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COURSE CODE: PENG 6023

COURSE TITLE: Research Methods

LECTURER: Dr. Raffie Hosein

STUDENT ID: 807007199

NAME: ANDREW GRANT

Supervisors: Dr. Hosein

Dr. Sobers

Title: Simultaneous design of CO2 geo-sequestration and enhance heavy oil recovery

Cover page
Abstract

This paper seeks to research current mechanisms that were involved in subsurface storage of
carbon dioxide and miscible enhance heavy oil recovery. Since carbon dioxide was an increasing
concern because of its green house gases effect, proper greenhouse reducing technologies were
captured and were explored in this paper. To this effect, key molecular parameters were
investigated. Such as, capillary trapping, frontal advance, snap-off as well as vertical permeability
of seals and residual carbon dioxide saturation. Furthermore, this article seeks to highlight the
various numerical simulated models and equation of state (EOS) that goes into designing a
simultaneous technique for recycling carbon dioxide with the aim of enhancing the production of
heavy oils. As conventional, hydrocarbons dwindled over the years, techniques of producing
heavy oil while reducing its operational carbon footprint has become of paramount importance.
Results from various empirical studies of this review would show, the volumes of carbon dioxide
deposited within the subsurface, the amount of incremental heavy oil recovery experienced and
the techniques involved to simultaneously achieve both. Such techniques were WAG injection
strategies, water over gas injection strategies, secondary CO2 flooding as well as tertiary CO2
flooding. Results would provide insights as to why water over gas injection had 50% more carbon
dioxide storage than the water alternating gas technique. As well as why secondary miscible CO2
flooding showed 29.1% increase in oil recovery as to oppose to 26% when tertiary CO2 flooding
was used.

Introduction

Capture and geological storage of CO2 provide a way to avoid emitting CO2 into the atmosphere,
by capturing CO2 from major stationary sources. Carbon dioxide is an important greenhouse gas
and the most obvious impact of CO2 release is global warming. However, CO2 is also
physiologically active in plants and animals, it is of great importance to ecological systems and it
is an acid that critically affects the chemistry of ocean water. The subsurface is the Earth’s largest
carbon reservoir, where the vast majority of the world’s carbon is held in coals, oil, gas organic-
rich shales and carbonate rocks. Geological storage of CO2 has been a natural process in the
Earth’s upper crust for hundreds of millions of years. In order to curb the greenhouse gas effect
that is pervasive worldwide, carbon dioxide geo-sequestration is currently been used as a
geoengineering solution to the endemic problem. This paper serves to explore and conceptualize
the simultaneous recycle and geologic storage of CO2 to enhance heavy oil recovery.
Literature Review
Heavy Oil Overview
According to Guo et al., (2016), natural bitumen (often called tar sands or oil sands) and heavy oil
differ from light oils by their high viscosity (resistance to flow) at reservoir temperatures, high
density (low API gravity), and significant contents of nitrogen, oxygen, and sulfur compounds
and heavy-metal contaminants. They resemble the residuum from the refining of light oil. Most
heavy oil is found at the margins of geologic basins and is thought to be the residue of formerly
light oil that has lost its light-molecular-weight components through degradation by bacteria,
water washing, and evaporation. The estimated volume of technically recoverable heavy oil (434
billion barrels) and natural bitumen (651 billion barrels) in known accumulations is about equal to
the Earth's remaining conventional (light) oil reserves (Meyer and Attanasi 2016).
Table 1 showing API gravity and viscosity of light, heavy and extra-heavy oils (Guo, Li and Yu
2016)
API gravity (0) Viscosity (cP) Density (kg/m 3)
Light oil >22 <100 <934
Heavy oil 10-22 >100 943-1000
Extra-heavy oil (bitumen) <10 >10,000 >1000

Meyer and Attanasi (2016) reported that the largest extra-heavy oil accumulation is the
Venezuelan Orinoco heavy-oil belt, which contains 90 percent of the world's extra-heavy oil
when measured on an in-place basis. Eighty-one percent of the world's known recoverable
bitumen is in the Alberta, Canada; together the two deposits contain about 3,600 billion barrels of
oil in place. Similar to Venezuela, Trinidad has oil and gas and tar sands resources. Hosein et al.,
(2010) reported that the majority of Trinidad’s oil is categorized as heavy oil of viscosity greater
than 100 cp. Approximately one and a half billion barrels are trapped in reservoirs in the
southwestern part of the island and 3.6 billion barrels offshore the west coast. Additionally, heavy
oil, tar sands deposits are located in the south west on land at depths of less than 500 feet and
contains about three billion barrels of oil (Hosein, Bertrand and Dawe 2010).

