Textbook Co2 Reservoir Oil Miscibility Dayanand Saini Ebook All Chapter PDF

CO2-Reservoir Oil Miscibility Dayanand
Saini
Visit to download the full and correct content document:
https://textbookfull.com/product/co2-reservoir-oil-miscibility-dayanand-saini/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...
Engineering Aspects of Geologic CO2 Storage Synergy

between Enhanced Oil Recovery and Storage 1st Edition
Dayanand Saini (Auth.)
https://textbookfull.com/product/engineering-aspects-of-geologic-
co2-storage-synergy-between-enhanced-oil-recovery-and-
storage-1st-edition-dayanand-saini-auth/
Integrated Reservoir Studies for CO2 Enhanced Oil

Recovery and Sequestration Application to an Indian
Mature Oil Field 1st Edition Shib Sankar Ganguli
(Auth.)
https://textbookfull.com/product/integrated-reservoir-studies-
for-co2-enhanced-oil-recovery-and-sequestration-application-to-
an-indian-mature-oil-field-1st-edition-shib-sankar-ganguli-auth/
Machine Learning in the Oil and Gas Industry :

Including Geosciences, Reservoir Engineering, and
Production Engineering with Python Yogendra Narayan
Pandey
https://textbookfull.com/product/machine-learning-in-the-oil-and-
gas-industry-including-geosciences-reservoir-engineering-and-
production-engineering-with-python-yogendra-narayan-pandey/
An Introduction to Reservoir Simulation Using MATLAB

GNU Octave User Guide for the MATLAB Reservoir
Simulation Toolbox MRST Lie
https://textbookfull.com/product/an-introduction-to-reservoir-
simulation-using-matlab-gnu-octave-user-guide-for-the-matlab-
reservoir-simulation-toolbox-mrst-lie/
Chemo biological systems for CO2 utilization First
Edition Kumar
https://textbookfull.com/product/chemo-biological-systems-for-
co2-utilization-first-edition-kumar/
Principles of Applied Reservoir Simulation John R.

Fanchi
https://textbookfull.com/product/principles-of-applied-reservoir-
simulation-john-r-fanchi/
Reservoir modelling: a practical guide First Edition

Cannon
https://textbookfull.com/product/reservoir-modelling-a-practical-
guide-first-edition-cannon/
Offshore Processing of CO2 Rich Natural Gas with

Supersonic Separator Multiphase Sound Speed CO2 Freeze
Out and HYSYS Implementation José Luiz De Medeiros
https://textbookfull.com/product/offshore-processing-of-co2-rich-
natural-gas-with-supersonic-separator-multiphase-sound-speed-
co2-freeze-out-and-hysys-implementation-jose-luiz-de-medeiros/
Cooking with Olive Oil: Simply Delicious Olive Oil

Cooking with Over 50 Olive Oil Recipes (2nd Edition)
Booksumo Press
https://textbookfull.com/product/cooking-with-olive-oil-simply-
delicious-olive-oil-cooking-with-over-50-olive-oil-recipes-2nd-
edition-booksumo-press/
SPRINGER BRIEFS IN
PETROLEUM GEOSCIENCE & ENGINEERING
Dayanand Saini
CO2-Reservoir Oil
Miscibility
Experimental and
Non-experimental
Characterization
and Determination
Approaches
SpringerBriefs in Petroleum Geoscience
& Engineering
Series editors
Dorrik Stow, Heriot-Watt University, Edinburgh, UK
Mark Bentley, AGR TRACS International Ltd, Aberdeen, UK
Jebraeel Gholinezhad, University of Portsmouth, Portsmouth, Hampshire, UK
Lateef Akanji, King’s College, University of Aberdeen, Scotland, UK
Khalik Mohamad Sabil, Heriot-Watt University, Putrajaya, Malaysia
Susan Agar, Houston, USA
Kenichi Soga, Department of Civil and Environmental Engineering, University of
California, Berkeley, CA, USA
A. A. Sulaimon, Department of Petroleum Engineering, Universiti Teknologi
Petronas, Seri Iskandar, Perak, Malaysia
The SpringerBriefs series in Petroleum Geoscience & Engineering promotes and
expedites the dissemination of substantive new research results, state-of-the-art
subject reviews and tutorial overviews in the field of petroleum exploration,
petroleum engineering and production technology. The subject focus is on upstream
exploration and production, subsurface geoscience and engineering. These concise
summaries (50–125 pages) will include cutting-edge research, analytical methods,
advanced modelling techniques and practical applications. Coverage will extend to
all theoretical and applied aspects of the field, including traditional drilling,
shale-gas fracking, deepwater sedimentology, seismic exploration, pore-flow
modelling and petroleum economics. Topics include but are not limited to:
• Petroleum Geology & Geophysics

• Exploration: Conventional and Unconventional
• Seismic Interpretation
• Formation Evaluation (well logging)
• Drilling and Completion
• Hydraulic Fracturing
• Geomechanics
• Reservoir Simulation and Modelling
• Flow in Porous Media: from nano- to field-scale
• Reservoir Engineering
• Production Engineering
• Well Engineering; Design, Decommissioning and Abandonment
• Petroleum Systems; Instrumentation and Control
• Flow Assurance, Mineral Scale & Hydrates
• Reservoir and Well Intervention
• Reservoir Stimulation
• Oilfield Chemistry
• Risk and Uncertainty
• Petroleum Economics and Energy Policy
Contributions to the series can be made by submitting a proposal to the responsible

Springer contact, Charlotte Cross at charlotte.cross@springer.com or the Academic
Series Editor, Prof Dorrik Stow at dorrik.stow@pet.hw.ac.uk.
More information about this series at http://www.springer.com/series/15391

Dayanand Saini
CO2-Reservoir Oil
Miscibility
Experimental and Non-experimental
Characterization and Determination
Approaches
123
Dayanand Saini
Department of Physics and Engineering
California State University
Bakersfield, CA, USA
ISSN 2509-3126 ISSN 2509-3134 (electronic)

SpringerBriefs in Petroleum Geoscience & Engineering
ISBN 978-3-319-95545-2 ISBN 978-3-319-95546-9 (eBook)
https://doi.org/10.1007/978-3-319-95546-9
Library of Congress Control Number: 2018948131
© The Author(s), under exclusive licence to Springer International Publishing AG, part of Springer
Nature 2019
This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar
methodology now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publication does not imply, even in the absence of a specific statement, that such names are exempt from
the relevant protective laws and regulations and therefore free for general use.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authors or the editors give a warranty, express or implied, with respect to the material contained herein or
for any errors or omissions that may have been made. The publisher remains neutral with regard to
jurisdictional claims in published maps and institutional affiliations.
Printed on acid-free paper
This Springer imprint is published by the registered company Springer International Publishing AG
part of Springer Nature
The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland
I dedicate this work to my good friend and
former fellow student Daryl S. Sequeira, who
guided and mentored me through my first
exposure to the topic of CO2-reservoir oil
miscibility and its experimental
characterization and determination in terms
of minimum miscibility pressure (MMP)
during my early days as a graduate student at
the Craft and Hawkins Department of
Petroleum Engineering, Louisiana State
University (LSU), Baton Rouge. This work is
also dedicated to my Ph.D. Advisor,
Dr. Dandina Rao, Emmett C. Wells Jr.
Distinguished Professor of Petroleum
Engineering at LSU, who provided me with
many opportunities to expand my knowledge
of the phenomenon of CO2-reservoir oil
miscibility.
Preface
A reliable knowledge of the minimum miscibility pressure (MMP) of carbon

dioxide (CO2) plays a key role in developing cost-effective and efficient miscible
CO2 flooding projects for both enhanced oil recovery (EOR) and simultaneous
EOR and storage purposes. Hence, interested students and industry professionals
who are either planning to join or are already involved in such projects will greatly
benefit from a text that can enhance their understanding of both the phenomenon of
CO2-reservoir oil miscibility and the various experimental and non-experimental
approaches that are used to characterize and determine it in terms of MMP. This
book is meant to serve that very purpose.
Bakersfield, USA Dayanand Saini
vii
Acknowledgements
I would like to thank the Department of Physics and Engineering and the School of
Natural Sciences, Mathematics, and Engineering (NSME) for providing me an
opportunity to continue my research in the area of CO2-reservoir oil miscibility at
the California State University, Bakersfield (CSUB).
The research performed at CSUB during 2013–16 had later prompted me to
publish two publications: “Modeling of Pressure Dependence of Interfacial Tension
Behaviors of a Complex Supercritical CO2 + Live Crude Oil System Using a Basic
Parachor Expression” in the Journal of Petroleum and Environmental Biotechnology
(Vol 7: 277) and “An Investigation of the Robustness of Physical and Numerical
Vanishing Interfacial Tension Experimentation in Determining CO2 + Crude Oil
Minimum Miscibility Pressure” in the Journal of Petroleum Engineering (Vol 2016,
Article ID 8150752). The contribution of the above-mentioned publications in
developing the content for this book is duly acknowledged.
A special thanks to Ms. Charlotte Cross, Assistant Editor (Engineering),
Springer London, for her time, effort, and encouragement that made the publication
of this book a reality. Last but not least, thanks to my daughter, Lalima, and my
wife, Rekha, for their unwavering support and understanding during the preparation
of the manuscript.
ix
Contents
1 Fundamentals of CO2 -Reservoir Oil Miscibility . . . . . . . . . . . . . . . . 1

1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Miscibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Solvent Properties of Supercritical CO2 . . . . . . . . . . . . . . . . . . . . 6
1.4 Attainment of Miscibility Between Injected CO2
and Reservoir Oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4.1 Molecular Dynamics-Based Approach . . . . . . . . . . . . . . . . 9
1.4.2 Interfacial Energy-Based Approach . . . . . . . . . . . . . . . . . . 12
1.4.3 Thermodynamics-Based Approach . . . . . . . . . . . . . . . . . . 13
1.5 Other Considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2 Characterization and Determination of CO2 -Reservoir Oil
Miscibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.1 Needs to Determine the MMP . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.2 Technical Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.1 Thermodynamic Variables . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2.2 Natural Forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.2.3 Operational Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.3 Economic Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.4 Is It Necessary to Characterize and Determine CO2 -Reservoir
Oil Miscibility? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 30
2.5 CO2 -Reservoir Oil Miscibility Characterization
and Determination Approaches . . . . . . . . . . . . . . . . . . . . . . . ... 31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 32
3 Experimental Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
3.2 The Slim-Tube Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.3 The Rising-Bubble Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
xi
xii Contents
3.4 The Experimental Vanishing Interfacial Tension (VIT)

Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ 46
3.4.1 Experimental Data Collection and Interpretation
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . ........ 47
3.4.2 Robustness of the VIT Method . . . . . . . . . . . . . ........ 50
3.4.3 Theoretical Concerns About the Robustness
of the VIT Method . . . . . . . . . . . . . . . . . . . . . ........ 52
3.4.4 Pressure Dependence of the IFT Behaviors
of CO2 -Reservoir Oil Systems . . . . . . . . . . . . . ........ 55
3.4.5 Prediction of Prevailing Drive Mechanism(s) . . . ........ 60
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ........ 63
4 Non-experimental Approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
4.2 Empirical Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.2.1 Emera-Sarma Correlation . . . . . . . . . . . . . . . . . . . . . . . . . 71
4.2.2 Li et al. Correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
4.2.3 Zhang et al. Correlation . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.2.4 Valluri et al. Correlation . . . . . . . . . . . . . . . . . . . . . . . . . 74
4.3 Analytical Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.3.1 The MOC-Based Key-Tie-Line Approach . . . . . . . . . . . . . 75
4.3.2 The Simulated VIT Methods . . . . . . . . . . . . . . . . . . . . . . 77
4.4 Numerical Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.4.1 1D Slim-Tube Simulation . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.4.2 The Multiple-Mixing-Cell Method . . . . . . . . . . . . . . . . . . 81
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
5 Recent Advancements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
5.2 Improvements in Existing Experimental Approaches . . . . . . . . . . . 88
5.2.1 The Novel Slim-Tube Protocol . . . . . . . . . . . . . . . . . . . . . 88
5.2.2 The Fast Slim-Tube Method . . . . . . . . . . . . . . . . . . . . . . . 89
5.3 Newly Developed Experimental Approaches . . . . . . . . . . . . . . . . 90
5.3.1 The Fast Fluorescence-Based Microfluidic MMP
Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
5.3.2 The Sonic Response Method . . . . . . . . . . . . . . . . . . . . . . 92
5.3.3 The Rapid Pressure Increase Method . . . . . . . . . . . . . . . . 93
5.4 Recent Developments in Numerical Approaches . . . . . . . . . . . . . . 95
5.4.1 The Molecular Dynamic Simulation Method . . . . . . . . . . . 95
5.5 Determination and Characterization of CO2 -Reservoir Oil
Miscibility in Unconventional Reservoirs . . . . . . . . . . . . . . . . . . . 96
5.5.1 The RBA Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
5.5.2 The Capillary-Rise-Based VIT Method . . . . . . . . . . . . . . . 97
5.5.3 Integrated MMP Correlation . . . . . . . . . . . . . . . . . . . . . . . 99
Contents xiii
5.5.4 PC-SAFT EOS Model . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

5.5.5 The Diminishing Interface Method . . . . . . . . . . . . . . . . . . 101
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
Abbreviations
1D One-Dimensional
AMS Acoustically Monitored Separator
ARI Advanced Resources International
CCUS Carbon Capture, Use, and Storage
CO2 Carbon Dioxide
DIM Diminishing Interface Method
DOE Department of Energy
EOR Enhanced Oil Recovery
EOS Equation of State
FC-MMP First Contact Minimum Miscibility Pressure
GA Genetic Algorithm
H 2S Hydrogen Sulfide
HCPV Hydrocarbon Pore Volume
HPHT High-Pressure High-Temperature
ICA Imperialistic Competitive Algorithm
IFT Interfacial Tension
LGT Linear Gradient Theory
LPG Liquefied Petroleum Gas
LSIPs Large-Scale Integrated Carbon Capture and Storage Projects
MCM Multicontact Miscibility
MC-MMP Multicontact Minimum Miscibility Pressure
MCT Multicontact
MMP Minimum Miscibility Pressure
MMV Monitoring, Management, and Verification
MOC Method of Characteristics
MVA Monitoring, Verification, and Accounting
NETL National Energy Technology Laboratory
OXY Occidental Petroleum Corporation
P/T Pressure/Temperature
PC-SAFT Perturbed-Chain Statistical Associating Fluid Theory
xv
xvi Abbreviations
PREOS Peng–Robinson Equation of State

PVT Pressure, Volume, Temperature
RBA Rising Bubble Apparatus
RBF Radial Basis Function
ROZ Residual Oil Zone
RPI Rapid Pressure Increase
SACROC Scurry Area Canyon Reef Operators Committee
ScCO2 Supercritical Carbon Dioxide
SFE Supercritical Fluid Extraction
SRM Sonic Response Method
UCSP Upper Critical Solution Pressure
VIT Vanishing Interfacial Tension
VLE Vapor–Liquid Equilibrium
WAG Water Alternating Gas
Chapter 1
Fundamentals of CO2 -Reservoir Oil
Miscibility
Abstract The efficient and coeffective implementation and operation of CO2

injection-based enhanced oil recovery (CO2 -EOR) and/or simultaneous CO2 -EOR
and storage projects often rely on accurate characterization and determination of the
phenomenon of CO2 -reservoir miscibility in terms of the minimum miscibility pres-
sure (MMP). Hence, for a better understanding of both the CO2 -reservoir oil miscibil-
ity and the MMP it is necessary that various fundamental aspects of CO2 -reservoir oil
miscibility are understood first. Different approaches, including molecular dynamics-
based, interfacial energy-based, and thermodynamics-based approaches can be used
to better understand the complex interactions occurring between injected CO2 and
reservoir oil that ultimately lead to the development of miscibility at the MMP. To
enhance our understanding of the phenomenon of CO2 -reservoir oil miscibility, a
discussion of the key differences between solubility and miscibility and the solvent
properties of supercritical CO2 is also presented.
1.1 Introduction
The beneficial role of high miscibility between carbon dioxide (CO2 ) and reservoir
oil at pressures more than 6.8 MPa (1,000 psi) was clearly recognized by Whorton
et al. (1952) when they filed the first U.S. patent for a method for producing oil by
means of CO2 in the 1950s. Later, a large-scale commercial enhanced oil recovery
(EOR) project, which involved the injection of CO2 for recovering more oil from
depleted reservoirs, was first implemented in the Permian Basin of West Texas by
the Scurry Area Canyon Reef Operators Committee (SACROC) Unit of the Kelly-
Snyder Field and North Cross floods in the early 1970s (Meyer 2007; Global CCS
Institute 2011). These innovations opened the door for CO2 injection-based miscible
flooding techniques to become among the most popular EOR methods to date for
improving overall oil recovery factors in conventional reservoirs.
According to Qin et al. (2015), there are 152 CO2 -EOR projects around the world
(as per 2014 data) and majority of them (137) are in the United States. Out of 137
US CO2 -EOR projects, 128 projects are miscible flooding projects accounts. As
© The Author(s), under exclusive licence to Springer International Publishing AG, 1

