
mL/min to establish the brine permeability at 78oC. The pressure drops during steady
state conditions were used to calculate brine permeability. The brine permeability at 78oC
38
was compared to that at 24oC (Table 4.2). Section 1 experienced the largest decrease in
brine permeability by 25%, while the average core permeability decreased by 5%.
Table 4.2 Brine Permeability at 24oC and 78oC for Experimnet S-1
Sectional Brine Perm at Brine Perm at
permeability (mD) 24oC (mD) 78oC (mD)
Section 1 223 167
Section 2 220 228
Section 3 338 339
Section 4 159 175
Whole 219 209
Chemical Flood
The surfactant slug and polymer drive were prepared based on the steps described
in section 3.2.3 Chemical Slug and Polymer Drive. Polymer was added to the chemicals
to emulate a chemical flood to recover oil. A 0.6 PV surfactant slug was injected at 1
ft/day followed by a polymer drive containing 0.50 wt% Phenol-6EO at the same
velocity. Table 4.3 lists the properties of the surfactant slug and polymer drive. Table 4.4
describes the ionic composition of SW, SP Slug, and PD.
Table 4.3 Surfactant Slug and Polymer Drive Properties for Experiment S-1
Surfactant Slug Polymer Drive
PV Injected 0.6 2.4
Polymer FP 3330S FP 3330S
Polymer cc (ppm) 3500 3500
Frontal Velocity
(ft/day) 1 1
Filtration Ratio 1.03 1.14
pH 8.2 7.2
Co-solvent 0.5% IBA-1PO-5EO 0.5% Phenol-6EO
Salinity (ppm TDS) 80,000 49,994
Viscosity at 7.31 s-1
and 78 C 5.4 6.8
39
Experiment S-1
Ionic Waterflood Brine ASP Slug Polymer Drive
Species (SW) (ppm) (ppm) (ppm)
Na+ 15163 26964 15163
K+ 552 552 552
Ca2+ 651 651 651
Mg2+ 1946 1946 1946
Cl- 27982 46181 27982
SO42- 3700 3700 3700
TDS 49994 79994 49994
Chemical Flood Results
After 3 PV of injection, the chemical flood was stopped. Effluent surfactant
concentration was determined by hyamine titration. Surfactant adsorption was determined
to be 0.287 mg/g-rock with 0.444 mg/g-rock being injected. Surfactant broke through at
0.79 PV and reached a peak concentration of 5500 ppm at 1.2 PV (Figure 4.4).
6000
SUrfactant Concentration (ppm)
5000
4000
3000
2000
1000
0
0 0.5 1 1.5 2 2.5 3
Pore Volumes
Figure 4.4 Effluent Surfactant Concentration for Experiment S-1
40
The pressure drop during the chemical flood is presented in Figure 4.5. The
pressure drops continually increased throughout the flood, indicating there was polymer
plugging. The synthetic seawater brine used was not stable based on geochemical
calculations using PHREEQC; however, the solutions were clear with no signs of
precipitation during injection. The unstable synthetic seawater brine most likely
precipitated during the chemical flood causing the increase in pressure drop.
Chemical Flood for S-1

5
Whole
Sec 1 0.041 mL/min (1ft/day)
Sec 2
Sec 3
Pressure Drop [psi]
4
Sec 4
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Figure 4.5 Pressure Drop for Experiment S-1
The effluent pH remained at the buffered pH of the core (~7.5) throughout the
chemical flood (Figure 4.6). At a pH of 7.5, the surface charges are positive, which
contributes to the high surfactant adsorption.
41
9
pH
pH,
injected
8
pH
6
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Figure 4.6 Effluent pH for Experiment S-1
Effluent salinity reached a peak salinity of 73,000 ppm TDS at 1.12 PV (Figure
4.7). This shows how the salinity of the slug propagated well throughout the core with
minimal dilution.
42
100000
Effluent Salinity
Injected Salinity
80000
Salinity (ppm TDS)
60000
40000
20000
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Figure 4.7 Chemical Flood Effluent Salinity for Experiment S-1
Effluent viscosity started to increase at 0.62 PV and took 1.74 PV to reach the
influent viscosity (Figure 4.8). This indicates the viscosity propagated very well
throughout the core.
43
25 80000
Effluent Viscosity
Viscosity measured at 24 C (cP)
injected viscosity
Salinity
20
60000
Salinity (ppm TDS)

15
40000
10
20000
5
0 0
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
Figure 4.8 Effluent Viscosity for Experiment S-1
Discussion of Results
The surfactant adsorption was determined to be 0.287 mg/g-rock. The surfactant
adsorption is relatively high because surface charges on limestone are positive at near
neutral pH. The next step was to investigate the oil recovery and surfactant retention
using the same formulation.
4.1.3 Oil Recovery Experiment S-2
Coreflood S-2 was an oil recovery experiment to determine the surfactant
retention and oil recovery in Indiana limestone cores in synthetic seawater brine using a
formulation without any alkali. The slug size was adjusted accordingly such that the
amount of surfactant injected was roughly the same as the surfactant adsorbed in the
previous experiment. The core’s dimensions and mass were measured and recorded
44
(Table 4.5). Afterward, the core was prepared as described in the 3.2.7 Coreflood Setup.
The dead volume in the core holder was 2 ml. The core was saturated with 2 wt% KCl.
Table 4.5 Core Properties for Experiment S-2

Rock Type INLS
Diameter 3.81 cm
length 29.67 cm
mass 766.0 g
porosity 0.167
area 11.40 cm2
o
Brine perm (78 C) 199 mD
Pore volume 56.6 mL
Temperature 78 °C
Brine Flood and Tracer Test
The core was brine flooded with 2% KCl at 2 mL/min and 4 mL/min for 1.9 PV
to establish the brine permeability at 24oC. The pressure drop at steady state were used
calculate the brine permeability. Afterward a 6 wt% KCl tracer brine was injected at a
flow rate of 2 mL/min with a sample taken every 2 minutes to establish the core
heterogeneity and pore volume. The tracer fluid broke through at 0.4 PV of injection, and
the tracer test took more than 2 PV before the effluent salinity reached the influent
salinity (Figure 4.9), indicating the core was very heterogeneous.
45
1.0
PV =56.6 ml
0.8
Normalized Salinity
0.6
0.4
0.2
0.0
0 50 100 150
Figure 4.9 Tracer Test for Experiment S-2
Once the tracer test was completed, the core was placed in an oven with the
temperature at 78oC. After equilibrating for several hours, 6 wt% KCl was injected at 2
mL/min and 4 mL/min to measure the brine permeability at 78oC. The brine permeability
data at 24oC and 78oC are presented in Table 4.6. The brine permeability at 78oC
decreased by 14% compared to that at 24oC with Section 4 decreasing the most.
Table 4.6 Brine Permeability at 24oC and 78oC for Experiment S-2
Sectional Brine Perm at Brine Perm at

permeability (mD) 24oC (mD) 78oC (mD)
Section 1 199 186
Section 2 192 207
Section 3 249 214
Section 4 359 188
Whole 232 199
46
Oil Flood
A column with diluted oil was placed in the oven at 78oC and was heated for three
hours. A backpressure regulator (bpr) was added to the coreflood setup to increase the
pressure so gas would not evolve from the oil in the core. This problem is caused by the
high vapor pressure of the hexane added to the dead crude oil. Oil was injected at 120 psi
using argon with the bpr set to ~30 psi. This allowed for a ~90 psi pressure differential
across the core during the oil flood. The oil flood was stopped after the water cut was less
than 1%. The initial oil saturation (Soi) was estimated as 0.44 based on a volume balance.
The endpoint oil relative permeability kroo was determined to be 0.76 based on the steady
state pressure drop across the entire core. Table 4.7 shows the kroo values across each
section of the core.
Table 4.7 Sectional Oil Permeability and Oil Relative Permeability for Experiment S-2
Section Oil Permeability (mD) kroo

Section 1 111 0.72
Section 2 95 0.61
Section 3 123 0.79
Section 4 168 1.07
Whole 119 0.76
Waterflood
SW brine was injected at 10 ft/day until the oil cut was less than 1% and the
pressure drop had reached steady state after 2 PV. During the waterflood, the pressure
taps did not communicate. It is likely that the rubber sleeve interfered with the pressure
taps; therefore, the pressure drop across the entire core was used to calculate the endpoint
water relative permeability. At the end of the waterflood, the residual oil saturation to
water (Sorw) was estimated to be 0.21 based on volume balance and the endpoint water
relative permeability krwo was 0.10 (Table 4.8).

47
Table 4.8 Oil Flood and Waterflood Summary for Experiment S-2
Oil flood Waterflood
Soi 0.44 Sorw 0.21
o o
kro 0.76 krw 0.10
Mobility Control
Using the relative permeability parameters given in Table 4.9 to calculate the total
relative mobility curve, a viscosity of 9.8 cP was estimated as the minimum viscosity
required for a stable displacement (Figure 4.10).

12 0.4
10
lrtot (1/cP)
1/lrtot (cP)
6 0.2
0 0.0
0 0.2 0.4 0.6 0.8 1
Sw
Figure 4.10 Total Relative Mobility Curve for Experiment S-2
48
Table 4.9 Total Relative Mobility Curve Parameters for Experiment S-2
krwo 0.10
o
kro 0.76
nw 2.5
no 2.5
Swr 0.56
Sor 0.21
µw 0.4 cp
µo 2.4 cp
The viscosity of the SP slug and polymer drive using 3500 ppm FP 3330S
polymer is shown in Figure 4.11. At an injection rate of 1 ft/day, the equivalent shear rate
in the core is 7.31 s-1 assuming C is 2 and n is 0.6. The viscosities of the SP slug and
polymer drive at 7.31 s-1 and 78oC are 9.2 cP and 9.7 cP, respectively.
100
Surfactant-Polymer Slug
Polymer Drive
Viscosity (cP)
10
1
1 10 100
Shear Rate (s^-1)
Figure 4.11 Viscosities for SP and PD at 78oC for Experiment S-2
Chemical Flood
in section 3.2.3 Chemical Slug and Polymer Drive. The injected slug size was less than
49
the previous experiment. Based on the surfactant adsorption, a 0.4 PV slug was sufficient
to satisfy surface adsorption. Both the surfactant slug and polymer drive contain 2500
ppm hardness. The surfactant slug and polymer drive properties are presented in Table
4.10. The compositions of SW, SP slug, and polymer drive are presented in Table 4.11.
Table 4.10 Surfactant Slug and Polymer Drive Properties for Experiment S-2
PV Injected 0.4 2.1
Frontal Velocity
(ft/day) 1 1
pH 8.1 7.8
Co-solvent 0.5% IBA-1PO-5EO 0.5% Phenol-6EO
and 78 C 9.2 9.7
Experiment S-2
Species (SW)(ppm) (ppm) (ppm)
Na+ 15163 26964 15163
K+ 552 552 552
Ca2+ 651 651 651
Mg2+ 1946 1946 1946
Cl- 27982 46181 27982
SO42- 3700 3700 3700

TDS 49994 79994 49994
At the end of the chemical flood, Sorc was 0.12 and the tertiary oil recovery was
43.4% (Figure 4.12). All the injected surfactant was retained, indicating the surfactant
50
retention was at least 0.296 mg/g-rock. Oil broke through early due to the high
heterogeneity of the core as seen from the tracer test.
Figure 4.12 Oil Recovery for Experiment S-2
During the chemical flood, the pressure taps failed to communicate. The pressure
drop across the whole core showed more scatter than typically observed in chemical
floods (Figure 4.13); however, the general trend shows the pressure drop did not reach a
steady state. Similarly to the previous experiment S-1, the SW brine was unstable and
most likely precipitated during the chemical flood causing the increase in pressure drop.
51
Whole Flood
Chemical
4
0.041 ml/min Whole
Pressure Drop [psi]
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Figure 4.13 Pressure Drop for Experiment S-2
The pH remained at the buffered pH of the core (~8) throughout the core flood
(Figure 4.14). At a pH of 8, the surface charges of calcite are positive, which contributes
to the high surfactant retention.
52
Figure 4.14 Effluent pH for Experiment S-2
As shown in Figure 4.15, the injected salinity broke through early at 0.3 PV due
to the high heterogeneity of the core. The salinity reached a peak of 60,000 ppm TDS at
0.91 PV. This is less than the injected slug salinity of about 80,000 ppm TDS because the
slug was diluted in front and back by the lower salinity of the waterflood and polymer
drive of about 50,000 ppm TDS (Table 4.11). The peak effluent salinity was lower than
that of the previous experiment because the slug size was smaller. At 1.98 PV, the
effluent salinity reached the injected polymer drive salinity of 50,000 ppm TDS, which is
Type I.
53
Figure 4.15 Effluent Salinity for Experiment S-2
Effluent viscosity started to increase at 0.56 PV (Figure 4.16). Effluent viscosity
reached the injected polymer drive viscosity at 1.27 PV. The polymer drive viscosity
degraded from 9.7 cP before chemical injection to 6.9 cP after chemical injection at 7.31
s-1 during the ~2.5 days of injection.
54
30 80000
Effluent Viscosity
Viscosity at 7.31 s-1 and 24 C (cP)
injected viscosity
25 Salinity
60000
Salinity (ppm TDS)