Enhance Oil Recovery Overview


Precendently, oil recovery processes were classified as primary, secondary and EOR process.
Primary recovery ensues the use of natural energy present in a reservoir as the main source of
energy for the displacement of oil to producing wells. These natural energy sources are solution
gas drive, gas-cap drive, natural waterdrive, fluid and rock expansion and gravity drainage.
Secondary recovery results from the augmentation of natural energy through injection of water or
gas to displace oil toward producing wells. However, enhance oil recovery results principally
from the injection of gases or liquid chemicals and / or the use of thermal energy. Hydrocarbon
gases, CO2 , nitrogen, and flue gases are among the EOR processes (Green and Willhite 1998).

Geologic sequestration
Geologic Sequestration (GS) is the process of injecting carbon dioxide (CO2), captured from an
industrial (e.g., steel and cement production) or energy-related source (e.g., a power plant or
natural gas processing facility), into deep subsurface rock formations for long-term storage. This
is part of a process frequently referred to as “carbon capture and storage” or CCS (United States
Environmental Protection Agency 2017).
The United States Environmental Protection Agency (2017), has considered the possibility that
99% or more of the injected CO2 will be retained for 1000 years. Depleted oil and gas reservoirs,
possibly coal formations and particularly saline formations (deep underground porous reservoir
rocks saturated with brackish water or brine), can be used for storage of CO2. At depths below
about 800–1000 m, supercritical CO2 has a liquid-like density that provides the potential for
efficient utilization of underground storage space in the pores of sedimentary rocks
(Intergovernmental Panel on Climate Change 2005).