part of Springer Nature 2019
D. Saini, CO2 -Reservoir Oil Miscibility, SpringerBriefs in Petroleum
Geoscience & Engineering, https://doi.org/10.1007/978-3-319-95546-9_1
2 1 Fundamentals of CO2 -Reservoir Oil Miscibility
both the data and the name suggest, CO2 -reservoir oil miscibility plays a key role in
the success of CO2 injection-based miscible flooding EOR as well as simultaneous
CO2 -EOR and storage projects in conventional reservoirs. However, a knowledge
of the fundamentals (theory, scientific principles, and engineering applications) of
CO2 -reservoir oil miscibility is desired for a better understanding of its role in the
successful design, implementation, and operation of a miscible CO2 -EOR project. It
is worth mentioning here that in contrast to unconventional reservoirs where certain
reservoir and reservoir fluids characteristics (i.e., low permeability, porosity, and oil
viscosity) require the use of specialized drilling (e.g., horizontal wells), completion
(e.g., hydraulic fracturing), and production (e.g., steamflooding) techniques for com-
mercial exploitation of hydrocarbon reserves, conventional reservoirs use relatively
simple and standard drilling, completion, and production methods for producing
hydrocarbons in commercial quantities.
Before the fundamentals of CO2 -reservoir oil miscibility are discussed in detail,
we need to appreciate the fact that it is an injection fluid of choice for the petroleum
industry. Obviously, it shows high miscibility with reservoir oils; however, it is also
less expensive than other similarly miscible fluids (NETL 2010) such as nitrogen
and liquified petroleum gas (LPG). On another hand, a significant portion of injected
CO2 is lost in the reservoir anyway. This incidental storage of injected CO2 in an
EOR project, in the form of carbon capture, utilization, and sequestration (CCUS),
provides another value-added benefit, and the industry has already seized upon it.
The recent significant growth in the portfolio of large-scale integrated carbon capture
and storage projects (LSIPs), which mainly rely on the utilization of commercially-
captured anthropogenic CO2 for maximizing both aspects (i.e., oil recovery and CO2
storage) of miscible CO2 -EOR projects, clearly indicates the increased importance
and acceptance of this value-added benefit. A detailed discussion of the synergy of
EOR and storage in miscible CO2 -EOR operations can be found elsewhere (Saini
2017).
1.2 Miscibility
Before discussing the specifics of the tools and techniques that are current available
for characterizing and determining CO2 -reservoir oil miscibility, a brief discussion on
the basic definition and general theory of miscibility is necessary. The term miscibility
is often used to refer the ability of a liquid solute to dissolve in a liquid solvent,
whereas, solubility is a more general term, often referring to the ability of a solid
solute to dissolve in a liquid solvent (Suico 2017). Hence, miscibility, a qualitative
rather than a quantitative observation, means how completely two or more liquids
dissolve in each other (Net Industries 2017). Formally, miscibility or infinite mutual
solubility can be described as “physical condition between two fluids that will permit
them to mix in all proportions without an interface being formed by the materials”
(Clark et al. 1958).
1.2 Miscibility 3
Miscible liquids generally mix without limit, meaning they are soluble at all
amounts (Suico 2017). For example, two common liquids—namely water and ethyl
alcohol—are completely miscible whether the solution is 1% water and 99% ethyl
alcohol, 50% of both, or 1% ethyl alcohol and 99% water (Net Industries 2017). In this
example, mixing (i.e., mutual solubility) of water and ethyl alcohol is independent of
their individual concentrations. Hence, they have infinite mutual solubility and are
completely miscible. However, it was recognized long ago, that without a knowledge
of the law of molecular attraction, the required conditions for complete miscibility
or infinite solubility cannot be dealt with quantitatively (Tyrer 1912).
The extent of miscibility between two liquids can be explained on the basis of
molecular attractions. According to Burke (1984), a certain amount of intermolecular
stickiness holds the molecules of the liquid together. This intermolecular stickiness
or sticky forces between molecules are called van der Waals forces, which are the
result of electromagnetic interactions between the molecules (Burke 1984). Further-
more, compared to a neutral (i.e., neither positively charged nor negatively charged)
molecule, an individual molecule itself may possess a different electron shell density,
which turns a molecule in a small magnet, or dipole. The extent of the deviations in
electron shell density depends on the physical architecture of the molecule, hence,
certain molecular geometries may result in strongly polar substances, while other
configurations may result in only a weakly polar substance (Burke 1984). Thus, the
substances that have similar polarities are easily soluble in each other, but as, the
deviations in polarity increases, solubility becomes increasingly difficult. As further
discussed by Burke (1984), the extent of solubility not only depends on the differ-
ent degrees of similar polarities, but it is also affected by the degree of similarity
between other intramolecular interactions such as hydrogen bonding, induction and
orientation effects, and dispersion forces.
Normally, polar liquids (solute molecules) tend to mix easily with polar liquids
(solvent molecules), because the dipole-dipole attractions (or hydrogen bonding) of
the solute molecules are at least as strong as those between molecules in the pure
solute or in the pure solvent (OpenStax 2016). Similarly, non-polar liquids mix eas-
ily with each other because there is no appreciable difference in the strengths of
solute-solute, solvent-solvent, and solute-solvent intermolecular attractions (Open-
Stax 2016). Thus, polar molecules in polar solvents and nonpolar molecules in non-
polar solvents show miscible behavior. An example of miscible behavior between two
fluids (e.g., water and isopropyl alcohol) is demonstrated in Fig. 1.1. As can be seen
in Fig. 1.1, when colored water (Fig. 1.1a) and dyed isopropyl alcohol (Fig. 1.1b) are
mixed, they immediately form a miscible phase (i.e., a dark colored solution shown
in Fig. 1.1c).
Certain liquids, such as bromine and water, which show moderate mutual solubil-
ity are said to be partially miscible (OpenStax 2016). In case of bromine and water,
when mixed together, two distinct layers, a top layer containing saturated solution
of bromine in water and a bottom layer consisting a saturated solution of water in
bromine, can be easily distinguished. Bromine, being a nonpolar liquid shows limited
solubility (i.e., partial miscibility) in water, which is the most common polar solvent.
On the other hand, many non-polar liquids (e.g., hydrocarbons such as benzene,
Fig. 1.1 Example of miscible (complete mutual solubility) behavior between colored water and
dyed isopropyl alcohol (dark) phases
dodecane etc.) do not mix to an appreciable extent with polar liquids such as water.
Because they show very low (i.e., non-zero) mutual solubility, they are called immis-
cible. The attraction between the molecules of such non-polar liquids and polar water
molecules is ineffectively weak and the only strong attractions in such a mixture are
between the water molecules, so they effectively squeeze out the molecules of the
non-polar liquid (OpenStax 2016). The immiscible behavior, as shown by mineral
oil (Fig 1.2a) and isopropyl alcohol (Fig 1.2b) phases by forming two distinct phases
(Fig. 1.2c), is clearly visible in Fig. 1.2.
As further summarized by OpenStax (2016), the distinction between immiscible
and miscible fluids is essentially the extent of miscibility as miscible liquids are of
infinite mutual solubility, while liquids said to be immiscible are of very low (though
not zero) mutual solubility. Also, in case of miscibility, conventional concepts of
solute (the minor component in a solution) and solvent (the liquid in which solute is
dissolved to form a solution) do not matter as miscibility itself is a manifestation of
infinite solubility, which is independent of the relative concentrations of individual
liquids forming the solution. The same is true for a solution resulting from the mixing
of multiple liquids.
In nutshell, solubility is determined by the balance of intermolecular forces
between solute and solvent as well as the entropy change that occurs on the dis-
persal of the solute in the solvent, thereby depending on the system’s pressure and
temperature (Peach and Eastoe 2014). Obviously, a system’s total volume remains
constant when two liquids are mixed to form a solution. On the other hand, when
it comes to mutual solubility (i.e., miscibility) of CO2 and reservoir oils, first, we
need to appreciate the fact that the injection of CO2 for EOR purposes is carried
out at the conditions of elevated pressure (i.e., injection pressure) and temperature
1.2 Miscibility 5
Fig. 1.2 Example of immiscible (a very low mutual solubility) behavior between mineral oil (clear)
and dyed isopropyl alcohol (dark) phases
Fig. 1.3 Variation in key characteristics of CO2 in different states (i.e., gas phase, supercritical
phase, and liquid phase)
(i.e., reservoir temperature). These pressure and temperature conditions are always
well beyond the critical pressure and critical temperature of CO2 . When placed at
a pressure and temperature above its critical pressure and critical temperature (i.e.,
in a supercritical state), CO2 exhibits certain unique, interesting, and useful char-
acteristics (Fig. 1.3) including gas-like diffusivity and liquid-like solvent densities.
Secondly, CO2 is generally considered as a non-polar solvent, primarily because of its
zero-molecular dipole moment and its low dielectric constant; however, it may also
show polar attributes (Raveendran et al. 2005). In contrast, reservoir oils, because
they are a complex mixture of substances, may show a variety of polarities ranging
from extremely nonpolar, low polar, polar, highly polar, extrapolar (Bruening 1991).
Nevertheless, supercritical CO2 (ScCO2 ) is one of the most commonly used sol-
vent as well as displacing agent (like other oil solvents and displacing agents such as
nitrogen and LPG) in miscible flooding projects meant to improve oil recovery. How-
ever, the condition of complete miscibility (i.e., infinite solubility) between CO2 (i.e.,
ScCO2 ) and a given reservoir oil occurs at certain operating pressure and reservoir
temperature. Depending on the nature of contacts (i.e., first contact or multiple con-
tacts) occurring between injected CO2 and reservoir oil for establishing miscibility,
the pressure is referred to as first contact-minimum miscibility pressure (FC-MMP)
or multiple contact-minimum miscibility pressure (MC-MMP). The MC-MMP is
simply referred as the MMP throughout the text.
The first-contact miscibility refers to a condition wherein injected CO2 and reser-
voir oil become miscible at their first ever contact. The phenomenon of achieving
miscibility through first-contact process is generally exhibited by solvents like LPG
and light oils; however, CO2 cannot achieve first-contact miscibility in most oil reser-
voirs within a reasonable range of pressures and reservoir temperature. In the case of
a given reservoir oil and injected CO2 system, for complete miscibility to occur, mul-
tiple contacts between the two phases are needed. In a multicontact process, CO2 and
various components of reservoir oil make numerous contacts by moving back and
forth within the contacting phases (i.e., the CO2 -rich phase and the oil-rich phase)
until a completely miscible phase (i.e., a homogeneous phase) is formed. The lowest
operating pressure at which condition of multicontact miscibility between injected
CO2 and reservoir oil occur is termed as minimum miscibility pressure (MMP).
Whether a CO2 -reservoir oil system achieves miscibility through the process of
first-contact or miscibility is achieved through the process of multicontact, it is nec-
essary that, for developing a better understanding of CO2 -reservoir oil miscibility at
fundamental level, one look at the phase behavior of ScCO2 and some of the basic
characteristics responsible for its infinite ranging and inherent solvent properties.
1.3 Solvent Properties of Supercritical CO2
As can be seen in Fig. 1.4, a supercritical region is the region of CO2 phase diagram,
which is beyond the critical point of CO2 (i.e., critical pressure of 7.38 MPa (1,070.3
psi) and critical temperature of 30.98 °C (87.76 °F)). In a supercritical state, which
is easily achieved in such processes a CO2 -injection-based EOR operations, CO2
possesses both liquid-like (high density) and gas-like (low viscosity and high diffu-
sivity) properties as well as an intermediate or transitional behavior between that of
a liquid and a gas (Supercriticalfluid website 2017), recognized by the widom region
(Fig. 1.4). Certain properties of ScCO2 can be exploited for many useful scientific
purposes and industrial processes (Kaziunas and Schlake 2016). In case of conven-
tional liquid solvents such as propane and other supercritical fluids such as nitrogen,
due to their relatively low compressibilities, very large pressures are required to make
any appreciable change in their densities, whereas, a significant change in the density
of ScCO2 can be obtained by a change in pressure (Fig. 1.5).
It is also well known that all the thermodynamic properties of a pure substance,
in our case ScCO2 , can be obtained by the derivative form of a fundamental equation
1.3 Solvent Properties of Supercritical CO2 7
Fig. 1.4 CO2 phase diagram, reprinted with modification by permission from Copyright Clearance
Center: Springer Nature, Environmental Earth Sciences, Anomalous fluid properties of carbon
dioxide in the supercritical region: application to geological CO2 storage and related hazards, Imre
AR, Ramboz C, Deiters UK et al., © 2015
Fig. 1.5 Example of significant change (more than 25%) in supercritical CO2 density due to an
isothermal pressure drop (T 32.6 °C) of 0.1 MPa, reprinted with modification by permission from
Copyright Clearance Center: Springer Nature, Environmental Earth Sciences, Anomalous fluid
properties of carbon dioxide in the supercritical region: application to geological CO2 storage and
related hazards, Imre AR, Ramboz C, Deiters UK et al., © 2015
of state explicit in the Helmholtz energy, which is a function of two independent