20
15 40000
10
20000
5
0 0
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
Figure 4.16 Effluent Viscosity for Experiment S-2
All the injected surfactant was retained, indicating surfactant retention of at least
0.296 mg/g-rock. The effluent pH remained constant at a value of 8, indicating the
surface charges were positive which contributed to the high surfactant retention. The low
tertiary oil recovery was due to all the surfactant being retained, moderate degradation of
the polymer and the high heterogeneity of the core.
4.2 Alkali-Surfactant-Polymer Experiments with Ammonia

After establishing the surfactant retention in Indiana limestones using an SP
formulation was ~0.29 mg/g-rock, the next step was to investigate the effects of alkali on
the surfactant retention. Ammonia was tested with a pH of ~11 which is higher than the
isoelectric point of calcite with iron bearing minerals. With a pH greater than the
55
isoelectric point, the zeta potential is negative, thereby reducing surfactant adsorption.
These coreflood experiments involve conducting a preflood of soft brine and adding 2
wt% Na2SO4 to the surfactant-polymer slug and polymer drive. Sodium sulfate was
added to the chemical solutions to prevent gypsum dissolution.
Multiple ASP phase behavior experiments were done with various surfactants and
co-solvents. Formulation ASP-1 containing 0.65 wt% C24-45PO-30EO-COONa, 0.35
wt% C15-18 IOS, 0.5 wt% C19-23IOS, and 0.25 wt% phenol-4EO was selected since it
showed favorable characteristics of ultra-low IFT, high solubilization ratios, and
favorable aqueous stability.
0.65% C24-45PO-30EO-COONa, 0.35% C15-18 IOS, 0.5% C19-23

IOS, 0.25% Phenol-4EO, 0.75% NH4OH and 2% Na2SO4
110000
100000 Type II
90000
TDS (ppm)
80000
Type III
70000
60000
50000
Type I
40000
0 10 20 30 40 50 60
Oil Concentration
Figure 4.17 Activity Diagram for Formulation ASP-1
56
The activity diagram shown in Figure 4.17 displays a negative slope with the
Type III window shifting to a lower salinity with a greater oil volume fraction. As the oil
volume fraction increases, more in-situ soap was generated from the alkali reacting with
the naphthenic acids, shifting the optimal salinity. The activity diagram shows a minor
decrease in the Type III window by 10,000 ppm TDS from 10 vol% oil to 50 vol% oil;
however, the Type III window itself is relatively broad with a 15,000 ppm TDS window.
Since the Type III window shifted to a lower salinity with a higher oil concentration, the
generated soap was determined to be more hydrophobic than the surfactants used in the
formulation.
Aqueous stability = 91000 ppm TDS
Temp. :78 ºC
20 After 84 days
30% Oil
15
Solubilization Ratio (cc/cc)
10
0
40000 50000 60000 70000 80000 90000 100000
Salinity (ppm TDS)
Figure 4.18 Salinity Scan with 30 Vol% Oil for Formulation ASP-1
The microemulsion phase behavior at 30% oil volume fraction shown in Figure
4.18 displayed a solubilization ratio of 17 at a salinity of 72,500 ppm TDS. The aqueous
57
stability was at 91,000 ppm TDS with 1500 ppm of FP 3330S polymer which is greater
than the optimum salinity. The high solubilization ratio and sufficient aqueous stability
made this formulation a good candidate to test in a coreflood.
4.2.2 Single-Phase Dynamic Adsorption Experiment A-1
Coreflood A-1 was a single phase dynamic adsorption experiment to determine
the surfactant adsorption in Indiana limestone using ammonia in the ASP slug. The core’s
dimensions and mass were recorded (Table 4.12). The core was prepared as described in
section 3.2.7 Coreflood Setup. The dead volume in the core holder was 2 ml. The core
was saturated with 2 wt% KCl.
Table 4.12 Core Properties for Experiment A-1

Rock Type INLS
Diameter 3.81 cm
length 30.39 cm
mass 776.90 g
porosity 0.164
area 11.42 cm2
Pore volume 57.0 mL
Temperature 78 °C
The brine permeability was established at 2 mL/min and 4 mL/min after 1.4 PV of
injection. The pressure drop at steady state conditions was applied to Darcy’s law to
calculate the brine permeability. A tracer brine of 7.725 wt% NaCl was injected at 3
mL/min with a sample rate of 1 min per tube to determine the core heterogeneity and
58
pore volume. The tracer brine broke through at 0.5 PV and took 2.07 PV before the
effluent salinity reached the influent salinity (Figure 4.19), indicating the core was very
heterogeneous. The tracer test determined the pore volume to be 57 mL.
1.0
PV =57 ml
0.8
Normalized Salinity
0.6
0.4
0.2
0.0
0 50 100 150
Figure 4.19 Tracer Test Profile for Experiment A-1
Brine Flood at 78oC
The core was then placed in an oven and heated to 78oC. Once the core
equilibrated at 78oC , 7.725 wt% NaCl was injected for 1.5 PV. The steady state pressure
drops at 2 mL/min and 4 mL/min were used to determine the brine permeability at 78oC.
The brine permeability did not vary much with the increase in temperature. Table 4.13
details the brine permeability at 24oC and 78oC.
59
Table 4.13 Brine Permeability at 24oC and 78oC for Experiment A-1
Section Permeability (mD)
Temp: 24oC Temp: 78oC
Section 1 279 295
Section 2 387 393
Section 3 261 269
Section 4 299 285
Whole 299 303
Chemical Flood
The ASP slug and polymer drive (PD) were prepared using the procedure
described in section 3.2.3 Chemical Slug and Polymer Drive. Polymer was added to the
slug and drive to mimic an oil recovery experiment with mobility control. The equivalent
shear rate in the core was calculated to be 5.87 s-1 at a frontal velocity of 1 ft/day
assuming C=2. Sodium sulfate was added to the slug and drive to suppress gypsum
dissolution. Table 4.14 lists the properties of the ASP slug and PD.
Table 4.14 Surfactant Slug and Polymer Drive Properties for Experiment A-1
PV Injected 0.4 3.1
Frontal Velocity (ft/day) 1 1
pH 10.7 10.8
Co-solvent 0.25% Phenol-4EO 1% Phenol-4EO
Viscosity at 5.87 s-1 and 78 C 14.3 17
60
Experiment A-1
Species (ppm) (ppm) (ppm)
Na+ 30388 28110 19259
Cl- 46862 33365 19715
-2
SO4 0 13526 13526
NH4OH 0 7500 7500
TDS 77250 75000 52500
After 3.5 PV of injection, the chemical flood was stopped. Effluent surfactant
concentration was calculated by hyamine titration. Surfactant adsorption was determined
to be 0.155 mg/g-rock. Surfactant broke through at 0.64 PV and reached a peak
concentration of 4300 ppm at 1.31 PV (Figure 4.20). The surfactant adsorption using
formulation ASP-1 was lower than that of formulation SP-1 because of the higher pH.
This indicates ammonia provides a pH greater than the estimated pHiep of Indiana
limestone to turn the surface charges negative.
61
5000
4000
Surfactant Concentration (ppm)
3000
2000
1000
0
0.00 0.50 1.00 1.50 2.00 2.50 3.00 3.50
PV
Figure 4.20 Effluent Surfactant Concentration for Experiment A-1
During the chemical flood, the pressure drop was recorded to observe polymer
transport. Figure 4.21 shows the pressure drop increased as polymer displaces the in-situ
brine and reached steady state. There was no indication of plugging or precipitation.
62
Chemical Flood
1.5
Whole
Sec 1 0.04 ml/min
Sec 2
Sec 3
Pressure Drop [psi]
Sec 4
1.0
0.5
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Pore Volumes
Figure 4.21 Chemical Flood Pressure Drop for Experiment A-1
The effluent pH was measured using a pH probe. The injected pH broke through
at 0.5 PV and reached a pH of 10 at 1 PV. This indicates the pH showed good
propagation with minimal alkali consumption (Figure 4.22). The effluent pH shows an
increase followed by a sharp decrease. This is due to the effluent samples being exposed
to the open air overnight. Carbon dioxide in the air mixed with the samples and caused
the pH to decrease. The pH measured at 1.58 PV, 2.39 PV, and 3.31 PV were measured
when the sample was ready, so those samples had the least amount of time exposed to
carbon dioxide. Using those three points, the effluent pH reached 10.5 which is above the
estimated pHiep of Indiana Limestone.
63
11
10
pH
pH
pH, injected
9
7
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Pore Volumes
Figure 4.22 Effluent pH for Experiment A-1
The effluent salinity was determined using a refractometer. The injected salinity
broke through at 0.77 PV and reached the injected salinity at 2.39 PV of injection (Figure
4.23).
64
Salinity (ppm TDS)
100,000
Salinity
Salinity, injected
80,000
60,000
40,000
20,000
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Pore Volumes
Figure 4.23 Chemical Flood Effluent Salinity for Experiment A-1
The effluent viscosity began increasing at 0.64 PV and reached the injected
viscosity at 2.25 PV of injection (Figure 4.24). This indicates the viscosity propagated
well.
65
Viscosity at 24 C and 5.87 s-1 (cP) 50 100000
40 80000
Salinity (ppm TDS)

30 60000
20 40000
Effluent Viscosity
10 20000
injected viscosity
Salinity
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Pore Volumes
Figure 4.24 Effluent Viscosity for Experiment A-1
Surfactant adsorption using ammonia was determined to be 0.155 mg/g-rock
which was a significant decrease compared to that of SP experiments. This indicates
ammonia provides a pH greater than the pHiep thus changing the surface charges to
negative. The next step was to determine the surfactant retention with an oil recovery
experiment.
4.2.3 Oil Recovery Experiment A-2
Coreflood experiment A-2 was an oil recovery experiment to determine the
surfactant retention in Indiana limestone using ammonia as an alkali with softened brine.
The core’s dimensions and mass were recorded (Table 4.16). Afterward, the core was
66
prepared as described in the 3.2.7 Coreflood Setup. The dead volume in the core holder
was 2 ml. The core was saturated with 2 wt% KCl.
Dilution tests were done with the waterflood brine and ASP slug. Ultra-low IFT
occurred between 50 to 60% slug. A dilution test done with ASP slug/oil and polymer
drive containing 1 wt% Phenol-4EO demonstrated Type I behavior starting from 60%
polymer drive. Type I behavior in the core prevents microemulsion phase trapping, which
results in high surfactant retention.