Capillary trapping mechanisms for CO2 storage – from pore scale to field scale implications
Theory
The trapping of CO2 by capillary forces in the pore space of rocks is a key process for
maximizing capacity and ensuring the integrity of CO2 sequestration at industrial scales. When
CO2 is injected into a deep subsurface geologic formation it will displace the resident fluid,
usually brine and in other cases hydrocarbons and migrate in response to buoyancy and pressure
gradients. As the reservoir brine imbibes back into the pore space pursuant to the migrating
carbon dioxide plume, small isolated pockets of CO2 will be trapped by capillary forces: this is
known as capillary or residual trapping (Krevor, et al. 2015).
However, because the trapping is pervasive over hundreds of meters to hundreds of kilometers of
the plume extents, it plays a major role in plume migration, immobilization, and storage capacity
and ultimately the capacity to store injected CO2 safely (Krevor, et al. 2015). To this end,
observations underlying the treatment of capillary trapping as a continuum property of rock-fluid
system have been gathered from experimental techniques.
Pore scale physics
In order to visualize fluid displacement inside the pore space of a rock at the micron level, the use
of imaging and microfluidics technology were employed. The framework of CO2 storage was first
elucidated by Silin et al. (2011)Iglauer et al (2011) and Andrew et al. (2013, 2014b) they used an
X-ray transparent carbon fibre core holder to maintain high temperatures (50- 70 0) and pressures
within the vicinity of 10 MPa in fluids, which are indicative of reservoir storage acquifers.
The premise of rock core analysis for reservoir characterization and flow modeling, were
developed from empirical and analytical concepts of rock physics, namely, piston-like advance
and snap-off and wetting layers. As a result, a universal definition of residual saturation of a non-
wetting fluid as a function of saturation with increasingly negative capillary pressure (Anderson,
1987; Morrow, 1990) was demonstrated for water-wet and mixed-wet CO2-brine systems (see
figure 1 in results section).
The initial-residual characteristic curve
The initial – residual characteristic curve (IR curve) showed the association between initial and
residual non-wetting saturations, which was initially developed by Land (1968). This empirical
𝑆𝑐𝑜2,𝑖
model suggested by Land (1968) was given by 𝑆𝑐𝑜2,𝑟 = 1+𝐶𝑆𝑐𝑜2,𝑖 ………..(1)
Where CO2 saturation, SCO2, was scaled by the irreducible water saturation, Sw,irr, to obtain the
normalized CO2 saturation, SCO2 = 𝑆𝑐𝑜2,𝑟 /(1 − 𝑆𝑤,𝑖𝑟𝑟 ). Consequently, IR curves were derived for
following values of the constant C: 0.2, 1, and 5 (See figure 2 in results section).
Residual trapping and hysteresis in multiphase flow
Models of hysteresis comprised of: relationship between relative permeability of the non-wetting
phase and coupled with its flowing saturation. The relationship between the capillary pressure and
the connected or flowing non-wetting phase saturation; a model for the connected saturation
asymptotic of saturation history and a model that associated the disconnected residual saturation
of the non-wetting phase to the maximum saturation obtained prior to imbibition. The above
empirical models suggested by Land (1968), Kumar et al. (2005) and Qi et al. (2009) were given
as follows:
Imbibition relative permeability to CO2, Kir,CO2,(SCO2), at a given saturation, SCO2, was equivalent
to the drainage relative permeability function, kdr,CO2 evaluated at the connected saturation,
kirco2(Sco2)=kdr,co2(Sco2,C)………………(2)
When this expression was added to water-wet capillary pressure hysteresis, where pic(Sco2), the
imbibition capillary pressure at a given saturation was set as equivalent to the drainage capillary
pressure function, pdrc(SCO2), evaluated at the connected phase saturation, 𝑝𝑐𝑖 (𝑆𝑐𝑜2 ) =
𝑑𝑟
𝑝 𝑐 (𝑆𝑐𝑜2 ) 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 … . (3). This model assumed that the residual was achieved at a Pc = 0 and
was not applicable to mixed-wet systems. The connected saturation could be obtained from the
following model proposed by Land (1968)
1 4
𝑆𝑐𝑜2,𝑐 = [(𝑆𝑐𝑜2 − 𝑆𝑐𝑜2 ) + √(𝑆𝑐𝑜2 − 𝑆𝑐𝑜2 )2 + (𝑆𝑐𝑜2 − 𝑆𝑐𝑜2,𝑟 )]
2 𝑐
The parameter C was found by fitting an empirical association correlating the scaled residual
saturation, Sco2,i prior to the imbibition process that led to trapping equation 1 above. As a result
the IR curve is generally empirical premise for parameterizing hysteries in flow modeling. The
initial residual curves for a range of values of the constant C and the analogous tracking hysteries
curves were illustrated for capillary pressure and relative permeability relationships.

Capillary Trapping of CO2 in Oil reservoirs: Observations in a Mixed Wet Carbonate Rock
The key component of this study conducted by Krevor and Al-Menhali (2016), was to analyze the
effect of the wetting state of carbonate reservoirs on trapping for CO2 storage.

Evaluation of CO2 Storage Mechanisms in CO2 Enhanced Oil Recovery Sites: Application
to Morrow Sandstone Reservoir.
The Morrow sandstone reservoir was investigated by (Ampomah, et al. 2016), because it
presented opportunities for simultaneous enhanced oil recovery and carbon dioxide storage. This
article imparts field-scale compositional simulations of CO2 storage capacity as a function of
different trapping mechanisms within the Farnsworth Unit in the Texas panhandle.

The Nanoscale Basis of CO2 Trapping for Geologic Storage


Boug et al. (2015), presents three parameters used in field scale geologic carbon storage models
that are intrinsically on a nanoscale basis and contribute considerably to the uncertainty of field
scale predictions of CO2 trapping i.e. vertical permeability of seals, residual CO2 saturation in
reservoir rocks and reactive surface area of silicate solids.

Laboratory core flooding experimental systems for CO2 geosequestration: An updated


review over the past decade
The intention of this paper presented by (Sun, Yang and Liu 2016) was to methodically review
the most recent empirical core flooding experiments and facilities available from 2006 for
investigating core-scale supercritical CO2-brine-rock interactions under reservoir conditions
during CO2 injection as well as to conceptualize optimal core flooding device and experimental
methods for ascertaining CO2 storage in deep saline aquifers.