variables—density and temperature (Span and Wagner 1996). On the other hand, we
know that, like its other thermodynamic properties, the solvating power of ScCO2 can
also be easily adjusted by manipulating the pressure and temperature conditions of
the system. However, there are certain basic characteristics that need to be considered
for a fundamental understanding of the solvating power of ScCO2 . Raveendran et al.
(2005) have provided a detailed discussion of the fundamental nature of CO2 (i.e.,
ScCO2 ) as a solvent, which is summarized below.
According to Raveendran et al. (2005), a more molecular level “chemical” descrip-
tion of the solvation behavior of CO2 suggests that CO2 can act as a weak Lewis
acid (i.e., a substance, such as H+ ion, with capability to accept a pair of nonbonding
electrons) as well as a Lewis base (i.e., a substance, such as OH− ion, that can donate
a pair of nonbonding electrons). Also, various theoretical and experimental evidence
indicates that CO2 can participate in hydrogen-bonding interactions (Raveendran
et al. 2005). Hence, at a fundamental level, CO2 needs to be considered as a polar
solvent, and its solvent properties depend on the solute-solute, solute-solvent, and
solvent-solvent interactions. It is the nature of site-specific solute-solvent interactions
(i.e., how easily the pairwise solute-solute interaction energies can be overcome by
the pairwise solute-solvent interaction energies), that ultimately decides the solubil-
ity of materials in CO2 (Raveendran et al. 2005). The term “site-specific interactions”
used here is a qualitative representation of variety of intermolecular and intramolec-
ular interactions taking place between the atomic-level sites of CO2 molecules and
the molecules of liquid in question.
These above-mentioned interesting and useful properties put CO2 into a unique
position among supercritical fluids. It is the most widely used supercritical fluid
with a wealth of industrial applications and processes such as superfluid extraction
(SFE), enhanced oil recovery (EOR), and ScCO2 Brayton power cycles. On the
other hand, in the case of EOR, the most efficient use of CO2 (i.e., ScCO2 ) as an
oil-recovery agent (i.e., solvent as well as displacing agent) is obtained at flooding
pressures at which miscible displacement is achieved (Holm and Josendal 1974).
Hence, achieving miscibility between injected CO2 and reservoir oil is key for any
successful EOR project. However, what is the fundamental nature of infinite solubility
(i.e., complete miscibility) that occurs between injected CO2 and reservoir oils and
is thermodynamically manifested by the MMP (first contact or multiple contacts)?
This issue is worth considering and is discussed next.
1.4 Attainment of Miscibility Between Injected CO2

and Reservoir Oil
When used for EOR purposes, CO2 recovers reservoir oil by generating miscibil-
ity, swelling the oil, lowering the oil viscosity, and lowering the interfacial tension
between the non-contacted reservoir oil and the CO2 -oil phase in the near-miscible
regions (Lyons and Plisga 2005). Not only can CO2 increase the oil density, but it can
also vaporize and extract portions of crude oil (Holm and Josendal 1974). Basically,
the physical interactions such as oil swelling, oil density increase, viscosity reduction
are the results of a certain process or mechanism that may ultimately result in the
1.4 Attainment of Miscibility Between Injected CO2 and Reservoir Oil 9
Injection well Near critical Production well

region
(CO2 and oil form
single phase in
this region
CO2
Pure condensing Non-contacted
CO2 into oil reservoir oil
Direction of displacement
Fig. 1.6 One dimensional schematic of the condensing drive mechanism responsible for the devel-
opment of CO2 -reservoir oil miscibility in the reservoir, reprinted by permission from Copyright
Clearance Center: Springer Nature, Evaluation of CO2 -Oil Miscibility, Saini D, © 2017
development of miscibility in CO2 -reservoir oil mixtures. This process or mecha-

nism is commonly referred to as the condensing drive mechanism in which injected
CO2 condenses into bulk oil phase while displacing it from the injector well to the
production well. A schematic description of condensing drive mechanism is shown
in Fig. 1.6.
On the other hand, CO2 can also selectively extract non-polar (apolar) components
from the reservoir crude oil (Fang et al. 2016). Hence, in case of certain CO2 -reservoir
oil mixtures, the extraction or vaporization of lighter hydrocarbons by injected CO2
may be the dominating mechanism (i.e., vaporizing drive mechanism), which ulti-
mately results in the development of multiple contact miscibility between injected
CO2 and reservoir oil while injected CO2 is displacing reservoir oil (Fig. 1.7). Most
often, it is a combined or mixed-drive mechanism called a vaporizing/condensing
drive mechanism (Zick 1986; Stalkup 1987), which ultimately leads to the devel-
opment miscibility between injected CO2 and real reservoir fluids through multiple
contacts as injected CO2 moves downstream while driving the reservoir oil towards
the production well. Figure 1.8 schematic depicts this mixed-drive mechanism.
A further understanding of the attainment of miscibility between injected CO2 and
reservoir oil (i.e., a CO2 -reservoir oil system) through multiple contacts, commonly
referred as multicontact miscible (MCM) displacement, can be developed on the
basis on various theoretical approaches. Some of the sound theoretical approaches
are discussed next.
1.4.1 Molecular Dynamics-Based Approach
From a molecular dynamics point of view, miscibility between injected CO2 and a
reservoir oil (i.e., a CO2 -reservoir oil system) can be considered a manifestation of
Injection well Near critical Production well

region
(CO2 and oil form
single phase in
this region
CO2
Pure vaporizing Non-contacted
CO2 oil components reservoir oil
Fig. 1.7 One dimensional schematic of the vaporizing drive mechanism responsible for the devel-
opment of CO2 -reservoir oil miscibility in the reservoir, reprinted by permission from Copyright
Clearance Center: Springer Nature, Evaluation of CO2 -Oil Miscibility, Saini D, © 2017
Injection well Near critical region

Production well
(CO2 and oil form
single phase in this
region)
Pure CO2 CO2 Non-contacted

CO2 vaporizing condensing reservoir oil
oil oil
components components
Fig. 1.8 One dimensional schematic of mixed (vaporizing + condensing) drive mechanism respon-
sible for the development of CO2 -reservoir oil miscibility in the reservoir, reprinted by permission
from Copyright Clearance Center: Springer Nature, Evaluation of CO2 -Oil Miscibility, Saini D, ©
2017
molecular motion and interaction of molecules (Yang et al. 2016). Both the molecular
motion (i.e., thermal motion of molecules due to a system’s pressure and temperature
conditions) and molecular interactions (i.e., resultant molecular forces arising from
intermolecular [van der Waals, electrostatic] and intramolecular [bonding] interac-
tions) dictate the extent of mutual diffusivity (i.e., mass transfer) between injected
CO2 and reservoir oil phases and the reduction in CO2 -reservoir oil interfacial ten-
sion (CO2 -reservoir oil IFT). Also, as noted by Orr et al. (1983), molecular size
distribution of pentane plus (C5+ ) fraction present in reservoir oil also play a key role
in the development of miscibility between injected CO2 and reservoir oil.
The mass transfer is caused by the difference in density or temperature of the
two-phase system (Mengshan et al. 2017). For an isothermal process, molecules
move from the phase with the larger density to the phase with the smaller density
until an equilibrium state is reached (Mengshan et al. 2017). Because CO2 -reservoir
oil miscibility is always evaluated at given temperature (i.e., reservoir temperature),
density difference is the governing mechanism for the mass transfer via molecular
diffusion that takes place between injected CO2 and reservoir oil phases when they
first come in contact of each other.
On the other hand, at lower operating pressures (i.e., injection pressures < MMP),
CO2 -reservoir oil mixtures are known to show significant interfacial tension (IFT);
however, as pressure approaches near MMP, CO2 -reservoir oil IFT reduces signifi-
cantly or almost vanishes (e.g., Ayirala and Rao 2006; Sequeira et al. 2008; Saini and
Rao 2010). Obviously, the existence of significant IFT between injected CO2 and a
given reservoir oil at lower pressures (< MMP) will result in limited mutual diffusion
interactions. However, a significant reduction in IFT at a pressure near MMP facil-
itates uninterrupted mutual diffusion (i.e., mass transfer) between injected CO2 and
reservoir oil molecules; thus, a homogeneous phase (i.e., no interface) is formed at
MMP and the condition of infinite solubility (i.e., complete miscibility) for a given
CO2 -reservoir oil system is achieved.
The pressure dependence of CO2 -reservoir oil IFT and its implications for mass
transfer can be visualized through Figs. 1.9 and 1.10, which include images taken
during the high-pressure high-temperature (HPHT) experimentation conducted by
Saini and Rao (2010) for studying the pressure dependence of IFT between pure CO2
and a real reservoir oil. As can be seen from Fig. 1.9, the regular shape of a freshly
introduced pendant drop of reservoir formed with the help of an available injector
tip in a HPHT cell, which was initially filled with pure CO2 and was kept at 20 MPa
(2,900 psi) and 142.7 °C (289°F), clearly indicates the presence of significant IFT
(2.16 mN/m) between pure CO2 and fresh reservoir oil. Also, formation of couple
of fluid streaks (Fig. 1.9) indicated the presence of week mutual interactions (i.e.,
limited mass transfer) between freshly-introduced reservoir oil and bulk CO2 phase.
In contrast, when the pressure is increased to 23.1 MPa (3,500 psi) by injecting
fresh CO2 , now a pendant drop of freshly introduced reservoir oil (i.e., reservoir
oil of original composition) in the CO2 -rich phase, which is already present in the
HPHT cell, could hardly be formed (Fig. 1.10). The system (i.e., CO2 -rich gas phase
and oil-rich liquid phase) exhibits a low IFT (0.19 mN/m). Further, the formation of
multiple fluid streaks and an immediate distortion of a pendant oil drop (Fig. 1.10)
as soon as the reservoir oil (of initial composition) was brought in contact with an
existing CO2 -rich phase indicate the presence of strong mutual interactions between
freshly-introduced pendant drop of reservoir oil and CO2 -rich phase, which is due to
the lack of any significant IFT between the two phases. It is worth mentioning here
that the equilibrium compositions of both the phases (i.e., a CO2 -rich gas phase and
an oil-rich liquid phase) are significantly different from the original compositions of
CO2 and reservoir oil (i.e., pure CO2 and reservoir oil of original composition).
Fig. 1.9 Visualization of weak mutual interactions (i.e., limited mass transfer) between freshly-
introduced pendant drop of reservoir oil and bulk CO2 phase at experimental pressure step below
MMP and reservoir temperature, as observed during HPHT experimentation conducted by Saini and
Rao (2010), modified figure reproduced by permission: Soc Pet Eng, Experimental determination
of minimum miscibility pressure (MMP) by gas/oil IFT measurements for a gas injection EOR
project. https://doi.org/10.2118/132389-ms, Saini and Rao © 2010
Fig. 1.10 Visualization of strong mutual interaction (i.e., significant mass transfer) between
freshly-introduced pendant drop of reservoir oil and CO2 -rich phase at experimental pressure step
close to MMP and reservoir temperature, as observed during HPHT experimentation conducted by
Saini and Rao (2010), modified figure reproduced by permission: Soc Pet Eng, Experimental deter-
mination of minimum miscibility pressure (MMP) by gas/oil IFT measurements for a gas injection
EOR project. https://doi.org/10.2118/132389-ms, Saini and Rao © 2010
1.4.2 Interfacial Energy-Based Approach
To further understand the delicate interplay of the phenomena of mutual diffusivity