Rock Type INLS
Diameter 5.11 cm
length 31.00 cm
mass 1445.94 g
porosity 0.157
area 20.51 cm2
o
Pore volume 99.8 mL
Temperature 78 °C
The core was injected with 2 wt% KCl at 2 mL/min and 4 mL/min to establish the
brine permeability at 24oC. A 7.725 wt% NaCl tracer brine was injected to establish the
core heterogeneity and pore volume. The tracer brine broke through at 0.53 PV of
injection, and it took 2 PV for the influent brine to completely displace the in-situ brine
as shown in Figure 4.25. This indicates the core was very heterogeneous. The pore
volume was determined to be 99.8 ml. The core holder was then placed in an oven at
78oC.
67
1.0
PV =99.8 ml
0.8
Normalized Salinity
0.6
0.4
0.2
0.0
0 50 100 150 200 250
Figure 4.25 Normalized Salinity Tracer for Experiment A-2
After the core equilibrated at 78oC, 7.725 wt% NaCl was injected at 2 mL/min
and 4 mL/min to establish the brine permeability at 78oC. The pressure drops at steady
state were used to determine the brine permeability. Table 4.17 compares the brine
permeability at 24oC and 78oC.
o
24 C 78oC
Section 1 231 222
Section 2 315 384
Section 3 229 262
Section 4 339 327
Whole 271 286
Oil Flood
The core was oil flooded with diluted oil with an injection pressure of 120 psi and
the BPR set to ~30 psi, allowing for a 90 psi pressure differential. Oil was injected until
68
the water cut was less than 1%. Once the core was at residual water saturation, the
pressure drop at steady state conditions was recorded and applied to Darcy’s law to
determine kroo as 0.65 (Table 4.18). Soi was estimated to be 0.45 based on a volume
balance.
Section Permeability (mD) kroo

Section 1 197 0.89
Section 2 216 0.56
Section 3 147 0.56
Section 4 203 0.62
Whole 187 0.65
Waterflood
The core was waterflooded with 7.725 wt% NaCl brine at 10 ft/day (0.668
mL/min) until the oil cut was less than 1% and the pressure drop reached steady state.
The pressure drops were used to calculate krwo as 0.06 (Table 4.19). Sorw was determined
to be 0.27 from volume balance. Table 4.20 summarizes the results from the oil food and
waterflood.
Table 4.19 Water Permeability and Water Relative Permeability for Experiment A-2
Section Permeability (mD) krwo

Section 1 58 0.26
Section 2 22 0.06
Section 3 10 0.04
Section 4 15 0.05
Whole 17 0.06
Table 4.20 Summary of Oil Flood and Waterflood for Experiment A-2

Soi 0.45 Sorw 0.27
kroo 0.65 krwo
0.06
69
Mobility Control
The minimum viscosity needed for stable displacement was determined by
calculating the inverse of the minimum in the total relative mobility curve. The
parameters used in this calculation are presented in Table 4.21. The minimum viscosity
needed for stable displacement was estimated to be 14.9 cP.
16 0.4
14
12
10
lrtot (1/cP)
1/lrtot (cP)
8 0.2
0 0.0
0 0.2 0.4 0.6 0.8 1
Sw
Figure 4.26 Total Relative Mobility Curve for Experiment A-2
Table 4.21 Total Relative Mobility Curve Parameters for Experiment A-2
krwo 0.06
o
kro 0.65
nw 2.5
no 2.5
Swr 0.55
Sor 0.27
µw 0.43 cp
µo 2.4 cp
70
The viscosity of the ASP slug and polymer drive using 4000 ppm FP 3330S
polymer is shown in Figure 4.27. At an injection rate of 1 ft/day, the equivalent shear rate
in the core is 6.12 s-1 assuming C is 2 and n is 0.6. The viscosities of the ASP slug and
polymer drive at 6.12 s-1 and 78oC were 18.7 cP and 20.6 cP, respectively.
100
ASP Slug
Polymer Drive
Viscosity at 78 C (cP)
10
1 10 100
Shear Rate (s^-1)
Figure 4.27 Viscosities of ASP Slug and PD at 78oC for Experiment A-2
Chemical Flood
The ASP slug and polymer drive were prepared based on the steps described in
section 3.2.3 Chemical Slug and Polymer Drive. After the chemicals were prepared and
placed in the oven, a sample from the surfactant slug was taken. A phase behavior pipette
was made using the slug at optimal salinity as a quality control to observe if ultra-low
IFT was achieved. The chemicals were injected at 1 ft/day (0.068 mL/min) at 78oC with
the effluent samples being collected every 78 minutes for a sample volume of 5 ml. Table
71
4.22 lists the properties of the ASP slug and PD. Table 4.23 details the composition of the
waterflood brine, ASP slug, and polymer drive.

PV Injected 0.4 2.4
pH 10.7 10.8
Viscosity at 6.12 s-1 and 78 C 18.7 20.6
Experiment A-2
Na+ 30388 28110 19259
Cl- 46862 33365 19715
SO4=2 0 13526 13526
NH4OH 0 7500 7500
TDS 77250 75000 52500
After 2.8 PV of injection, the chemical flood was stopped. The effluent samples
were centrifuged for 10 minutes at 2000 rpm and 24oC. Sorc was 0.05 with a tertiary oil
recovery of 82%. Figure 4.28 shows the oil recovery during the chemical flood. Oil broke
through early at 0.14 PV. The oil cut remained at ~35% for 0.5 PV with 75% of the oil
being recovered within 1 PV of injection.
72
0.40 PV Polymer Drive
ASP
Slug 1 wt% phenol-4EO
100%
Cumulative Oil Recovery
Oil Cut
So
Cumulative Oil Recovery (%)
80%
Oil Cut (%) So (%)
60%
40%
20%
0%
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Figure 4.28 Oil recovery for Experiment A-2
The effluent surfactant concentration was measured by hyamine titration.
Surfactant retention was determined to be 0.244 mg/g-rock. Surfactant broke through at
0.5 PV and reached a peak concentration at 1 PV (Figure 4.29). The surfactant retention
using ammonia was lower than for experiment S-2, which had a surfactant retention
greater than 0.296 mg/g-rock and did not use any alkali.
73
2500
2000
1500
1000
500
0
0.00 0.50 1.00 1.50 2.00 2.50 3.00
Pore Volumes
The pressure drop during the chemical flood indicated there was no plugging as
the pressure drop reached steady state at 1.5 PV of injection. Figure 4.30 shows sectional
pressure drop data increasing as the oil bank was being displaced through the core.
74
Chemical Flood
8
Whole
Sec 1
Sec 2
Pressure Drop [psi]
6 Sec 3
Sec 4
.068 ml/min
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Figure 4.30 Pressure Drop for Experiment A-2
Effluent pH was measured using a pH probe. pH broke through at 0.35 PV and
reached 10.3 at 1 PV of injection (Figure 4.31). The effluent pH plateaued at 10.4, which
is slightly lower than the injected pH of 10.8.
75
11
10
pH
pH, injected
pH
7
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Effluent salinity was determined using a refractometer. Effluent salinity broke
through at 0.76 PV of injection and reached the polymer drive salinity after 2.21 PV
(Figure 4.32).
76
Salinity (ppm TDS) 90,000
Salinity
80,000
Salinity,
70,000 injected
60,000
50,000
40,000
30,000
20,000
10,000
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Effluent viscosity began increasing at 0.66 PV and reached influent viscosity at
1.9 PV of injection (Figure 4.33). This showed the viscosity propagated effectively.
77
Viscosity at 24o C and 6.12 s-1 (cP) 50 100000
40 80000
Salinity (ppm TDS)

30 60000
20 40000
10 Effluent Viscosity 20000

injected viscosity
Salinity
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
The surfactant retention using ammonia was 0.244 mg/g-rock which was lower
than the surfactant retention from SP floods. The pH propagated well during the chemical
flood, indicating there was little retardation from consumption. The next step was to
investigate the effects of adding sodium hydroxide to the polymer drive. Sodium
hydroxide has a pH that is ~2 pH units greater than ammonia, which should further
reduce the surfactant retention.
Coreflood experiment A-3 was an oil recovery experiment to determine the oil
recovery and surfactant retention in Indiana limestone cores using formulation ASP-1
with soft brine. The slug contained ammonia and the polymer drive contained sodium
78
hydroxide. The purpose of the experiment was to determine if the surfactant retention
could be reduced by adding sodium hydroxide to the polymer drive since sodium
hydroxide has a pH greater than ammonia, which would lead to a more negative surface
charge on the limestone core.
The dilution test with the waterflood brine/oil and ASP slug showed ultra-low IFT
between 50% to 60% ASP slug. The dilution test with ASP slug and polymer drive
showed a Type I behavior starting with 40% polymer drive. pH measurements shown in
Table 4.24 exhibited a high pH with only minimal mixing between the ASP slug and
polymer drive.
Table 4.24 Dilution Test with ASP Slug and Polymer Drive for Experiment A-3
% PD w/t 1 wt% Phenol
% oil bank/Slug TDS
4-EO Comments pH
10.00% 90.00% 70,909 11.80

20.00% 80.00% 67,500 low IFT 12.08
30.00% 70.00% 64,615 12.21
40.00% 60.00% 62,143 Type I 12.31
50.00% 50.00% 60,000 12.36
60.00% 40.00% 58,125
70.00% 30.00% 56,471
80.00% 20.00% 55,000
90.00% 10.00% 53,684
The core’s dimensions and mass were recorded (Table 4.25). Afterward, the core
was prepared as described in section 3.2.7 Coreflood Setup. The dead volume in the core
holder was 2 mL. The core was saturated with 2.0 wt% KCl.
79
Rock Type INLS
Diameter 5.10 cm
length 30.65 cm
mass 1420.20 g
porosity 0.16
area 20.43 cm2
o
Pore volume 99.8 mL
Temperature 78 °C
2.0 wt% KCl brine was injected at 2 ml/min and 4 ml/min to determine the brine
permeability. The pressure drop at steady state was used to obtain the brine permeability
at 24oC. A tracer brine of 6.0 wt% KCl was injected at 2 mL/min with a sample collected
every 2 minutes to determine the core heterogeneity and pore volume. The pore volume
was determined to be 99.8 ml. Tracer brine broke through at 0.5 PV of injection and
reached the influent salinity after 1.65 PV of injection (Figure 4.34). The early
breakthrough of the tracer brine and the amount of brine injected before the effluent
salinity reached the influent salinity indicated the core was very heterogeneous. The core
was then placed in an oven and left overnight to equilibrate to 78oC After equilibrating
6.0 wt% KCl was injected at 78oC to determine the brine permeability at 78oC. The core
permeability decreased from 386 mD at 24oC to 369 mD at 78oC. Table 4.26 shows the
brine permeability at 24oC and 78oC.
80
1.0
PV =99.8 ml
0.8
Normalized Salinity
0.6
0.4
0.2
0.0
0 50 100 150 200
Figure 4.34 Normalized Tracer Profile for Experiment A-3

Section 1 342 314
Section 2 373 354
Section 3 524 480
Section 4 370 377
Whole 386 369
Oil Flood
The core was oil flooded with diluted oil with an upstream pressure of 120 psi and
a downstream pressure of 30 psi until the water cut was less than 1%. Soi was determined
to be 0.51 by a volume balance. The steady-state pressure drop was used to calculate kroo
as 0.59 (Table 4.27).
81
Section 1 216 0.69
Section 2 204 0.57
Section 3 249 0.52
Section 4 203 0.54
Whole 218 0.59
Waterflood
The core was then waterflooded to with 7.725 wt% NaCl brine at 10 ft/day until
the oil cut was less than 1%. Sorw was determined to be 0.28 and krwo to be 0.06 using
stead-state pressure drop data (Table 4.28). Table 4.29 summarizes the results from the
oil flood and waterflood.
Section 1 20.5 0.06
Section 2 29.4 0.08
Section 3 24.4 0.05
Section 4 17.5 0.04
Whole 22.1 0.06
Soi 0.51 Sorw 0.28
o o
kro 0.59 krw 0.06
Mobility Control
needed for stable displacement was 21.9 cP as shown by Figure 4.35.
82
Table 4.30 Total Relative Mobility Curve Parameters for A-3
krwo 0.06
o
kro 0.65
nw 2.5
no 2.5
Swr 0.55
Sor 0.27
µw 0.43 cp
µo 2.4 cp
25 0.4
20
lrtot (1/cP)
1/lrtot (cP)
15
0.2
10
0 0.0
0 0.2 0.4 0.6 0.8 1
Sw
The viscosity of the ASP slug and polymer drive is shown in Figure 4.36Figure
4.11. At an injection rate of 1 ft/day, the equivalent shear rate in the core is 5.25 s-1
83
assuming C is 2 and n is 0.6. The viscosities of the ASP slug and polymer drive at 5.25 s-1
and 78oC were 24.3 cP and 36.2 cP, respectively.