Immiscible Displacements and Capillary Trapping in CO2 storage


The residual non-wetting phase saturation of super-critical CO2 in Brea sandstone was measured;
along with carbon dioxide contact angles on porous plate to elucidate the wetting behavior in the
experiment. Pentland et al., (2011) suggested that super-critical CO2 is the non-wetting phase in
sandstones with significant trapping ability and storage in acquifers.

Estimation of Three-Phase Relative Permeability Isoperms in Heavy Oil/Water/Carbon


Dioxide and Heavy Oil/Water/Methane Systems
This paper written by Akhlaghinia et al., (2013) proposed a technique to utilize two and three
phase displacement experiments in order to estimate relative permeability isoperms for a fluid
system of heavy oil/water/gas. The three-phase flow zone was determined in a ternary diagram
with residual oil and irreducible water saturations obtained from two-phase heavy oil/water
displacements experiments (Akhlaghinia, Torabi and Chan 2013).
Minimum miscibility pressure determination for systems carbon dioxide & heavy
Hydrocarbon (N-Eicosane) & Light (Ethane or Propane) Using Peng-Robinson Equation of
State
In this experiment, empirical studies conducted by Al-Marri and the Kuwait Institute for
Scientific Research (2009), delve into binary and ternary equilibrium studies involving a heavy
hydrocarbon such as n-eicosane, light hydrocarbon such as ethane and propane with carbon
dioxide. Peng-Robinson equation of state with binary interaction parameters were applied to
represent vapor-liquid equilibria and to optimize the representation with minimum use of ternary
parameters. The Minimum Miscibility Pressure (MMP) was obtained from the prediction of
experimental data using pseudo-ternary conceptualization (Al-Marri and Kuwait Institute for
Scientic Research 2009).

Reducing heavy oil carbon footprint and enhancing production through CO2 injection
In this study, Emadi et al., (2010) presented results obtained from a series of micromodel and
core-flooded experiments in order to ascertain the performance of carbon dioxide injection in an
extra-heavy crude oil as a method for EOR and carbon dioxide storage simultaneously. In this
experiment, pore-scale interactions of CO2-heavy oil-water were discovered and the volume of
CO2 that can be stored in reservoirs were quantified. Results from experiments demonstrated that
CO2 injection could provide an effective and environmentally alternative method for heavy oil
recovery. This paper also concluded that CO2 injection could be utilized independently or in
conjunction with thermal recovery methods to reduce the carbon footprint by injecting the CO2
produced during steam generation in the reservoirs rather than releasing it in the atmosphere
(Emadi, et al. 2011).

An Overview of CO2 Enhanced Heavy Oil Recovery Activities


This paper inscribed by Sohrabi et al. (2012), is concerned with CO2 injection for enhanced heavy
oil recovery and CO2 storage. The authors investigated how CO2 injection should be utilized for
heavy oil recovery and during sequestration to support investment decisions at the commercial
scale. To this end, theoretical predictions in areas such as pore-scale fluid flow, heavy oil
extraction and wettability alternation have been closely followed with experiments conducted at
reservoir conditions. The major goals of a heavy oil field development are viscosity reduction,
and sweep efficiency. It was determined that foam combinations considerably enhance heavy oil
recovery (Sohrabi, Farzaneh, et al., An Overview of CO2 Enhanced Heavy Oil Recovery
Activities in the "Centre for Enhanced Oil Recovery and CO2 solutions" of Heriot-Watt
University 2012).