and interfacial tension and their implications for the development of CO2 -reservoir
oil miscibility, we need to look at the concept of interfacial energy (i.e., surface
free energy or free surface energy). The theory of the origin of interfacial energy
given by Antonoff (1907) in Nosonovsky and Ramachandran (2015) is the simplest
way intended to describe the tension at the interface (i.e., IFT) between two liq-
uids (Nosonovsky and Ramachandran 2015). According to Antonow’s theory, as
explained by Nosonovsky and Ramachandran (2015), the atoms of the surface layer
have, on average, fewer bonds with their neighbors; therefore, their energy is larger
than that of the atoms or molecules in the bulk (i.e., away from the surface). When
two liquid surfaces come into contact, the lack of neighboring bonds in the surface
layer is partially compensated by the atoms or molecules in the opposite substance
(Nosonovsky and Ramachandran 2015). The total number of interactions are defined
by the substance providing the lower numbers of bonds of the two; thus, the interfa-
cial energy is proportional to the difference in the available bonds (Nosonovsky and
Ramachandran 2015).
In our case, two liquids will be ScCO2 and a given reservoir oil. Also, it can be
expected that reservoir oils, which may possess a wide range of polarities due to
the presence of hundreds of different types of hydrocarbon components and various
chemical compounds, would have a significantly higher number of available bonds
compared to CO2 . Hence, ScCO2 , which can act as a weak Lewis acid as well as a
Lewis base (i.e., possesses certain polar attributes), is expected to dictate the extent
of mutual interactions for a given CO2 -reservoir oil system. It is also noted here that,
in the reservoir, due to the simultaneous flow of the injected CO2 and the displaced
reservoir oil, some physical mixing between the two phases always occurs. It is also
expected to enhance the physical and chemical interactions that take place when
injected CO2 comes into repeated contacts with reservoir oil present in a confined
space (i.e., pore space of the reservoir rock) while moving towards the production
well from the injection well.
1.4.3 Thermodynamics-Based Approach
Thermodynamically, for an isothermal and isobaric system, which is the case for
the process of CO2 -reservoir oil miscibility, any variation in the chemical potential
will tend to lead to mass transport. The chemical potential is actually the Gibbs free
energy. the Gibbs free energy represents all the reversible work (such as electric
work and work creating surface area) expect mechanical work that can be obtained
from the system. The equilibrium IFT, which is a measure of the surface free energy
of the system, reflects the condition of the minimization of the Gibbs free energy.
The Gibbs free energy must decrease if such a system departs from equilibrium or
remains unchanged if an equilibrium has been achieved. Hence, CO2 and reservoir
oil, when encountering each other, attempt to attain an equilibrium by minimizing
the Gibbs free energy. In contrast, the Helmholtz free energy, which represents all the
reversible work including mechanical work, seeks a minimum, a change in a process
occurring at constant temperature and volume.
Fig. 1.11 Schematic representation of a multicomponent CO2 -reservoir oil mixture as a pseudo
ternary system
Nevertheless, CO2 -reservoir oil miscibility, whether it is achieved through the

process of first-contact or it is achieved through multiple contacts between injected
CO2 and reservoir oil, is always described in terms of the thermodynamic state
of the system. The thermodynamics state of the system is recognized or identified
by the system’s pressure (either FC-MMP or MC-MMP [i.e., MMP]) at reservoir
temperature.
Even though a CO2 -reservoir oil system is a complex multicomponent mixture,
it can be simplified to a pseudo ternary system (Fig. 1.11), comprising CO2 and
two pseudo hydrocarbon components—namely light and intermediate hydrocarbons
and heavy hydrocarbons. As can be seen from Fig. 1.11, the composition of the
reservoir oil can be represented by a point on the line joining pseudo hydrocarbon
components of the ternary system. Depending on the thermodynamic conditions of
imposed pressure and reservoir temperature, CO2 and reservoir oil may form a two-
phase mixture, if resultant composition of CO2 -reservoir oil mixture is such that
it falls within the boundary of two-phase envelope. Outside of the two-phase area,
CO2 and reservoir oil can be mixed in any proportion without forming two phases,
which will represent the attainment of first-contact miscibility. In other words, if
the resultant composition of a CO2 -reservoir oil mixture is such that it falls outside
the two-phase envelope, first-contact miscibility between CO2 and reservoir oil will
occur.
The apex of the two-phase envelope, which is equivalent to the critical point found
in traditional thermodynamic phase behavior and is often referred as a plait point,
represents the situation where two phases (i.e., a CO2 -rich phase and an oil-rich
phase) cease to co-exist, and a critical mixture is formed. The system’s pressure that
corresponds to the achievement of the condition of plait point on a pseudo ternary

diagram (e.g., Fig. 1.11) is recognized as the upper critical solution pressure (UCSP)
or the FC-MMP.
From a thermodynamic point of view, at the plait point and beyond (i.e., away
from two-phase area), it is immaterial if the resulting critical mixture was achieved
through the extraction or vaporization of hydrocarbon components by CO2 (i.e.,
mixing followed along the dew point line) or CO2 -rich phase condensed into oil-
rich phase (i.e., mixing followed along the bubble point line) or a combined effect
(i.e., mixing was achieved through vaporizing/condensing mechanism) led to the
formation of a critical mixture. In other words, if the phase behavior of a given CO2 -
reservoir oil mixture, as a pseudo ternary system, is evaluated at a pressure equal to
or higher than UCSP (i.e., FC-MMP), no two-phase mixture will ever form. Hence,
CO2 and reservoir oil, irrespective of their mixing ratio, will be infinitely soluble
(i.e., completely miscible).
Thermodynamically, attaining first-contact miscibility does not depend on the
mixing ratio of CO2 and reservoir oil. However, in the pore space of reservoir rock
(i.e., pores), after making first ever contact with reservoir oil, both the freshly injected
CO2 and the newly formed CO2 -rich phase continue to move away from the injection
well and continue to contact both the fresh reservoir oil and oil-rich phase. These
multiple and repetitive contacts between varied combination of different phases (i.e.,
fresh CO2 , CO2 -rich phase, oil-rich phase, and fresh reservoir oil) along the path
of fluid movement (i.e., towards the production well from the injection well) may
lead to the development of miscibility at a lower pressure than UCSP or FC-MMP.
Hence, the development of miscibility through multiple contacts resulting from the
imposed constraints of fluid flow through porous reservoir rock and the phase behav-
ior (i.e., lowest operating pressure and reservoir temperature that results in miscible
displacement) is recognized by the MC-MMP (i.e., MMP).
During a miscible flood, injected CO2 and reservoir oil attain a critical mixture
composition through multiple contacts to reduce the residual oil saturation to zero
while moving downstream (injection well to production well). Hence, the MMP
signifies the thermodynamic condition of lowest operating pressure and reservoir
temperature at which CO2 and reservoir oil develop miscibility through multiple
contacts while achieving a local displacement efficiency of 100%. It is important
to recognize that it is the combination of flow and phase equilibrium that creates
the compositions that lead to high displacement efficiency (Orr and Jessen 2007).
The MMP itself is also considered a reservoir-specific parameter because crude oil
composition and the reservoir temperature greatly influence its value.
1.5 Other Considerations
It is well recognized that the achievement of miscibility between CO2 and reservoir
oil is critical for miscible CO2 -EOR as well as simultaneous CO2 -EOR and storage
projects. However, operating a miscible CO2 flood at a pressure equal or greater
than MMP may not necessarily result in maximized oil recovery. There may be
other factors and physical processes which may result in lower recoveries in the field
compared to the ones observed in laboratory settings.
For example, both viscous fingering and gravitational fingering (or segregation)
can seriously affect the sweep efficiency, thus resulting in low recoveries as found in
water alternating gas (WAG) projects involving CO2 injection in miscible mode (Rao
et al. 2004). Generally, traditional miscible gas (e.g., CO2 , hydrocarbon gas) EOR
projects are very sensitive to geological heterogeneity (Muggeridge et al. 2014), and
CO2 -EOR recovery factor generally shows a dependence to injected volume (Olea
2017). The precipitation of asphaltenes, even in low amounts, may hinder fluid flow
and significantly reduces the mobility of injected CO2 (Perera et al. 2016).
The role of the above-mentioned factors and physical processes in influencing
the performance of miscible CO2 flooding needs to be thoroughly examined while
planning, designing, and implementing EOR projects. Nevertheless, for a given CO2
and reservoir oil system, the determination of CO2 -reservoir oil miscibility in terms
of the MMP and the characterization of the drive mechanism(s) that are responsible
for the attainment of CO2 -reservoir oil miscibility serves as a guide to decide the
operating pressure at which an effective miscible displacement, and thus high oil
recovery, can be achieved.
References
Antonoff GN (1907) Sur La Tension Superficielle Des Solutions Dans La Zone Critique. J Chim
Phys 5:364–371
Ayirala SC, Rao DN (2006) Comparative evaluation of a new MMP determination technique. Soc
Pet Eng. https://doi.org/10.2118/99606-MS
Bruening IMRA (1991) Crude oil polarity measures quality, predicts behavior. Oil Gas J
89(31). http://www.ogj.com/articles/print/volume-89/issue-31/in-this-issue/refining/crude-oil-p
olarity-measures-quality-predicts-behavior.html. Accessed 31 Dec 2017
Burke J (1984) Solubility parameters: theory and application. In: The book and paper group annual
3. The American Institute for Conservation. https://cool.conservation-us.org/coolaic/sg/bpg/ann
ual/v03/bp03-04.html. Accessed 30 Dec 2017
Clark NJ, Shearin HM, Schultz WP et al (1958) Miscible drive—its theory and application. Soc Pet
Eng. https://doi.org/10.2118/1036-G
Fang T, Shi J, Sun X et al (2016) Supercritical CO2 selective extraction inducing wettability alter-
ation of oil reservoir. J Supercrit Fluids 113:10–15
Global CCS Institute (2011) Bridging the commercial gap for carbon capture and stor-
age. http://www.globalccsinstitute.com/publications/bridging-commercial-gap-carbon-capture-
and-storage. Accessed 25 Dec 2017
Holm LW, Josendal VA (1974) Mechanisms of oil displacement by carbon dioxide. Soc Pet Eng.
https://doi.org/10.2118/4736-PA
Imre A, Ramboz C, Kraska T et al (2015) Anomalous fluid properties of carbon dioxide in the
supercritical region—Application to geological CO2 storage and related hazards. Environ Earth
Sci Springer 73:4373–4384
Kaziunas A, Schlake R (2016) Why is CO2 a green solvent. ACS Green Chemistry
Institute. https://communities.acs.org/community/science/sustainability/green-chemistry-nexus-
blog/blog/2016/06/10/why-is-co2-a-green-solvent. Accessed 29 Dec 2017
Another random document with
no related content on Scribd:
Fig. 16.—Plan of the south-western palace at Nimroud; from Layard.
As to the buildings on the other sides of the court and the total
extent of the palace, we know very little; towards the west the walls
of several saloons have been recognized, but they have been left
half cleared. On the east, landslips have carried away part of the
buildings.[46]
Between the palace of Assurnazirpal and that of Esarhaddon
Layard found what seemed to him the remains of the second story of
some building, or at least of a new building erected over one of
earlier date (Fig. 17). Impelled, no doubt, by the rarity of the
circumstance, he gives a plan of these remains, and goes so far as
to express his belief that the arrangements shown in the plan were
repeated on the three other faces of a tower of which he
encountered the summit, still partly preserved.[47]
Although Calah was never abandoned, it fell, after the accession
of the Sargonids, from the first place among Assyrian cities; on the
other hand Sargon’s attempt to fix the seat of government in his own
town of Dour-Saryoukin does not seem to have met with permanent
success. From the eighth century to the end of the seventh the
Assyrian kings appear to have made Nineveh their favourite place of
residence.
The site of this famous city has been much discussed,[48] but at
last the question appears to be settled. Nineveh was built on the left
bank of the Tigris, opposite to the site occupied by modern Mossoul.
Two great mounds rising some five-and-thirty feet above the level of
the plain, represent the substructures upon which the royal homes of
the last Assyrian dynasty were raised; they are now famous as
Kouyundjik and Nebbi-Younas. Like the mound of Khorsabad these
two artificial hills were in juxtaposition with the city walls, which may
still be traced in almost their whole extent by the ridge of earth
formed of their materials (Fig. 18).
Fig. 17.—Upper chambers excavated at