100
ASP Slug
Polymer Drive
10
0.1 1 10 100
Shear Rate (s^-1)
Chemical Flood
in section 3.2.3 Chemical Slug and Polymer Drive. After the chemicals were prepared
and placed in the oven, a sample from the surfactant slug was taken. The slug sample was
added with oil to a phase behavior as a double check for ultra-low IFT. The chemicals
were injected at 1 ft/day (0.069 mL/min) at 78oC with the effluent samples being
collected every 76 minutes for a sample volume of 5 ml. Table 4.31 lists the chemical
properties of the ASP slug and PD. Table 4.32 details the ionic composition of the
waterflood brine, ASP slug, and PD.
84
PV Injected 0.4 2.4
pH 10.8 12.4
and 78 C 24.3 36.2
Experiment A-3
Na+ 30388 28110 19803
Cl- 46862 33365 17895
SO42- 0 13526 13526
OH- 0 0 1276
NH4OH 0 7500 0
TDS 77250 75000 52500
were centrifuged for 10 minutes at 2000 rpm and 24oC. Sorc was 0.07 with a tertiary oil
recovery of 75%. The oil recovery was very comparable to the previous oil recovery
experiment coreflood A-2. Figure 4.37 shows the oil cut was greater than 30% for ~0.4
PV with a tertiary recovery of 62% at 1 PV.
85
ASP
100%
Oil Cut
So
80%
Oil Cut (%) So (%)
60%
40%
20%
0%
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
The effluent surfactant concentration was determined by hyamine titration.
Surfactant retention was 0.218 mg/g-rock. Surfactant broke through at 0.47 PV and
reached a peak concentration at 0.96 PV (Figure 4.38). The surfactant retention using
ammonia in the slug and sodium hydroxide in the polymer drive was slightly lower than
for experiment A-2 (0.244 mg/g-rock). However, more experiments are needed to
determine if there is a significant benefit to adding sodium hydroxide to the polymer
drive. The results may depend on the residence time of the coreflood, the slug size and
other variables that were not be investigated in this study.
86
3000
2500
2000
1500
1000
500
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Pressure drop was recorded during the chemical flood. The pressures reached
steady-state indicating there was no issue with polymer plugging (Figure 4.39). The
section pressure drops clearly show the oil bank moving throughout the core with the oil
bank being displaced from the core at 1.1 PV. This corresponds well with the produced
oil cut.
87
Chemical Flood
4
Whole
Sec 2
Sec 3
0.691 ml/min
Sec 4
Pressure Drop [psi]
3 Sec 1
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Effluent pH was measured using a pH probe. Figure 4.40 shows pH through at
0.16 PV and reached 10.6 at 1 PV of injection. The effluent pH reached the injected
polymer drive pH after 2.4 PV of injection.
88
13
12
11 pH
pH
pH, injected
10
7
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
through at 0.43 PV of injection and reached the polymer drive salinity at 2.33 PV of
injection (Figure 4.41).
89
90,000
Salinity
Salinity (ppm TDS)
80,000
Salinity, injected
70,000
60,000
50,000
40,000
30,000
20,000
10,000
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
90
100
80
Viscosity (cP)
60
40
20 injected viscosity
Effluent Viscosity
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
The effluent pH reached the injected pH of 12.3, but the surfactant retention
decreased only slightly compared to experiment A-2. However, more experiments are
needed to determine if there is a significant benefit to adding sodium hydroxide to the
polymer drive. The results may depend on the residence time of the coreflood, the slug
size and other variables that were not be investigated in this study.
4.3 Alkali Surfactant Polymer Experiments with Sodium Hydroxide

After establishing the surfactant retention in Indiana limestones using an ASP
formulation with ammonia was ~0.22 mg/g-rock, the next step was to investigate the
effects of using sodium hydroxide on the surfactant retention. Sodium hydroxide is a
much stronger alkali than ammonia with a pH of ~12.5. This increase in pH further
reduces the zeta potential of calcite and other minerals in the core. This in turn is
expected to reduce surfactant retention.

91
Multiple phase behavior experiments were done using sodium hydroxide to find a
good surfactant formulation with ultra-low IFT, high fluidity, and high aqueous stability.
Formulation ASP-2 containing 0.65 wt% C24-45PO-30EO-COONa, 0.35 wt% C15-18 IOS,
0.5 wt% C19-23IOS, and 0.25 wt% phenol-4EO showed favorable characteristics with 0.30
wt% NaOH.
0.65 wt% C24-45PO-30EO-COONa, 0.35 wt% C15-18 IOS, 0.50%

C19-23 IOS, 0.25 wt% Phenol-4EO, 0.30 wt% NaOH
90000
Type II
75000
TDS (ppm)
Type III
60000
Type I
45000
30000
0 10 20 30 40 50 60
Oil Concentration
Figure 4.43 Activity Diagram for Formulation ASP-2
Figure 4.43 illustrates the activity diagram for formulation ASP-2. The activity
diagram shows a steeper negative slope compared to that of formulation ASP-1.
Formulation ASP-2 has a steeper slope than ASP-1 since sodium hydroxide is a stronger
alkali than ammonia, which causes more hydrophobic soaps to be generated. As the oil
volume fraction increases, the optimum salinity decreases. That is because more
92
hydrophobic soap is generated as there is more oil. Formulation ASP-1 and ASP-2 are
similar formulations except the alkali differs.
Aqueous stability = 78000 ppm TDS Oil :

Temp. :78ºC
40 After 57 days
Solubilization Ratio (cc/cc)
30% Oil
30
20
10
0
40000 50000 60000 70000 80000 90000 100000
Salinity (ppm TDS)
Figure 4.44 Solubilization Ratios for 30% Oil Vol for Formulation ASP-2
Figure 4.44 shows the solubilization ratios for a salinity scan with 30% oil
volume. The optimum solubilization ratio was 16 at an optimum salinity of 63,000 ppm
TDS for 30% oil volume. The aqueous stability was 78,000 ppm TDS with 2000 ppm FP
3330S. This formulation had the desirable characteristics of a high solubilization ratio
and sufficient aqueous stability.
4.3.2 Single-Phase Dynamic Adsorption Experiment A-4
Coreflood experiment A-4 was a single phase dynamic adsorption experiment to
determine the surfactant adsorption in Indiana limestone cores using sodium hydroxide.
The core’s mass and dimensions were measured and recorded (Table 4.33). The core was
93
prepared as described in section 3.2.7 Coreflood Setup. The dead volume in the core

Rock Type INLS
Diameter 5.07 cm
length 30.48 cm
mass 1382.4 g
porosity 0.155
area 20.20 cm2
o
Pore volume 95.5 mL
Temperature 78 °C
Brine permeability was determined by taking the steady state pressure drops at an
injection rate of 2.0 wt% KCl at 2 mL/min and 4 mL/min were used to determine the
brine permeability. A tracer brine of 6.5 wt% NaCl was injected to determine the core’s
heterogeneity and pore volume. Tracer brine broke through at 0.31 PV and took 2.13 PV
to fully displace the in-situ brine (Figure 4.45). This indicated the core was very
heterogeneous. The pore volume was determined to be 95.5 ml. After the tracer test, the
core was placed in an oven set to 78oC.
94
1.0
PV = 95.5 ml
0.8
Normalized Salinity
0.6
0.4
0.2
0.0
0 50 100 150 200 250
Figure 4.45 Normalized Tracer Test for Experiment A-4
Waterflood
Once the core equilibrated at 78oC, 6.5% NaCl brine was injected to determine
the brine permeability at 78oC. The brine permeability did not change with the increase in
temperature. Table 4.34 lists the brine permeability at 24oC and 78oC.
Section 1 212 208
Section 2 450 443
Section 3 604 599
Section 4 262 253
Whole 313 312
95
Chemical Flood
The surfactant slug and polymer drive were prepared using the procedure
described in section 3.2.3 Chemical Slug and Polymer Drive. Polymer was added to the
surfactant slug and drive to mimic an oil recovery experiment using polymer. Sodium
sulfate was added to suppress gypsum dissolution. The equivalent shear rate in the core
was calculated to be 11.2 s-1 with C as 2 and n as 0.6. Table 4.35 lists the properties of the
ASP slug and PD. Table 4.36 describes the ionic compositions of the waterflood brine,
ASP slug, and polymer drive.
PV Injected 0.4 3.1
Filtration Ratio 1 1
pH 12.6 12.6
and 78 C 12.8 19.7
Experiment A-4
Na+ 25556 24068 11939
Cl- 39444 24486 5765
SO42- 0 13521 13521
OH- 0 1275 1275
TDS 65000 63150 32500
After 3.5 PV of injection, the chemical flood was stopped. Effluent surfactant
concentration was determined by HPLC. The surfactant adsorption was determined to be
96
0.15 mg/g-rock. Surfactant broke through at 0.74 PV and quickly increased to a peak
concentration of 5300 ppm at 1.23 PV (Figure 4.46).
6000
5000
4000
3000
2000
1000
0
0.0 0.5 1.0 1.5 2.0 2.5
PVs Injected
Figure 4.46 Chemical Flood Effluent Surfactant Concentration for Experiment A-4
Effluent pH broke through at 0.43 PV and reached a pH of 12.3 at 1.5 PV (Figure
4.47). The pH plateaued around 12.4, showing good pH propagation with minimal alkali
consumption.
97
13
12
pH
11
pH, injected
pH
10
7
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Pore Volumes
The effluent salinity broke through at 0.76 PV of injection and reached the
injected polymer drive salinity at 2.6 PV of injection (Figure 4.48).
98
70,000
Salinity
Salinity (ppm TDS)
60,000 Salinity, injected
50,000
40,000
30,000
20,000
10,000
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Pore Volumes
Effluent viscosity broke through at 0.76 PV of injection and reached the injected
viscosity at 2.5 PV (Figure 4.49).
99
140 80000
120
Viscosity (cP)
60000
100
Salinity (ppm TDS)

80
40000
60
40
20000
20 injected viscosity
Effluent Viscosity
Salinity
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
The surfactant adsorption using sodium hydroxide was 0.15 mg/g-rock. The pH
propagated well in the core with 0.30 wt% NaOH. The good pH propagation and low
surfactant retention were good indicators that sodium hydroxide would reduce the
retention more than ammonia. The next step was to determine the surfactant retention in
an oil recovery experiment.
with soft brine to prevent precipitation. The core’s dimensions and mass were recorded
100
(Table 4.37). The core was prepared as described in the 3.2.7 Coreflood Setup. The dead
volume in the core holder was 2 mL. The core was saturated with 2.0 wt% KCl.

Rock Type INLS
Diameter 3.79 cm
length 30.48 cm
mass 770.94 g
porosity 0.165
area 11.30 cm2
o
Pore volume 56.9 mL
Temperature 78 °C
2.0 wt% KCl was injected at 2 ml/min and 4 ml/min to determine the brine
permeability. The pressure drop at steady state was used to calculate the brine
permeability at 24oC. A tracer brine of 6.0 wt% KCl was injected at 3 mL/min to
determine the core heterogeneity and pore volume. The pore volume was determined to
be 56.9 ml. The tracer brine broke through at 0.56 PV of injection and reached the
influent salinity after 1.8 PV of injection (Figure 4.50). The early breakthrough of the
tracer brine and the amount of brine injected before the effluent salinity reached the
influent salinity indicated the core was very heterogeneous. The core was then placed in
an oven and left overnight to equilibrate to 78oC After equilibrating a 6.0 wt% KCl was
injected at 78oC to determine the brine permeability at 78oC. The core permeability
decreased from 389 mD at 24oC to 305 mD at 78oC. Table 4.38 lists the brine

101
Section 1 270 212
Section 2 414 283
Section 3 480 391
Section 4 488 411
Whole 389 305
Oil Flood
a downstream pressure of 30 psi. Once water cut was less than 1%, the oil flood was
stopped. Soi was estimated to be 0.38 based on volume balance. The steady-state pressure
drop was used to determine kroo as 0.73 (Table 4.39).
102
Section 1 204 0.96
Section 2 217 0.77
Section 3 233 0.60
Section 4 242 0.59
Whole 218 0.73
Waterflood
The core was then waterflooded with 6.5 wt% NaCl brine at 10 ft/day until the
oil cut was less than 1%. Sorw was estimated to be 0.20 based on volume balance. Steady-
state pressure drop was used to determine krwo to be 0.03 (Table 4.40). Table 4.41
summarizes the results from the oil flood and waterflood.
Section 1 16 0.07
Section 2 8 0.03
Section 3 10 0.02
Section 4 7 0.02
Whole 9 0.03
Soi 0.38 Sorw 0.20
o o
kro 0.73 krw 0.03
Mobility Control
calculating the inverse of the minimum in the total relative mobility curve (Figure 4.51).
The parameters used in this calculation are presented in Table 4.42. The minimum
viscosity needed for stable displacement was 21.3 cP.
103
krwo 0.03
o
kro 0.73
nw 2.5
no 2.5
Swr 0.624
Sor 0.197
µw 0.41 cp
µo 2.4 cp
25 0.5
20 0.4
15 0.3
1/lrtot (cP)
lrtot (1/cP)
10 0.2
5 0.1
0 0
0 0.2 0.4 0.6 0.8 1
Sw
The viscosity of the ASP slug and polymer drive is shown in Figure 4.52 Figure
4.11. At an injection rate of 2 ft/day, the equivalent shear rate in the core is 11.6 s-1
assuming C is 2 and n is 0.6. The viscosities of the ASP slug and polymer drive at 11.6 s-1
and 78oC were 17.5 cP and 21 cP, respectively.
104
Figure 4.52 Viscosities for ASP slug and PD at 78oC for Experiment A-5
Chemical Flood
added with oil to a phase behavior as a quality control to check for ultra-low IFT. The
chemicals were injected at 2 ft/day (0.079 mL/min) at 78oC with the effluent samples
being collected every 57 minutes for a sample volume of 4.3 mL. Table 4.43 lists the
waterflood brine, ASP slug, and polymer drive.
105
PV Injected 0.4 1.75
pH 12.7 12.8
Viscosity at 11.6 s-1 and 78 C 17.5 21
Experiment A-5
Na+ 25569 23992 11955
Cl- 39431 24356 5793
SO42- 0 13526 13526
OH- 0 1276 1276
TDS 65,000 63150 32550
After 2.15 PV, the chemical flood was stopped. The effluent samples were
centrifuged for 10 minutes at 2000 rpm and 24oC. Sorc was determined to be 0 within
measurement error with a tertiary oil recovery of 100%. Figure 4.53 shows the oil broke
through at 0.20 PV. The oil cut was ~40% for ~0.3 PV with 97% of oil being recovered
within 1 PV.
106
0.40 PV
ASP Slug Polymer Drive
100%
80%
Oil Cut (%) So (%)
60% Oil Cut

So
40%
20%
0%
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
The effluent surfactant concentration was determined by HPLC. Surfactant
retention was 0.099 mg/g-rock. Surfactant broke through at 0.55 PV and reached a peak
concentration at 1.09 PV (Figure 4.54). The surfactant retention using sodium hydroxide
was much lower than both the SP flood and the ASP flood using ammonia.
107
5,000
4,000
3,000
2,000
1,000
0
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
The pressure data was recorded during the chemical flood. Figure 4.55 shows the
oil bank forming and being displaced throughout the core. The pressure drop reached
steady state at the end of the coreflood.
108
Chemical flood
15
Whole
0.076 Sec 1
Sec 2
ml/min Sec 3
Pressure Drop [psi]
Sec 4
10
0
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
Figure 4.55 Pressure Drop for Experiment A-5 at 2 ft/D
reached 11.7 at 1 PV of injection (Figure 4.56). The effluent pH plateaued at 12.6 which
is slightly lower than the injected pH of 12.8.
109
14
pH
pH, injected
13
12
pH
11
10
8
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
110
70,000
Salinity
50,000
Salinity (ppm TDS)
40,000
30,000
20,000
10,000
0
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
Effluent viscosity reached 95% of the injected viscosity at the end of the flood.
Using sodium hydroxide yielded a low surfactant retention of 0.099 mg/g-rock
with an Sorc of 0 within measurement error. The surfactant retention was much lower than
that of using ammonia. This is due to sodium hydroxide having a pH higher than
ammonia. The higher pH further increases the negative surface charges. As these results
were done at 2 ft/day, the next step was to investigate the effect of residence time by
decreasing the flowrate to 1 ft/day.
111
with soft brine. The velocity was reduced to 1 ft/D. The core’s dimensions and mass were
recorded (Table 4.45). The core was prepared as described in section 3.2.7 Coreflood
Setup. The dead volume in the core holder was 2 ml. The core was saturated with 2.0
wt% KCl.

Rock Type INLS
Diameter 5.08 cm
length 30.40 cm
mass 1400.6 g
porosity 0.146
area 20.27 cm2
o
Pore volume 90.1 mL
Temperature 78 °C
at 24oC. A tracer brine of 6.0 wt% KCl was injected at 3 mL/min to determine the core
heterogeneity and pore volume. The pore volume was determined as 90.1 ml. The tracer
brine broke through at 0.47 PV of injection and reached the influent salinity after 2.1 PV
of injection (Figure 4.58). The early breakthrough of the tracer brine and the amount of
brine injected before the effluent salinity reached the influent salinity indicated the core
was very heterogeneous. The core was then placed in an oven and left overnight to
equilibrate 78oC. After equilibrating a 6.0 wt% KCl was injected at 78oC to determine the
112
brine permeability at 78oC. The core permeability decreased from 334 mD at 24oC to 285
mD at 78oC. Table 4.46 presents the brine permeability at 24oC and 78oC.
1.0
PV = 90.1 ml
0.8
Normalized Salinity
0.6
0.4
0.2
0.0
0 50 100 150 200 250
Section 1 271 234
Section 2 318 292
Section 3 432 323
Section 4 337 305
Whole 338 285
Oil Flood
a downstream pressure of 30 psi. The upstream pressure was increased in order to
113
achieve a higher pressure differential. The objective was to achieve a greater oil
saturation than the previous coreflood experiment A-5. Once water cut was less than 1%,
the oil flood was stopped. Soi was estimated to be 0.42 using a volumetric balance. kroo
was determined to be 0.83 using stead-state pressure drop (Table 4.47).
Section 1 208 0.92
Section 2 225 0.80
Section 3 263 0.86
Section 4 218 0.72
Whole 232 0.83
Waterflood
The core was then waterflooded to with 6.5 wt% NaCl brine at 10 ft/day until the
oil cut was less than 1%. Sorw was estimated to be 0.24 and krwo to be 0.03 (Table 4.48).
Table 4.49 summarizes the results from the oil flood and waterflood.
Section 1 9 0.03
Section 2 15 0.06
Section 3 7 0.02
Section 4 9 0.03
Whole 8 0.03
Soi 0.42 Sorw 0.24
o o
kro 0.83 krw 0.03
Mobility Control
The minimum viscosity needed for a stable displacement was determined by
114
krwo 0.03
o
kro 0.83
nw 2.5
no 2.5
Swr 0.58
Sor 0.23
µw 0.41 cp
µo 2.4 cp
25 0.5
20 0.4
15 0.3
1/lrtot (cP)
lrtot (1/cP)
10 0.2
5 0.1
0 0
0 0.2 0.4 0.6 0.8 1
Sw
The viscosity of the ASP slug and polymer drive is shown in Figure 4.60. At an
injection rate of 1 ft/day, the equivalent shear rate in the core is 5.4 s-1 assuming C is 2
115
and n is 0.6. The viscosities of the ASP slug and polymer drive at 5.4 s-1 and 78oC were
20.1 cP and 27.2 cP, respectively.
Figure 4.60 Viscosities for ASP Slug and PD at 78oC for Experiment A-6
Chemical Flood
added with oil to a phase behavior as a double check for ultra-low IFT. The chemicals
collected every 90 minutes for a sample volume of 5 mL. Table 4.51 details the
properties of the ASP slug and PD. Table 4.52 describes the ionic composition of the
116
PV Injected 0.4 2.4
pH 12.6 12.8
Viscosity at 5.4 s-1 and 78
20.1 27.2
C
Experiment A-6
Na+ 25569 23992 11955
Cl- 39431 24356 5793
SO42- 0 13526 13526
OH- 0 1276 1276
TDS 65,000 63150 32550
were centrifuged for 10 minutes at 2000 rpm and 24oC. Sorc was determined to be 0.024
with a tertiary oil recovery of 90%. Figure 4.61 shows the oil recovery. The chemical
flood produced a large stable oil bank with an oil cut greater than 30% for 0.5 PV.
117
0.40 PV
ASP Polymer Drive
Slug
100%

80%
Oil Cut
Oil Cut (%) So (%)
So
60%
40%
20%
0%
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Surfactant retention was 0.165 mg/g-rock with 0.386 mg/g-rock being injected.
Surfactant broke through at 0.26 PV (Figure 4.62). The surfactant retention from this
coreflood was similar to that of the previous experiment.
118
6,000
4,000
2,000
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
The pressure drop during the chemical flood indicated there was no issue with
polymer plugging (Figure 4.63). Although the pressure drop data are scattered, the oil
bank can be seen propagating through the core.
119
Chemical flood
6
Whole
Sec 4
Sec 1
Pressure Drop [psi]
Sec 2
4 Sec 3
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
reached 12 at 1 PV of injection (Figure 4.64). The effluent pH reached 12.4 at the end of
the chemical flood which is slightly lower than the injected pH of 12.8.
120
14
pH
pH, injected
13
12
pH
11
10
8
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
121
70,000
Salinity
Salinity (ppm TDS)
50,000
40,000
30,000
20,000
10,000
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Effluent viscosity reached injected viscosity at 1.5 PV showing the viscosity
propagated well.
The surfactant retention was determined to be 0.165 mg/g-rock with a Sorc of
0.024. The results indicate that a flow rate of 1 ft/day yielded similar results to those at 2
ft/day. To be confident that the surfactant retention using sodium hydroxide was lower
than ammonia, a repeat of this coreflood was conducted at the same flow rate.
Coreflood experiment A-7 was a repeat of oil recovery coreflood experiment A-6
to determine the reproducibility of the results. The core’s dimensions and mass were
recorded (Table 4.53). Afterward, the core was prepared as described in the 3.2.7
122
Coreflood Setup. The dead volume in the core holder was 2 mL. The core was saturated
with 2.0 wt% KCl.

Rock Type INLS
Diameter 5.07 cm
length 30.51 cm
mass 1393.65 g
porosity 0.16
area 20.19 cm2
o
Pore volume 97.8 mL
Temperature 78 °C
permeability. The pressure drop at steady state was applied to Darcy’s law to obtain the
brine permeability at 24oC. A tracer brine of 6.0 wt% KCl was injected at 3 mL/min to
determine the core heterogeneity and pore volume. The pore volume was determined to
be 97.8 ml. The tracer brine broke through at 0.48 PV of injection and reached the
influent salinity after 2 PV of injection (Figure 4.66). The early breakthrough of the tracer
brine and the amount of brine injected before the effluent salinity reached the influent
salinity indicated the core was very heterogeneous. The core was then placed in an oven
and left overnight to equilibrate to 78oC. After equilibrating a 6.0 wt% KCl was injected
at 78oC to determine the brine permeability at 78oC. Table 4.55 presents the brine
123
Section 1 204 210
Section 2 351 332
Section 3 323 291
Section 4 321 304
Whole 287 282
Oil Flood
stopped. Soi was estimated to be 0.42 by volumetric balance with a kroo of 0.68 (Table
4.56).
124
Table 4.55 Sectional Oil Permeability and Oil Relative Permeability for A-7
Section 1 150 0.76
Section 2 233 0.68
Section 3 204 0.62
Section 4 203 0.65
Whole 193 0.68
Waterflood
The core was then waterflooded with 6.5 wt% NaCl brine at 10 ft/day until the oil
cut was less than 1%. Sorw was estimated to be 0.28 and krwo to be 0.09. Table 4.56 details
the water relative permeability. Table 4.57 summarizes the results from the oil flood and
waterflood.
Table 4.56 Water Permeability and Water Relative Permeability for A-7
Section 1 54 0.27
Section 2 24 0.07
Section 3 19 0.06
Section 4 21 0.07
Whole 25 0.09
Table 4.57 Summary of Oil Flood and Waterflood for A-7

Soi 0.42 Sorw 0.28
o o
kro 0.68 krw 0.09
Mobility Control
125
krwo 0.09
o
kro 0.68
nw 2.5
no 2.5
Swr 0.58
Sor 0.28
µw 0.42 cp
µo 2.4 cp
14 0.4
12
10
lrtot (1/cP)
1/lrtot (cP)
8
0.2
6
0 0.0
0 0.2 0.4 0.6 0.8 1
Sw
126
100
Polymer Drive
ASP Slug
Viscosity (cP)
10
1
0.1 1 10 100
Shear Rate (s^-1)
Chemical Flood
added with oil to a phase behavior as a quality check for ultra-low IFT. The chemicals
collected every 77 minutes for a sample volume of 5 mL. Table 4.59 details the chemical
properties of the ASP slug and Polymer Drive. Table 4.60 details the ionic composition
of the waterflood brine, ASP slug, and polymer drive.
127
PV Injected 0.4 2.4
pH 12.1 12.4
Experiment A-7
Na+ 25569 23992 11955
Cl- 39431 24356 5793
SO42- 0 13526 13526
OH- 0 1276 1276
TDS 65,000 63150 32550
centrifuged for 10 minutes at 2000 rpm and 24oC. Sorc was determined to be 0.053 with a
tertiary oil recovery of 81%. Figure 4.69 shows the oil cut was ~40% for ~0.25 PV which
caused the 75% of the residual oil to be recovered in 1 PV.
128
ASP
100%
Oil Cut
So
80%
Oil Cut (%) So (%)
60%
40%
20%
0%
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Surfactant retention was 0.116 mg/g-rock. Surfactant broke through at 0.2 PV and
reached a peak concentration at 0.86 PV (Figure 4.70). The surfactant retention was
comparable to that of the previous experiment A-6.
129
6000