Nimroud; from Layard.
The mound of Nebbi-Younas has so far remained almost
unexplored. It is fortified against the curiosity of Europeans by the
little building on its summit and the cemetery covering most of its
surface. The inhabitants of the country, Mussulman as well as
Christian, believe that Jonah lies under the chapel dome, and they
themselves hope to rest as near his body as possible. Some slight
excavations, little more than a few strokes of the pick-axe, have
been made in the scanty spots where no graves occur, but enough
evidence has been found to justify us in assuming that Nebbi-
Younas also hides its palaces. They too will have their turn. Thanks
to the prestige of the prophet they are reserved for excavations to be
conducted perhaps in a more systematic fashion than those hitherto
undertaken on the site of Nineveh.
Fig. 18.—Map of the site of Nineveh; from Oppert.

Fig. 19.—Plan of the mound of Kouyundjik; from Rassam’s Transactions.
At Kouyundjik, on the other hand, no serious obstacle was
encountered. The village transported itself to the plain; it was not
necessary to persuade the inhabitants to quit it, as it had been at
Khorsabad. When Botta, who had begun certain inquisitions at this
spot, abandoned his attempts, the English explorers were left free to
sound the flanks of the artificial hill at their leisure, and to choose
their point of attack. If they had gone to work in the same fashion as
Botta and Place, they might have laid bare palaces excelling that of
Sargon in the scale and variety of their arrangements. Of this we
may judge from Mr. Rassam’s plan (Fig. 19). But after the departure
of Mr. Layard the excavations, frequently interrupted and then
recommenced after long intervals, aimed only at discovering such
objects as might figure in a museum. A trench was opened here and
another there, on the inspiration of the moment. The explorers often
neglected to measure the buildings in which they were at work, so
that we have only partial plans of the two principal buildings of
Nineveh, those palaces of Sennacherib and Assurbanipal from which
so many beautiful monuments have been taken to enrich the British
Museum.
Fig. 20.—Part plan of the palace of Sennacherib; from Layard.

The mound of Kouyundjik in its present state is an irregular
pentagon. Its circumference is rather more than a mile and a half.
The palace of Sennacherib occupies the south-western corner, and
forms a rectangle about 600 feet long by 330 wide. The two chief
entrances were turned one towards the river, or south-west, the
other towards the town, or north-east. The latter entrance was
flanked by ten winged bulls. The four central ones stood out beyond
the line of the façade, and were separated from each other by
colossal genii.[49] About sixteen halls and chambers have been
counted round the three courtyards. As at Khorsabad, some of these
are long galleries, others rooms almost square. The fragmentary
plan shown in our Fig. 20 brings out the resemblance very strongly. It
represents a part of the building explored in Layard’s first campaign.
In the rooms marked 2, 3, and 4, small niches cut in the thickness of
the walls may be noticed. They are not unlike the spaces left for
cupboards in the modern Turkish houses of Asia Minor. The hall
marked 1 in the plan is about 124 feet long and 30 wide. In another
part of the palace a saloon larger than any of those at Khorsabad
has been cleared. It measures 176 feet long by 40 wide. The
average size of the rooms here is about one-third more than in the
palace of Sargon, suggesting that the art of building vaults and
timber ceilings made sensible progress during the reign of that king.
As in the case of the Khorsabad palace, the explorers believed they
could distinguish between the seraglio and the harem; but the plan
given by Layard has too many blanks and leaves too many points
uncertain for the various quarters to be distinguished with such ease
and certainty as at Khorsabad.[50] The walls were everywhere
covered with rich series of reliefs, from which we have already taken
some of our illustrations (Vol. I., Figs. 151 and 152), and shall have
to take more. The military promenade figured upon page 49 will give
a good idea of their general character (Fig. 21).
Assurbanipal, the grandson of Sennacherib, built his palace
towards the north of the mound. The excavations of Mr. Rassam
have been the means of recovering many precious bas-reliefs from
it, but we may see from the plan (Fig. 19) that a very small part of the
building has been cleared. Much more must remain of a palace so
richly decorated and with rooms so large as some of those explored
in the quarter we have called the sélamlik. One of these saloons is
145 feet long and 29 wide. The plan of its walls suggests a very
large building, with spacious courts and a great number of rooms.[51]
Fig. 21.—Sennacherib at the head of his army. Height 38 inches. British Museum.
Drawn by Saint-Elme Gautier.
In many other mounds of Assyria, such as those of Arvil,[52] of

Balawat,[53] of Kaleh-Shergat,[54] of Karamles,[55] and in the valley
of the Khabour,[56] the explorers have encountered the remains of
buildings and of ornamental figures that must have formed parts of
royal palaces, or at least of the dwellings of great nobles. We shall
not stop to notice all these discoveries. None of the mounds in
question have been explored with sufficient care and completeness
to add anything of importance to what we have learnt by our study of
Khorsabad. The chief thing to be gathered from these widely
scattered excavations is that during the great years of Assyria there
was no town of any importance in which the king did not possess a
habitation, arranged and decorated in the same spirit as the great
palaces at Calah and Nineveh, and differing from these chiefly in the
size of their courts and chambers.
No doubt the pavilions sprinkled about the park, or paradise, as
the Greek writers called it, in which the king sought amusement by
exercising his skill as an archer upon the beasts that roamed among
its trees, were ornamented in the same fashion, although in all
probability, wood and metal played a more important part in their
construction. As for the dwellings of the great officers of the crown
and of vassal princes, they must have reproduced on a smaller scale
the plan and ornamentation of the royal palace.
Of the house properly speaking, the dwelling of the artizan or
peasant, whether in Assyria or Chaldæa, we know very little. We are
unable to turn for its restoration to paintings such as those in the
Egyptian tombs, which portray the life of the poor with the same
detail as that of the rich or even of the monarch himself. The
Assyrian bas-reliefs, in which the sieges of towns are often
represented, always show them from the outside (Fig. 22), nothing is
to be seen but the ramparts and the towers that flank them. The only
bas-relief in which we can venture to recognize one of the ordinary
houses of the country belongs to the series of pictures in which
Sennacherib has caused the transport of the materials and colossal
bulls for his own palace to be figured. We there see two very
different types of edifice, one covered with hemispherical or elliptical
domes, the other with flat roofs supporting a kind of belvedere[57]
(Vol. I., Fig. 43).
This latter type may be found several times repeated in a relief
representing a city of Susiana (Vol. I., Fig. 157). Here nearly every
house has a tower at one end of its flat roof. Was this a defence, like
the towers in the old Italian towns and in the Greek villages of Crete
and Magnesia? We do not think so. The social conditions were very
different from those of the turbulent republics of Italy, where the
populace was divided into hostile factions, or of those mountainous
districts whose Greek inhabitants live in constant fear of attack from
the Turks who dwell in the plains. The all-powerful despots of Assyria
would allow no intestine quarrels, and for the repulse of a foreign
enemy, the cities relied upon their high and solid lines of
circumvallation. We think that the towers upon the roofs were true
belvederes, contrivances to get more air and a wider view; also,
perhaps, to allow the inhabitants to escape the mosquitoes by rising
well above the highest level reached by the flight of those tiny pests.
It was, then, between these two types, as Strabo tells us, that the
civil buildings of Mesopotamia were divided. They all had thick
terraced roofs but some were domical and others flat.[58] At Mugheir
Mr. Taylor cleared the remains of a small house planned on the lines
of an irregular cross; it was built of burnt brick and paved with the
same material. In the interior the faces of the bricks were covered
with a thin and not very adhesive glaze. Two of the doors were
round-headed; the arches being composed of bricks specially
moulded in the shape of voussoirs; but the numerous fragments of
carbonized palm-wood beams which were found upon the floors of
each room, showed that the building had been covered with a flat
timber roof and a thick bed of earth. Strabo justly observes that the
earth was necessary to protect the inmates of the house against the
heats of summer. As a rule houses must have been very low. It was
only in large towns such as Babylon, that they had three or four
stories.[59]
We need say no more. We have studied the palace in detail, and

the palace was only an enlarged, a more richly illustrated edition of
the house. It supplied the same wants, but on a wider scale than was
necessary in the dwelling of a private individual. To complete our
study of civil architecture it is only necessary to give some idea of
the fashion in which palaces and houses were grouped into cities,
and of the means chosen for securing those cities against hostile
assault.
§ 4. Towns and their Defences.
Of all barbarian cities, as the Greeks would say, Babylon has

been the most famous, both in the ancient and the modern world;
her name has stirred the imaginations of mankind more strongly than
any other city of Asia. For the Greeks she was the Asiatic city par
excellence, the eternal capital of those great oriental empires that
were admired and feared by the Hellenic population even after their
political weakness had been proved more than once. In the centuries
that have passed since the fall of the Greek civilization the name and
fame of Babylon have been kept alive by the passionate words of
those Hebrew prophets who filled some of the most eloquent and
poetic books of the Old Testament with their hatred of the
Mesopotamian city, an ardent hate that has found an echo across
the ages in the religion which is the heir of Judaism.
Fig. 22.—Town besieged by Sennacherib. Height 86 inches. British
Museum.
Drawn by Saint-Elme Gautier.
There is, then, no city of the ancient world in which both our
Christian instincts and our classic education would lead us to take a
deeper interest, or to make more patient endeavours towards the
recovery of some knowledge of its passed magnificence by the
interrogation of its site and ruins, than this town of Babylon. At the
same time it happens, by a strange series of chances, that of all the
great cities of the past Babylon is the least known and the most
closely wrapped in mystery. The descriptive passages of ancient
writers are full of gaps and exaggerations, while as for the
monuments themselves, although the size of their remains and the
vast extent of ground they cover allow us to guess at the power and
energy of the people to whom they owed their existence, there are
no ruins in the world from which so little of the real thoughts and
ideas of their constructors is to be learnt. Not only has the
ornamentation of palace and temple disappeared, the ruling lines
and arrangements of their plans are no longer to be traced. It is this
no doubt that has discouraged the explorers. While the sites of
Calah, Nineveh, and Dour-Saryoukin have been freed of millions of
cubic yards of earth, and their concealed buildings explored and laid
bare in every direction, no serious excavations have ever been made
at Babylon. At long intervals of time a few shafts have been sunk in
the flanks of the Kasr, of Babil and the Birs-Nimroud, but they have
never been pushed to any great depth; a few trenches have been
run from them, but on no connected system, and only to be soon
abandoned. The plain is broken by many virgin mounds into which
no pick-axe has been driven, and yet they each represent a structure
dating from some period of Babylonian greatness. It would be a
noble undertaking to thoroughly explore the three or four great ruins
that rise on the site itself, and to examine carefully all the region
about them. Such an exploration would require no slight expenditure
of time and money, but it could not fail to add considerably to our
present knowledge of ancient Chaldæa; it would do honour to any
government that should support it, and still more to the archæologist
who should conduct the inquiry to completion, laying down on his
plan the smallest vestige remaining of any ancient detail, and
allowing himself to be discouraged by none of the numerous
disappointments and deceptions that he would be sure to encounter.
Meanwhile it would be profitless to carry our readers into any
discussion upon the topography of Babylon. In the absence of
ascertained facts nothing could be more arbitrary and conjectural
than the various theories that have been put forward as to the
direction of the city walls and their extent. According to George
Smith the only line of wall that can now be followed would give a
town about eight English miles round. Now Diodorus says that what
he calls the Royal City was sixty stades, or within a few yards of
seven miles, in circumference.[60] The difference between the two
figures is very slight. “In shape the city appears to have been a
square with one corner cut off, and the corners of the walls of the city
may be said roughly to front the cardinal points. At the north of the
city stood the temple of Belus, now represented by the mound of
Babil; about the middle of the temple stood the royal palace and
hanging-gardens.”[61]
The Royal City was the city properly speaking, the old city whose
buildings were set closely about the great temple and the palace, the
latter forming, like the Old Seraglio at Constantinople, a fortified town
in itself with a wall some twenty stades (4043 yards) in
circumference. A second wall, measuring forty stades in total length,
turned the palace and the part of the city in its immediate
neighbourhood into a sort of acropolis. Perhaps the nobles and
priests may have inhabited this part of the town, the common people
being relegated to the third circle. In the towns of Asia Minor at the
present day the Turks alone live in the fortified inclosures, which are
called kaleh, or citadels, the rest of the town being occupied by the
rayahs of every kind, whether Greek or Armenian.
There is, then, nothing in the description of Diodorus at which we
need feel surprise. Our difficulty begins when we have to form a
judgment upon the assertion of Herodotus, who speaks of an
inclosure 120 stades (13 miles 1385 yards) square.[62] According to
this the circumference of Babylon must have been nearly 55¼
English miles, which would make it considerably larger than what is
called Greater London, and more than three times the size of Paris.
Here, strangely enough, Ctesias gives a more moderate figure than
Herodotus, as we find Diodorus estimating the circumference of the
great enceinte at 360 stades (41 miles 600 yards).[63]
We can hardly read of such measurements without some
astonishment. It seems difficult, however, to doubt the formal
statement of such a careful eye-witness as Herodotus. Although the
Greek historian was quite ready to repeat the fantastic tales he
heard in the distant countries to which his travels led him—a habit
we are far from wishing to blame—modern criticism has never
succeeded in convicting him of falsehood or exasperation in matters
of which he could judge with his own eyes. Our surprise at his
figures is diminished when we remember with what prodigious
rapidity buildings of sun-dried bricks could be erected. The material
was at hand in any possible quantity; the erection of such a length of
wall was only a question of hands. Now if we suppose, with M.
Oppert, that the work was undertaken by Nebuchadnezzar after the
fall of Nineveh, that prince may very well have employed whole
nations upon it, driving them into the workshops as the captive Jews
were driven. In such a fashion the great wall that united into one city
towns which had been previously separated—such as the original
Babylon, Cutha, and Borsippa—might have been raised without any
great difficulty. It is certain that the population of such a vast extent
of country cannot have been equally dense at all points. A large part
must have been occupied by royal parks, by gardens, vineyards, and
even cultivated fields. Babylon must, in fact, have been rather a vast
intrenched camp than a city in the true sense of the word.
At the time when Herodotus and Ctesias visited Babylon, this wall
—which was dismantled by the Persians in order to render revolt
more difficult—must have been almost everywhere in a state of ruin,
but enough of it remained to attract curious travellers, just as the
picturesque fortifications of the Greek emperors are one of the sights
of modern Constantinople. The more intelligent among them, such
as Herodotus, took note of the measurements given to them as
representing the original state of the great work whose ruins lay
before their eyes and confirmed the statements of their guides.[64]
The quarter then still inhabited was the Royal City, the true Babylon,
whose great public works have left such formidable traces even to
the present day. Naturally no vestige of the tunnel under the
Euphrates has been found; we may even be tempted to doubt that it
ever existed.[65] But we cannot doubt that the two sections of the
town were put in communication one with another by a stone bridge;
the evidence on that point is too clear to admit of question.[66] The
descriptions of the structure give us a high idea of the engineering
skill of the Chaldæans. To build such a bridge and insure its stability
was no small undertaking. The river at this point is about 600 feet
wide, and from twelve to sixteen deep at its deepest part.[67] We
need hardly say that for many centuries there has been no bridge
over the Euphrates either in the neighbourhood of Babylon or at any
other point in Mesopotamia. As for the quays, Fresnel found some
parts in very good preservation in 1853.[68] At the point where this
discovery was made the quay was built of very hard and very red
bricks, completely covered with bitumen so as to resist the action of
the water for as long as possible. The bricks bore the name of
Nabounid, who must have continued the work begun by
Nebuchadnezzar.
The description given by Herodotus of the way in which Babylon
was built and the circulation of its inhabitants provided for must also
be taken as applying to the Royal City. “The houses are mostly three
and four stories high; the streets all run in straight lines, not only
those parallel to the river, but also the cross-streets which lead to the
waterside. At the river end of these cross-streets are low gates in the
fence that skirts the stream, which are, like the great gates in the
outer wall, of brass and open on the water.”[69]
We may perhaps form some idea of Babylon from the
appearance of certain parts of Cairo. Herodotus seems to have been
struck by the regularity of the plan, the length of the streets, and the
height of the houses. In these particulars it was very different from
the low and irregularly built Greek cities of the fifth century b.c. The
height of the houses is to be explained partly by the necessity for
accommodating a very dense population, partly by the desire for as
much shade as possible.[70]
The decadence of Babylon had begun when Herodotus visited it
towards the middle of the fifth century before our era;[71] but the
town was still standing, and some of the colossal works of its later
kings were still intact. The last dynasty had come to an end less than
a century before. We are ready, therefore, to believe the simple and
straightforward description he has left us, even in those particulars
which are so well calculated to cause surprise. The evidence of
Ctesias, who saw Babylon some half century later, seems here and
there to be tainted with exaggeration, but on the whole it agrees with
that of Herodotus. Supposing that he does expand his figures a little,
Ctesias is yet describing buildings whose ruins, at least, he saw with
his own eyes, and sometimes his statements are borne out by those
of Alexander’s historians.[72]
The case of Nineveh is very different. Of that city Herodotus
hardly knew more than the name; he contents himself with mere
passing allusions to it.[73] Ctesias is trammelled by fewer scruples.
When he wrote his history Nineveh had ceased to exist for more
than two centuries; the statements of Xenophon[74] prove that at the
time of the famous retreat its site was practically deserted and its
name almost forgotten in the very district in which its ruins stood. But
the undaunted Ctesias gives us a description of the Assyrian capital
as circumstantial as if he had lived there in the days of Sennacherib
or Assurbanipal. According to his account it formed an elongated
rectangle, the long sides being 150 stades (17 miles 380 yards), and
the shorter 90 stades (10 miles 595 yards), in length, so that the total
circumference was 480 stades (55 miles 240 yards).[75] The whole of
this space was inclosed by a wall 100 Greek feet (103 feet English)
high, and with towers of twice that height.
It is hardly necessary to show that all this is pure invention. To
find room for such a Nineveh we should have to take all the space
between the ruins opposite Mossoul and those of Nimroud. But all
the Assyrian texts that refer to Nineveh and Calah speak of them as
two distinct cities, each with an independent life and period of
supremacy of its own, while between the two sites there are no
traces of a great urban population. The 1,500 towers on the walls
were the offspring of the same brain that imagined the tower of
Ninus nine stades (5458 feet) high. We can scent an arbitrary
assertion in the proportion of two to one given to the heights of the
towers over that of the wall. In the fortified walls of the bas-reliefs the
curtain is never greatly excelled in height by its flanking towers (see
Vol. I. Figs. 51, 60, 76, and 158, and above, Fig. 23).
Fig. 23.—Siege of a city; from Layard.