5000
4000
3000
2000
1000
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
The pressure drop showed the propagation of the oil bank despite the data
scattering (Figure 4.71). The pressure drop reached steady state as the polymer drive
saturated the core, indicating there was no polymer plugging.
130
Chemical Flood
3
Whole
Sec 1
Sec 2
Sec 3
Pressure Drop [psi]
Sec 4
2
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
reached 11.8 at 1 PV of injection (Figure 4.72). The effluent pH reached the injected pH
after 1.9 PV, indicating the pH propagated very well.
131
13
12
pH
11
pH, injected
pH
10
7
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
injection.
132
70,000
Salinity
60,000
Salinity, injected
Salinity (ppm TDS)
50,000
40,000
30,000
20,000
10,000
0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
133
80 80000
60 60000
Viscosity (cP)
Salinity (ppm TDS)

40 40000
20 Effluent 20000
Viscosity
injected
viscosity
Salinity
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
The surfactant retention was determined to be 0.116 mg/g-rock with an Sorc of
0.05. This experiment was a repeat of experiment A-6 to observe the reproducibility of
the results. The results from experiment A-6 and A-7 were very comparable. The average
surfactant retention using soft brine and sodium hydroxide is 0.127 mg/g-rock, which is
much lower than the surfactant retention using ammonia and less than half of the
surfactant retention from SP experiments. The next step was to investigate the effect of
not using a soft brine preflood.
4.3.6 Oil Recovery Hard Brine Experiment A-8
134
where hard seawater was used as the waterflood brine. The previous coreflood
experiments using sodium hydroxide were done using a soft brine preflood. This
experiment was done to determine the effect of hardness on surfactant retention and pH
propagation. The core’s dimensions and mass were recorded (Table 4.61). The core was
prepared as described in section 3.2.7 Coreflood Setup. The dead volume in the core

Rock Type INLS
Diameter 5.07 cm
length 30.44 cm
mass 1396.04 g
porosity 0.158
area 20.20 cm2
o
Pore volume 97 mL
Temperature 78 °C
at 24oC. A tracer brine of 2.0 wt% KCl was injected at 2 mL/min to determine the core
heterogeneity and pore volume. The pore volume was determined to be 97 ml. The tracer
brine broke through at 0.34 PV of injection and reached the influent salinity after 2.16 PV
of injection (Figure 4.75). The early breakthrough of the tracer brine and the amount of
brine injected before the effluent salinity reached the influent salinity indicated the core
was very heterogeneous. The core was then placed in an oven and left overnight to
135
equilibrate to 78oC. After equilibrating a 2.0 wt% KCl was injected at 78oC to determine
the brine permeability at 78oC. The core permeability increased from 422 mD at 24oC to
443 mD at 78oC. Table 4.62 details the brine permeability at 24oC and 78oC.
1.0
PV = 97 ml
0.8
Normalized Salinity
0.6
0.4
0.2
0.0
0 50 100 150 200 250
Section 1 327 418
Section 2 394 422
Section 3 472 436
Section 4 505 485
Whole 422 443
Oil Flood
136
stopped. Soi was estimated using a volumetric balance to be 0.43. Pressure drops taken at
steady-state were used to calculate kroo to be 0.65 (Table 4.63).
Section 1 302 0.72
Section 2 250 0.59
Section 3 292 0.67
Section 4 312 0.64
Whole 287 0.65
Waterflood
The core was then waterflooded with seawater brine at 10 ft/day until the oil cut
was less than 1%. Sorw was estimated to be 0.29 and krwo to be 0.03 (Table 4.64). Table
4.65 summarizes the results form the oil flood and waterflood.
Section 1 19 0.05
Section 2 14 0.03
Section 3 13 0.03
Section 4 18 0.04
Whole 15 0.03
Soi 0.43 Sorw 0.29
o o
kro 0.65 krw 0.03
Mobility Control
137
krwo 0.03
o
kro 0.65
nw 2.5
no 2.5
Swr 0.57
Sor 0.29
µw 0.4 cp
µo 2.4 cp
24 0.4
20
16
lrtot (1/cP)
1/lrtot (cP)
12 0.2
0 0.0
0 0.2 0.4 0.6 0.8 1
Sw
138
100
ASP Slug
Polymer Drive
Viscosity (cP)
10
0.1 1 10 100
Shear Rate (s^-1)
Chemical Flood
added with oil to a phase behavior as quality check for ultra-low IFT. The chemicals were
injected at 1 ft/day (0.067 mL/min) at 78oC with the effluent samples being collected
every 77 minutes for a sample volume of 5 mL. Table 4.67 describes the chemical
139
PV Injected 0.4 1.6
pH 12.5 12.5
Experiment A-8
Na+ 15163 23992 11955
K+ 552 0 0
Ca2+ 651 0 0
Mg2+ 1946 0 0
Cl- 27982 24356 5793
SO42- 3700 13526 13526
OH- 0 1276 1276
TDS 49994 63150 32550
tertiary oil recovery of 72% (Figure 4.78). The tertiary oil recovery using hard brine was
lower than that of using a soft brine preflood.
140
ASP Slug 1 wt% phenol-4EO
100%
Oil Cut
So
80%
Oil Cut (%) So (%)
60%
40%
20%
0%
0.0 0.5 1.0 1.5 2.0
Pore Volumes
The effluent surfactant concentration was determined by HPLC. Surfactant
retention was 0.186 mg/g-rock. Surfactant broke through at 0.4 PV (Figure 4.79). The
surfactant retention was higher than from the previous experiments.
141
10000
8000
6000
4000
2000
0
0.0 0.5 1.0 1.5 2.0
Pore Volumes
During the chemical flood, the section pressure taps failed to respond, making the
pressure drop across the whole core the only available data. From the whole core pressure
drop, the oil bank can be seen forming (Figure 4.80). The pressure drop reached steady
state at 1.1 PV, indicating there was no indication of plugging.
142
Whole
Chemical Flood
4
0.067 ml/min Whole
Pressure Drop [psi]
0
0.0 1.0 2.0
Pore Volumes
reached 9.2 at 1 PV of injection. The effluent pH plateaued at 12.5 at 1.84 PV. The pH
was delayed by 0.5 PV compared to experiment A-6, which explains the difference in
performance between the two experiments.
143
13
12
11
pH
10
9
pH (A-8)
8 pH (A-6)
pH injected
7
0.0 0.5 1.0 1.5 2.0
Pore Volumes
Figure 4.81 Effluent pH for Experiments A-6 and A-8
injection (Figure 4.82). The effluent salinity reached a peak salinity of 57,000 ppm TDS
at 0.60 PV of injection. The ASP slug was diluted in the front by the seawater and the
back from the polymer drive. Although the effluent salinity did not reach the Type III
region, the salinity in the core was constantly mixed and diluted. As the slug was injected
at optimum salinity, the inlet of the core saw optimum salinity.
144
70,000
Salinity
60,000
Salinity (ppm TDS)
Salinity, injected
50,000
40,000
30,000
20,000
10,000
0
0.0 0.5 1.0 1.5 2.0
Pore Volumes
Effluent viscosity broke through at 0.50 PV and reached influent viscosity at 1.63
PV of injection (Figure 4.83). This showed the viscosity propagated effectively.
145
Viscosity measured at 24 C (cP) 80
60
40
20
Effluent Viscosity
injected viscosity
0
0.0 0.5 1.0 1.5 2.0
Pore Volumes
ASP coreflood experiment A-8 had a worse performance compared to previous
ASP corefloods using sodium hydroxide. Mixing between the ASP slug and the
waterflood brine containing divalent cations delayed the pH propagation and increased
the surfactant retention. The surfactant retention was 0.186 mg/g-rock and Sorc was 0.082.
These results indicate that using a soft brine preflood is beneficial. The mixing zone in
the Indiana limestone is very large because of its heterogeneity. More than 2 PV are
required to reach influent tracer concentration.
recovery and surfactant retention in Indiana limestone using formulation ASP-2 without
146
adding additional sulfate to the softened seawater brine containing 3700 ppm sulfate. The
core’s dimensions and mass were recorded (Table 4.69). The core was prepared as
described in the 3.2.7 Coreflood Setup. The dead volume in the core holder was 2 mL.
The core was saturated with 2.0 wt% KCl.

Rock Type INLS
Diameter 5.12 cm
length 26.87 cm
mass 1242.04 g
porosity 0.169
area 11.30 cm2
o
Pore volume 93.4 mL
Temperature 78 °C
at 24oC. A tracer brine of 7.725 wt% NaCl was injected at 2 mL/min to determine the
core heterogeneity and pore volume. The pore volume was determined to be 93.4 ml. The
tracer brine broke through at 0.4 PV of injection and reached the influent salinity after
2.02 PV of injection (Figure 4.84). The early breakthrough of the tracer brine and the
amount of brine injected before the effluent salinity reached the influent salinity indicated
the core was very heterogeneous. The core was then placed in an oven and left overnight
to equilibrate to78oC. After equilibrating a 7.725 wt% NaCl was injected at 78oC to
147
determine the brine permeability at 78oC. The core permeability decreased from 455 mD
at 24oC to 436 mD at 78oC. Table 4.70 details the brine permeability at 24oC and 78oC.
1.0
PV =93.4 ml
0.8
Normalized Salinity
0.6
0.4
0.2
0.0
0 50 100 150 200 250
Section 1 311 301
Section 2 536 486
Section 3 781 703
Section 4 442 454
Whole 455 436
Oil Flood
stopped. Soi was estimated to be 0.48 from a volumetric balance. kroo was determined to
be 0.59 by using the steady-state pressure drop (Table 4.71).
148
Table 4.71 Sectional Oil Permeability and Oil Relative Permeability for A-9
Section 1 180 0.60
Section 2 222 0.46
Section 3 299 0.42
Section 4 189 0.42
Whole 210 0.48
Waterflood
The core was then waterflooded with seawater at 10 ft/day until the oil cut was
less than 1%. Sorw was determined to be 0.28 based on volumetric balance. and krwo to be
0.06 (Table 4.72). A preflush with softened seawater was injected with no additional
sulfate. The brine composition of softened seawater is listed in Table 4.76. This was done
for 1.9 PV with no additional oil being recovered. Table 4.73 summarizes the oil flood
and waterflood.
Section 1 33 0.06
Section 2 26 0.11
Section 3 27 0.05
Section 4 17 0.04
Whole 25 0.06
Soi 0.48 Sorw 0.28
o o
kro 0.48 krw 0.06
Mobility Control
needed for stable displacement was 13.8 cP at a shear rate of 4.96 s-1.
149
Table 4.74 Total Relative Mobility Curve Parameters for A-9
krwo 0.06
o
kro 0.48
nw 2.5
no 2.5
Swr 0.52
Sor 0.28
µw 0.40 cp
µo 2.4 cp
16 0.4
14
12
10
lrtot (1/cP)
1/lrtot (cP)
8 0.2
0 0.0
0 0.2 0.4 0.6 0.8 1
Sw
Figure 4.85 Total Relative Mobility for Experiment A-9
150
100
ASP Slug
Polymer Drive
10
0.1 1 10 100
Shear Rate (s^-1)
Chemical Flood
added with oil to a phase behavior as a quality control to observe for ultra-low IFT. The
chemicals were injected at 1 ft/day (0.071 mL/min) at 78oC with the effluent samples
being collected every 71 minutes for a sample volume of 5 mL. Table 4.75 lists the
chemical properties of the ASP slug and PD. Table 4.76 details the ionic composition of
the preflood brine, ASP slug, and PD.
151
PV Injected 0.4 2.4
pH 12.3 12.4
Table 4.76 Ionic Composition of Preflood Brine, ASP Slug, and Polymer Drive for
Experiment A-9
Ionic Preflood Brine ASP Slug Polymer Drive
Na+ 25188 25005 12967
Cl- 36112 33170 14607
SO4-2 3700 3700 3700
OH- 0 1276 1276
TDS 65000 63150 32550
tertiary oil recovery of 81%. The oil recovery was similar to previous experiments done
by adding sodium sulfate to the brine, indicating that additional sodium sulfate was not
necessary. Figure 4.87 shows 65% of the oil was recovered by 1 PV.
152
ASP
100%
Oil Cut
80% So
Oil Cut (%) So (%)
60%
40%
20%
0%
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
Surfactant retention was 0.17 mg/g-rock with 0.451 mg/g-rock being injected. Surfactant
broke through at 0.28 PV and reached a peak concentration at 1.16 PV (Figure 4.88). The
surfactant retention was slightly higher compared to experiments that had additional
sulfate in the ASP slug and PD.
153
4000
3500
3000
2500
2000
1500
1000
500
0
0.00 0.50 1.00 1.50 2.00 2.50 3.00
PV
The pressure drop was recorded during the chemical flood. Sectional pressure
drops failed to communicate periodically during the chemical flood. At 1.5 PV the
sectional pressure taps began to communicate (Figure 4.89). At the end of the flood, the
pressure drops reached steady state indicating polymer transported well.
154
Chemical Flood
2.0
Whole
Sec 1 0.736 ml/min
Sec 2
Sec 3
Pressure Drop [psi]
1.5 Sec 4
1.0
0.5
0.0
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
reached 11.9 at 1 PV of injection (Figure 4.90). This indicates that sulfate in the seawater
was sufficient to prevent gypsum from negatively impacting pH propagation.
155
13
12
pH
11
pH,
pH
injected
10
7
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
156
Salinity (ppm TDS) 70,000
Salinity
60,000 Salinity,
injected
50,000
40,000
30,000
20,000
10,000
0
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
Effluent viscosity broke through at 0.33 PV and reached influent viscosity at 2.43
PV of injection (Figure 4.92). This showed the viscosity propagated effectively.
157
100 80000
80
Viscosity (cP)
60000
Salinity (ppm TDS)