Ctesias has simply provided in his Nineveh a good pendant to
Babylon. Being quite free to exercise his imagination, he has laid
down even a greater circumference than that of the city on the
Euphrates. The superiority thus ascribed to the northern city is
enough by itself to arouse our suspicions. We cannot point to any
particular text, but contemporary history as a whole suggests that
Babylon was more populous than Nineveh, just as Bagdad is now
more populous than Mossoul. Nineveh, and Calah before it, were the
capitals of a soldier nation, they were cities born, like Dour-
Saryoukin, of the will of man. Political events called them into life,
and other political events caused them to vanish off the face of the
earth. Babylon, on the other hand, was born of natural conditions;
she was one of the eternal cities of the world. The Turks do their best
to make Hither Asia a desert, but so long as they do not entirely
succeed, so long as some light of culture and commerce still flickers
in the country, it will burn in that part of Mesopotamia which is now
called El-Jezireh (the island), where the two streams are close
together, and canals cut from one to the other can bring all the
intermediate tract into cultivation.
Sennacherib speaks thus of his capital: “Nineveh, the supreme
city, the city beloved of Istar, in which the temples of the gods and
goddesses are to be found.”[76] With its kings and their military
guards and courts, with the priests that served the sanctuaries of the
gods, with the countless workmen who built the great buildings,
Nineveh must have been a fine and flourishing city in the days of the
Sargonids; but even then its population cannot have equalled that of
Babylon under Nebuchadnezzar. The latter was something more
than a seat of royalty and a military post; it was the great entrepôt for
all the commerce of Western Asia.[77]
All the travellers who have visited the neighbourhood of Mossoul
are agreed that, on the left bank of the Tigris, there is no trace of any
wall but that which forms a rather irregular parallelogram and
embraces the two mounds of Nebbi-Yonnas and Kouyundjik (Fig.
18).[78] According to M. Oppert this wall was about ten thousand
metres (nearly 6¼ miles) in circumference, which would make it
cover about one-eleventh of the ground covered by modern Paris.
There is nothing here that is not in accord with our ideas as to the
character and importance of Nineveh. If we add to the town inclosed
within such a wall suburbs stretching along the right bank of the river
on the site of modern Mossoul, we shall have a city capable of
holding perhaps two or three hundred thousand people.
In the northern part of the inclosure, not far from the north-
western angle, Sir Henry Layard made some excavations that
brought one of the principal gates of ancient Nineveh to light.[79] The
passage was probably vaulted, but its upper part had disappeared.
The gateway, which was built by Sennacherib, had a pair of winged
bulls looking towards the city and another pair looking towards the
country outside. The limestone pavement in the entrance still bears
the mark of wheels. Two great chambers are hollowed out of the
thickness of the walls and open into the entrance passage. The walls
must be here about 116 feet thick, judging from the proportion, in
Layard’s plan,[80] between them and one of the two chambers, which
has a diameter, as we are told by its finder, of 23 feet. We need say
no more of this doorway. The town attached to the palace of
Khorsabad will give us a better opportunity for the study of a city
gate.
The “town of Sargon,” Dour-Saryoukin or Hisr-Sargon, according
as we follow one or the other method of transcribing the Assyrian
name, was far smaller than Babylon, was smaller even than
Nineveh. It formed a parallelogram two sides of which were about
1,950 yards, the other two about 1,870 yards long, which would give
a surface of considerably more than a square mile. This city is
interesting not for the part it played in history, for of that we know
nothing, and it is quite possible that after the death of Sargon it may
have been practically abandoned, but because, of all the cities of
Assyria, it is that whose line of circumvallation has been best
preserved and most carefully studied (Vol. I. Fig. 144).
Like all inhabited places of any importance Dour-Saryoukin was
carefully fortified. Over the whole of Mesopotamia the words town
and fortress seem to have been almost convertible terms. The
nature of the soil does not lend itself to any such distinctions as
those of upper and lower city, as it does in Italy and Greece; there
was no acropolis, to which the inhabitants could fly when the outer
defences were broken down. In case of great need the royal palace
with its massive gates and cincture of commanding towers might be
looked upon as a citadel; while in Babylon and some other towns
several concentric lines of fortification made an attack more arduous
and prolonged the defence. But, nevertheless, the chief care of the
Mesopotamian engineers was given to the strengthening of the
external wall, the enceinte, properly speaking.
At Khorsabad this stood on a plinth three feet eight inches high,
above which began the sun-dried brick. The whole is even now
nowhere less than forty-five feet high, while in parts it reaches a
height of sixty feet. If we remember how greatly walls built of the
materials here used must have suffered from the weather, we shall
no longer be astonished at the height ascribed by Herodotus to the
walls of Babylon: “These were, he says, 200 royal cubits (348 feet)
high.”[81] This height was measured, no doubt, from the summit of
the tallest towers into the deepest part of the ditch, which he adds,
“was wide and deep.” It is possible that the interpreters who did the
honours of Babylon to the Greek historian exaggerated the figures a
little, just as those of Memphis added something to the height of the
pyramids. That the exaggeration was not very great is suggested by
what he says as to the thickness of the wall; he puts it at fifty royal
cubits, or eighty-six feet six inches. Now those of Khorsabad are only
between six and seven feet thinner than this, and it is certain that the
walls of Babylon, admired by all antiquity as the masterpieces of the
Chaldæan engineers, must have surpassed those of the city
improvised by Sargon both in height and thickness.
Far from abusing our credulity, Herodotus is within the mark
when he says that on the summit of the wall “enough room was left
between the towers to turn a four-horse chariot.”[82] As for Ctesias,
he speaks of a width “greater than what is necessary to allow two
chariots to pass each other.”[83] Such thicknesses were so far
beyond the ideas of Greek builders that their historians seem to have
been afraid that if they told the truth they would not be believed, so
they attenuated rather than exaggerated the real dimensions. If we
give a chariot a clear space of ten feet, which is liberal indeed, it will
be seen that not two, but six or seven, could proceed abreast on
such walls.
The nature of the materials did not allow walls to be thin, and in
making them very thick there were several great advantages. The
Assyrians understood the use of the battering-ram. We see it
employed in several of the bas-reliefs for opening a breach in the
ramparts of a beleaguered town (Vol. I. Fig. 60 and above, Fig. 23).
They also dug mines, as soon as they had pierced the revetment of
stone or burnt brick.[84] To prevent or to neutralize the employment
of such methods of attack they found no contrivance more effectual
than giving enormous solidity to their walls. Against such masses the
battering-ram would be almost powerless, and mines would take so
much time that they would not be very much better. Finally, the
platform at the summit of a wall built on such principles would afford
room for a number of defenders that would amount to a large army.
Throughout the circumference of the enceinte the curtain was
strengthened by rectangular flanking towers having a front of forty-

Textbook Co2 Reservoir Oil Miscibility Dayanand Saini Ebook All Chapter PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Textbook Co2 Reservoir Oil Miscibility Dayanand Saini Ebook All Chapter PDF

Uploaded by

Copyright:

Available Formats

CO2-Reservoir Oil Miscibility Dayanand

Engineering Aspects of Geologic CO2 Storage Synergy

Integrated Reservoir Studies for CO2 Enhanced Oil

Machine Learning in the Oil and Gas Industry :

An Introduction to Reservoir Simulation Using MATLAB

Principles of Applied Reservoir Simulation John R.

Reservoir modelling: a practical guide First Edition

Offshore Processing of CO2 Rich Natural Gas with

Cooking with Olive Oil: Simply Delicious Olive Oil

• Petroleum Geology & Geophysics

Contributions to the series can be made by submitting a proposal to the responsible

More information about this series at http://www.springer.com/series/15391

ISSN 2509-3126 ISSN 2509-3134 (electronic)

Printed on acid-free paper

A reliable knowledge of the minimum miscibility pressure (MMP) of carbon

Bakersﬁeld, USA Dayanand Saini

1 Fundamentals of CO2 -Reservoir Oil Miscibility . . . . . . . . . . . . . . . . 1

3.4 The Experimental Vanishing Interfacial Tension (VIT)

5.5.4 PC-SAFT EOS Model . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

PREOS Peng–Robinson Equation of State

Abstract The efficient and coeffective implementation and operation of CO2

© The Author(s), under exclusive licence to Springer International Publishing AG, 1

1.3 Solvent Properties of Supercritical CO2

of state explicit in the Helmholtz energy, which is a function of two independent

1.4 Attainment of Miscibility Between Injected CO2

Injection well Near critical Production well

development of miscibility in CO2 -reservoir oil mixtures. This process or mecha-

1.4.1 Molecular Dynamics-Based Approach

Injection well Near critical Production well

Injection well Near critical region

Pure CO2 CO2 Non-contacted

1.4.2 Interfacial Energy-Based Approach

To further understand the delicate interplay of the phenomena of mutual diffusivity

1.4.3 Thermodynamics-Based Approach

Nevertheless, CO2 -reservoir oil miscibility, whether it is achieved through the

corresponds to the achievement of the condition of plait point on a pseudo ternary

1.5 Other Considerations

Fig. 17.—Upper chambers excavated at

Fig. 18.—Map of the site of Nineveh; from Oppert.

Fig. 20.—Part plan of the palace of Sennacherib; from Layard.

In many other mounds of Assyria, such as those of Arvil,[52] of

We need say no more. We have studied the palace in detail, and

§ 4. Towns and their Defences.

Of all barbarian cities, as the Greeks would say, Babylon has

Fig. 23.—Siege of a city; from Layard.

You might also like