60
40000
40
20000
20
injected viscosity
Effluent Viscosity
Salinity
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore Volumes
ASP coreflood experiment A-9 had a similar performance compared to previous
experiments with additional sulfate added to the brine in terms of oil recovery and pH
propagation. The surfactant retention was slightly higher without the additional of sulfate.
This indicates that concentration of sulfate in the seawater brine was sufficient to prevent
gypsum from interfering with pH propagation.
4.4 Effluent Ion Analysis and Geochemical Interpretation

Effluent ion analysis was done using ICP and IC to determine effluent sulfate,
calcium, magnesium, iron, and aluminum. These measurements are an indication of the
water-rock interactions and geochemistry. As the pH increases the effluent calcium and
158
magnesium concentrations decreased, effluent aluminum concentration increased, and
iron concentration was insensitive to pH.
The first three floods using sodium hydroxide (Figure 4.98 to Figure 4.100)
showed a decrease of the calcium concentration from 30 ppm at a buffered pH of 8 to 3
ppm at a pH of 12.5 (Figure 4.93). The fourth flood using ammonia (Figure 4.97) showed
a decrease of calcium to 8 ppm at a pH of 10.5. The trend with pH using ammonia is
similar to the trend using sodium hydroxide. Sodium sulfate contributed in decreasing the
calcium concentration by suppressing gypsum dissolution. Effluent magnesium
concentration decreased from 2 ppm at a buffered pH of 8 to 0.2 ppm at a pH of 12.5
(Figure 4.94). Sodium hydroxide decreased the effluent calcium and magnesium
concentrations compared to using ammonia. The dissolution of dolomite is about 100
times slower than calcite (Pokrovsky et al. 1999). The reactions may not have been at
equilibrium based on the reaction rates modeled by Tagavifar et al (2018). Since the
floods using ammonia and sodium hydroxide both contain sodium sulfate, the effect of
various alkalis was isolated.
The effluent iron concentration remained insensitive to pH with an effluent
concentration of 0.05 ppm (Figure 4.95). At high pH and in the oxidized state of the core,
Fe(OH)4- and Fe(OH)3 precipitate so the soluble Fe concentration is very low. However,
the role of iron is still considered significant despite the low effluent concentration for
several reasons. Surfactant and polymer adsorption is higher on Fe minerals. Ferric ions
may affect the transport of the HPAM polymer. Maubert et al. (2018) found that adding
co-solvent to the polymer drive improved polymer transport in oxidized carbonate cores
containing iron minerals. The mechanism is unknown but may be related to the
complexing of the ethylene oxide in the co-solvent with the ferric ions.
159
Effluent aluminum concentration increased from 0.6 ppm at a buffered pH of 8 to
20 ppm at a pH of 12.5 (Figure 4.96), indicating a higher pH dissolves more clay thus
releasing more aluminum ions (Tagavifar et al., 2018). At pH greater than 10, aluminum
primarily exists as Al(OH)4-. This indicates aluminum is not negatively impacting the
surfactant or polymer; however, aluminum does consume hydroxide. At a concentration
of 20 ppm, aluminum will react with 50 ppm hydroxide to form Al(OH)4-, which
corresponds to a 4% loss in hydroxide. This consumption of alkali causes a slight delay in
pH propagation.
100.00
A-2
A-4
Concentration (ppm)
A-6
A-7
10.00
1.00
7 8 9 10 11 12 13
pH
Figure 4.93 Effluent Calcium Concentration vs pH
160
10.0
A-2
A-4
A-6
Concentration (ppm)
A-7
1.0
0.1
7 8 9 10 11 12 13
pH
Figure 4.94 Effluent Magnesium Concentration vs pH
1
A-2
A-4
A-6
A-7
Concentration (ppm)
0.1
0.01
0.001
7 8 9 10 11 12 13
pH
Figure 4.95 Effluent Iron Concentration vs pH
161
100
10
Concentration (ppm)
0.1 A-2
A-4
A-6
A-7
0.01
7 8 9 10 11 12 13
pH
Figure 4.96 Effluent Aluminum Concentration vs pH
100.00 Magnesium
Iron
Calcium
10.00 Aluminum
Concentration (ppm)
1.00
0.10
0.01
0.0 0.5 1.0 1.5 2.0 2.5
Pore Volumes
Figure 4.97 Effluent Ion Concentrations for Experiment A-2
162
100.0000
10.0000
Concentration (ppm)
1.0000
0.1000
Magnesium
0.0100
Iron
Calcium
Aluminium
0.0010
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Pore volumes
100.00
Iron (ppm)
Calcium (ppm)
Aluminum (ppm)
Magnesium (ppm)
10.00
Concentration
1.00
0.10
0.01
0.00 0.40 0.80 1.20 1.60 2.00
Pore Volumes
163
100 Magnesium
Iron
Calcium
Aluminum
10
Concentration (ppm)
0.1
0.01
0 0.5 1 1.5 2 2.5 3
Pore Volumes
4.5 Discussion of Experiments

This section summarizes the results of the experiments described in this chapter.
All experiments were done in Indiana limestone. Table 4.77 summarizes the formulations
used in the experiments.
Table 4.77 Chemical Formulations used in Experiments
SP-1 ASP-1 ASP-2

Formulation: wt
Chemical (%) Chemical wt (%) Chemical wt (%)
C18-45PO- C24-45PO-30EO- C24-45PO-30EO-
Surfactant 1 30EO-SO4 0.5 COONa 0.65 COONa 0.65
Surfactant 2 C15-18 IOS 0.3 C15-18 IOS 0.35 C15-18 IOS 0.35
Surfactant 3 C19-23 IOS 0.2 C19-23 IOS 0.50 C19-23 IOS 0.50
IBA-1PO-
Co-Solvent 5EO 0.5 Phenol-4EO 0.25 Phenol-4EO 0.25
Alkali None 0 Ammonia 0.75 Sodium Hydroxide 0.30
Tables 4.78 and 4.79 include the core properties as well as the chemical flood
results. The first two corefloods measured the surfactant retention without alkali. The oil
recovery experiment S-2 had all the injected surfactant retained, indicating the surfactant
164
retention was at least 0.296 mg/g-rock, with a low oil recovery. The single-phase
experiment S-1 had a surfactant adsorption of 0.304 mg/g-rock, indicating the surfactant
retention for Indiana limestone at the buffered pH of the rock is ~0.30 mg/g-rock. The
next three corefloods measured the effect of ammonia alkali on surfactant retention.
Experiments A-1 and A-2 were single-phase and oil recovery experiments with
ammonia in the surfactant slug and polymer drive. Experiment A-2 had a better oil
recovery compared to S-2 with lower surfactant retention of ~0.20 mg/g-rock.
Experiment A-3 had sodium hydroxide in the polymer drive while ammonia was kept in
the surfactant slug to test the effect of a pH gradient on surfactant retention.
Experiments A-4 to A-7 measured the surfactant retention using a soft brine
preflood followed by a surfactant slug and polymer drive with sodium hydroxide alkali
and sodium sulfate. The surfactant retention was ~0.13 mg/g-rock with high oil recovery.
Experiment A-8 measured the effect of not conducting a soft brine preflood. The
surfactant retention increased to 0.19 mg/g-rock with a significant pH delay due to the
divalent ions reacting with the hydroxyl ions. This is an indication that soft brine preflood
greatly benefits the chemical flood performance.
Experiment A-9 measured the effect of not adding additional sulfate to the
chemical solutions. The surfactant retention was 0.17 mg/g-rock and there were no issues
with pH propagation. This indicates the sulfate concentration in seawater may be
sufficient to suppress or minimize the precipitation of calcium and magnesium
hydroxides in rock containing gypsum, but further investigation of the geochemical
reactions is recommended.
165
Table 4.78 Coreflood Summary for Experiments S-1 to A-3
Coreflood S-1 S-2 A-1 A-2 A-3

Rock INL INL INL INL INL
Perm (mD) 209 199 302 286 369
Type Single Phase Oil recovery Single Phase Oil recovery Oil recovery
Surfactant
Basic 0.304/ 0.296/ 0.155/ 0.244/ 0.218/
Retained/ Injected
Information 0.444 0.296 0.44 0.414 0.414
(mg/g of rock)
Sorc 0.119 0.049 0.065
Sorw 0.21 0.27 0.28
Formulation SP-1 SP-1 ASP-1 ASP-1 ASP-1
Hardness (ppm) 2600 2600
WF (ppm TDS) 49994 49994 77250 77250 77250
Salinity (ppm
80000 80000 75000 75000 75000
TDS)
Velocity (ft/day) 1 1 1 1 1
surfactant conc.
1 1 1.5 1.5 1.5
Wt.%
0.5 IBA- 0.5 IBA- 0.25% Ph- 0.25% Ph- 0.25% Ph -
co-solvent
1PO-5EO 1PO-5EO 4EO 4EO 4EO
PV 0.6 0.4 0.4 0.4 0.4
0.75% 0.75% 0.75%
SP/ASP Slug Alkali None None
NH4OH NH4OH NH4OH
Polymer type FP 3330S FP 3330S FP 3330s FP 3330s FP 3330s
polymer conc.
3500 3500 3500 4000 4000
(ppm)
filter (μm) 1.2 1.2 1.2 1.2 1.2
Viscosity (cP) 5.5 5.2 14.3 18.7 24.3
pH 8.2 8.6 10.7 10.7 10.8
Additive none none 2% Na2SO4 2% Na2SO4 2% Na2SO4
Salinity (ppm
49994 49994 52500 52500 52500
TDS)
0.5% Ph - 0.5% Ph -
co-solvent 1% Ph-4EO 1% Ph -4EO 1% Ph -4EO
6EO 6EO
0.75% 0.75%
Alkali none none 0.3% NaOH
NH4OH NH4OH
Polymer type FP 3330S FP 3330S FP 3330s FP 3330s FP 3330s
PD
C_polymer (ppm) 3500 3500 3500 4000 3750
filter (μm) 1.2 1.2 1.2 1.2 1.2
Viscosity (cP) 8 8.6 17 20.6 36.2
pH 6.1 7.8 10.8 10.8 12.4
Additive none none 2% Na2SO4 2% Na2SO4 2% Na2SO4
166
Table 4.79 Coreflood Summary for Experiments A-4 to A-9
Coreflood A-4 A-5 A-6 A-7 A-8 A-9
Rock INL INL INL INL INL INL
Perm (mD) 312 305 285 287 443 436
Single Oil Oil Oil Oil Oil
Type
Phase Recovery Recovery Recovery Recovery Recovery
Surfactant
Basic Retained/ 0.14/ 0.099/ 0.165/ 0.116/ 0.19/ 0.17/
Information Injected(mg/g of 0.414 0.443 0.386 0.421 0.422 0.451
rock)
Sorc - 0.00 0.01 0.05 0.08 0.049
Sorw - 0.20 0.23 0.28 0.29 0.28
Formulation ASP-2 ASP-2 ASP-2 ASP-2 ASP-2 ASP-2
Hardness (ppm) 2,600
WF (ppm TDS) 65,000 65,000 65,000 65,000 49,994 65,000
Sal. (ppm TDS) 63,350 63,000 63,000 63,150 63,150 63150
Velocity (ft/day) 2 2 1 1 1 1
surfactant conc.
1.5 1.5 1.5 1.5 1.5 1.5
(wt.%)
0.25% ph- 0.25% ph- 0.25% ph- 0.25% ph- 0.25% ph- 0.25% ph-
co-solvent
4EO 4EO 4EO 4EO 4EO 4EO
PV 0.4 0.4 0.4 0.4 0.4 0.4
0.3% 0.3% 0.3% 0.3% 0.3% 0.3%
Alkali
ASP Slug NaOH NaOH NaOH NaOH NaOH NaOH
Polymer type FP3330S FP3330S FP3330S FP3330S FP3330S FP 3330s
polymer conc.
3500 3500 3500 3500 3500 3500
(ppm)
filter (μm) 1.2 1.2 1.2 1.2 1.2 1.2
Viscosity (cP) 12.8 17.5 20 14.5 17.9 18.6
pH 12.6 12.7 12.6 12.4 12.6 12.3
2% 2% 2% 2% 2%
Additive none
Na2SO4 Na2SO4 Na2SO4 Na2SO4 Na2SO4
Sal. (ppm TDS) 32,550 32,550 32,550 32550 32,550 32550
1% Ph- 1% Ph- 1% Ph- 1% Ph- 1% Ph- 1% Ph-
co-solvent
4EO 4EO 4EO 4EO 4EO 4EO
0.3% 0.3% 0.3% 0.3% 0.3% 0.3%
Alkali
NaOH NaOH NaOH NaOH NaOH NaOH
Polymer type FP3330S FP3330S FP3330S FP3330S FP3330S FP 3330s
PD polymer conc.
3,500 3500 3500 3,500 3,500 3500
(ppm)
filter (μm) 1.2 1.2 1.2 1.2 1.2 1.2
Viscosity (cP) 19.7 21 21 25 36.5 30.2
pH 12.6 `12.8 `12.8 12.4 12.6 12.4
2% 2% 2% 2% 3700 ppm
Additive None
Na2SO4 Na2SO4 Na2SO4 Na2SO4 SO4
167
Maubert et al. (2018) performed SP and ASP coreflood experiments in Indiana
limestone using a light crude oil at 83oC. Figure 4.101 shows the surfactant retention
versus pH for the combined data from this study and their study. There is a clear trend of
decreasing surfactant retention with increasing pH. The corefloods where all the injected
surfactant was retained are not displayed on the figure. Coreflood A-2 is an example
where the injected surfactant (0.296 mg/g-rock) was all retained. All of the surfactant
(about 0.30 mg/g-rock) was retained in several SP corefloods reported by Maubert et al.
(2018). This indicates the surfactant retention at pH values of 8 or less may actually be
greater than 0.3 mg/g-rock.
0.35
78 C
Surfactant Retention (mg/g-rock)
0.3 83 C
0.25
0.2
0.15
0.1
0.05
0
7 8 9 10 11 12 13 14
pH
Figure 4.101 Surfactant Retention vs pH (including data from Maubert et al., 2018)
168
Chapter 5 Summary and Conclusions
This chapter discusses the conclusions drawn from the experimental results and
outlines possible future work.
5.1 Geochemistry
Understanding geochemical interactions between the injected solution and the
rock is important for chemical flood design. Measuring the effluent calcium, magnesium,
iron, and aluminum concentration helped identify the minerals in the limestone rock.
XRD data is useful but does not always indicate all the minerals in the rock.
Effluent magnesium concentration decreased with an increase in pH because the
solubility of magnesium hydroxide decreases as pH increases. The Indiana limestone
contained gypsum based on the sulfate concentration when KCl brine was injected at the
start of the coreflood experiment. Synthetic seawater and softened synthetic seawater
were used in all experiments and additional sodium sulfate was added to the chemical
solutions in all but one experiment to suppress the calcium ion concentration by the
common ion effect. The purpose of adding the additional sulfate was to prevent
precipitation of calcium hydroxide. The effluent calcium concentration decreased with an
increase in pH using this design.
An increase in the effluent aluminum concentration at high pH suggests
dissolution of clay. XRD data show a small amount of clay in the limestone cores (0.6
wt%). At high pH, aluminum exists as Al(OH4)-, which is not expected to adversely
interact with the surfactants and polymer; however, Al(OH)4- does consume hydroxide
thus slightly retarding the pH propagation. Using Figure 4.96, an aluminum concentration
of 20 ppm at a pH of 12.5 requires 50 ppm OH- to form Al(OH)4-. 0.30 wt% NaOH
provides 1,276 ppm OH-, indicating ~4% of the injected OH- will be consumed.
169
The effluent iron concentration was insensitive to pH with an effluent
concentration of 0.05 ppm (Figure 4.95). At high pH and in the oxidized state of the core,
Fe(OH)4- and Fe(OH)3 precipitate so the soluble Fe concentration is very low. However,
the role of iron, especially trivalent iron, is still considered significant despite its low
effluent concentration for several reasons. Surfactant and polymer adsorption is higher on
Fe minerals. Ferric ions appear to adversely affect the transport of the HPAM polymer.
Maubert et al. (2018) found that adding ethoxylated co-solvents such as ethoxylated
alcohols to the polymer drive improved polymer transport in oxidized carbonate cores
containing iron minerals. The mechanism is unknown but may be related to the
complexing of the ethylene oxide in the co-solvent with the ferric ions.
5.2 Surfactant Retention and pH

Systematic coreflood experiments were performed to determine the effect of
ammonia and sodium hydroxide alkalis on surfactant retention in Indiana limestone. No
data on the use of sodium hydroxide in ASP floods of carbonates was reported in the
literature at the time this study was initiated. The use of sodium hydroxide is known to
cause scaling problems in sandstones, especially at high temperature and high clay
content; however, many carbonates contain little if any clay.

Addition of alkali to the surfactant solutions resulted in a significant reduction in
surfactant retention. The average surfactant retention in Indiana limestone without any
alkali at an effluent pH of about 8 was ~0.30 mg/g-rock, or possibly somewhat greater
since all of the injected surfactant was retained in several experiments without alkali. The
average surfactant retention using ammonia at an effluent pH of 10.7 was 0.20 mg/g-
rock. The average surfactant retention using sodium hydroxide at an effluent pH of 12.5
was 0.14 mg/g-rock. This is a remarkably low retention compared to typical values of
surfactant retention in carbonates reported in the literature. The oil recovery was high
170
with a final oil saturation of nearly zero, the pressure gradient was low and the polymer
transport was favorable especially considering the cores were very heterogeneous based
on tracer tests. Without using a preflood, the surfactant retention using sodium hydroxide
increased to 0.19 mg/g-rock with a significant pH propagation delay caused by
consumption of hydroxyl ions by precipitation with the calcium and magnesium ions
when the ASP slug mixes with the hard waterflood brine. However, no plugging occurred
as a result of this scale formation in the core.
The cost of surfactant required to recover an incremental barrel of oil is directly
proportional to the surfactant retention. Thus, reducing the surfactant retention by a factor
of more than two by using sodium hydroxide also reduces the surfactant cost by a factor
of more than two. This study combined with the companion study of Maubert et al.
(2018) clearly demonstrates that high pH decreases the surfactant retention on limestone
by increasing its negative surface charge. The pH of sodium hydroxide is higher than
sodium carbonate or ammonia so this is why it gave the lowest surfactant retention.
Furthermore, a lower concentration of sodium hydroxide can be used because of its lower
molecular weight. Only 0.3 wt% NaOH was needed in these experiments. The pH
propagation was excellent even at this low concentration. However, the best choice of
alkali for ASP floods of carbonate reservoirs will depend on the mineralogy of the
carbonate formation and each case must be studied taking into account the relevant
geochemical reactions, scaling issues, facilities costs, alkali costs, and other factors
beyond the scope of this study.
5.3 Recommendations for Future Work

Although this work has established the effects of pH on surfactant retention, there
is still a need for more research. This work has primarily investigated a specific
limestone; however, dolomites and various other limestones may behave differently. This
171
is especially true as Indiana limestone is particularly clean limestone consisting mostly of
calcite. The isoelectric point for other carbonates will be different from Indiana
limestone. The surfactant retention and geochemical reactions at high pH must be
investigated for each particular rock, brine, temperature, oil and chemical formulation.
Active oils generate soap, which can potentially further reduce the surfactant retention.
However, the soap generated with some crude oils at very high pH can complicate the
microemulsion phase behavior, especially the activity diagram, and may not always be
beneficial. Sodium hydroxide is a new alkali being studied for use in ASP floods of
carbonates. It is vital to understand the geochemical interactions that occur in other
carbonates with varying degrees of iron-bearing minerals, clays and other minerals such
as dolomite. The amount of clays can significantly impact the pH propagation and
scaling. More research can and should be done to obtain a greater understanding of how
alkali can potentially reduce the cost of chemical EOR in carbonates.
172
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Certifies that this is the approved version of the following Thesis

Surfactant Retention in Limestones

Gary A. Pope, Supervisor

The University of Texas at Austin

for the Degree of

Master of Science in Engineering

The University of Texas at Austin

To my Family and my Friends

for being on my thesis committee.

Kang contributed greatly as undergraduate research assistants who aided in my research.

experiences were invaluable.

Surfactant Retention in Limestones

Denning Wang, M.S.E.

The University of Texas at Austin, 2018

Supervisor: Gary A. Pope

gypsum dissolution as was done in this study.

Systematic experiments were done to examine the effect of pH on surfactant

concentration of alkali to the chemical solutions is a minor additional expense, the

chemical cost to produce an incremental barrel of oil is greatly reduced.

1.1 Research Objectives ...........................................................................................1

CHAPTER 2 LITERATURE REVIEW 3

2.1 Chemicals ...........................................................................................................3

2.2 Microemulsion Phase Behavior .........................................................................9

CHAPTER 3 MATERIALS AND PROCEDURE 25

3.1 Materials ..........................................................................................................25

3.2 Procedures ........................................................................................................27

CHAPTER 4 EXPERIMENTAL RESULTS 34

4.1 Surfactant-Polymer Experiments .....................................................................34

4.2 Alkali-Surfactant-Polymer Experiments with Ammonia.................................55

4.3 Alkali Surfactant Polymer Experiments with Sodium Hydroxide ...................91

4.4 Effluent Ion Analysis and Geochemical Interpretation .................................158

CHAPTER 5 SUMMARY AND CONCLUSIONS 169

5.1 Geochemistry .................................................................................................169

what each chapter entails.

1.1 Research Objectives

As the world’s energy consumption continually increases and the amount of

positive to negative thus repelling the anionic surfactants, leading to a reduction in

being in carbonates, this thesis focuses on surfactant retention in limestones. Limestones

1.2 Description of Chapters

literature review on various components involved in chemical EOR. Chapter 3 discusses

the experimental results using surfactant-polymer, alkali-surfactant-polymer using

alkali-surfactant polymer processes.

Branching reduces microemulsion viscosity, reduces equilibration time, and promotes

microemulsion formation with fewer tendencies to form undesirable phases such as

Karasinghe et al., 2016).

many other advantages, prompting its use in chemical EOR.

Co-solvents possess many benefits. They lower microemulsion viscosity, increase

formations of viscous macroemulsions. Co-solvents also reduce the microemulsion

of the surfactants (Sahni et al., 2010).

Polymers are used to increase the viscosity of chemical solutions. An efficient

bank. Higher viscosity also increases the sweep efficiency.

A commonly used polymer is hydrolyzed polyacrylamide (HPAM) (Sorbie,

of unhydrolyzed polyacrylamide (PAM) at high salinities on the order of 40,000 ppm

cations. Therefore, for applications at high temperature in hard brine, alternative

Sheng et al., 2015).

Polymer solutions typically exhibit non-Newtonian behavior. At low shear rates,

polymer displays a Newtonian plateau. A non-Newtonian behavior occurs at intermediate

constants. At high shear rates, polymer rheology is Newtonian.