Comparison of WAG and Water Over Injection for Carbon Storage and Oil Recovery in a
Heavy Oil Field
This paper done by Sobers et al (2012) examines how carbon dioxide enhanced oil recovery
coupled with carbon storage using water over gas injection advances production performance and
carbon sequestration over WAG injection via compositional reservoir simulation studies.
Design of Simultaneous Enhanced Oil Recovery and Carbon Dioxide Storage Applied to a
Heavy Oil Field Offshore Trinidad
An injection method was established to recover adequate heavy oil and store carbon dioxide
simultaneously. Simulations were base on the premise of PVT data on oil acquired from an
unconsolidated deltaic sandstone deposit in the Gulf of Paria, offshore Trinidad (Sobers, et al.
2011).
Methodology
Capillary trapping for geologic carbon dioxide storage – From pore scale physics to field scale
implications
Core – scale measurements of trapping
Two primary core-flooding methods used for CO2-brine IR observations. Firstly, CO2-brine
characterizations for sandstone and carbonate rocks were conducted by Pentland et al (2011) and
later by El-Maghraby and Blunt, (2012) respectively was made by using a modified porous plate
(semi-permeable disk) method. In this experiment, a low permeability ceramic plate impregnable
to CO2 was placed at one end of the rock sample. The addition of the porous plate enabled precise
control over the primary drainage flow sequence with a uniform distribution of connected CO2
introduced into the rock sample at a known capillary pressure. The porous plate was modified by
adding a central bypassing flowline, which allowed the subsequent secondary imbibition flow
sequence to be performed to reach residual saturation conditions (Pentland et al 2014). The rock
sample and porous plate were housed in a Hassler type core holder, which was connected to the
necessary pumps and reactors. Saturations were ascertained by volume balance. Although this
method enables accurate monitoring of capillary pressures during drainage, capillary equilibrium
can be time consuming in particular with low permeability rocks.
Modelling the impact of capillary trapping at the field scale
A theoretical model based on the premise of fluid mechanics, which were 2D, depended on the
assumption that the pressure distribution was hydrostatic and that fluid migration was dominated
by lateral displacement. One such model utilized was the sharp interface model, where CO2
saturation, Sg, was either at a maximum, Sg = 1-Swc where Swc was the connate water saturation,
or at a single residual saturation, Sgr (Hesse et al., 2008) (see Figure 3 in the results section).
Engineering Capillary trapping
Injection was engineered to enhance or speed up trapping (King and Paterson, 2002). A method
used to reach optimal trapping was to plan the injection site, location of the well and injection
rates such that the plume would naturally move under the influence of buoyancy and the presence
of an acquifer. As sited by Goater et al 2013, these acquifers do not have a complete geological
seal; instead they have layers, which may extend to hundreds of kilometers to the seabed.
Simulation of 10,000 years of carbon dioxide migration in an open aquifer under the North Sea
was engaged; parameters included: natural ground water flow, trapped CO2 in the top surface of
the aquifer by capillary trapping as it slowly migrates in an upward direction (see figure 4 in
results section).

The NanoScale Basis of CO2 Trapping for Geologic Storage


Various research areas in the mechanisms of CO2 trapping was explored by available empirical
data and simulations.

Capillary Trapping of CO2 in Oil Reservoirs: Observations in a Mixed-Wet Carbonate


Rock
Materials
Fourteen core flood experiments were carried out on two Estaillades limestone core samples
before and after alteration with a hydrocarbon mixture.
Core-Flooding Test and Sequence.
A core flooding technique was applied in this experiment for the construction of initial-residual
characteristic trapping curves. The technique combined the deliberate creation of capillary
pressure gradients in the core with in situ saturation monitoring to rapidly construct the initial-
residual curve across a range of saturations. To create the initial saturation, a primary drainage
step was conducted, injecting CO2 at a constant rate of either 0.5 or 20 mL min -1 into an initially
water or brine saturated core sample. X-ray scan were taken to evaluate the initial saturation
along the length of the rock core. Imbibition was then performed by injecting brine or water, per-
equilibrated with CO2 and the limestone sample at 0.5 mL min -1. Saturations were determined at
each phase with X-ray CT using the standard approach. Numerous scans were taken to confirm
measurements of imbibition and to reduce the uncertainty associated with the computed
saturations.
Altering the Wetting State of the Rock.
After observations completed with the unaltered samples, an aging method using crude oil was
applied to change the wetting state of the core sample. A similar approach to that of Salathiel
(1973) was conducted by preparing a mixture of the evacuated crude oil with an organic
precipitant, heptane. Before aging the rock, observations were carried out with crude oil-heptane
mixtures to identify ratios of fluid resulting in sufficient asphaltene precipitates to induce a
limited wetting state change, so that the permeability of the rock core would not be significantly
altered.

Evaluation of CO2 Storage Mechanisms in CO2 Enhance Oil Recovery Sites: Application to
Morrow Sandstone Reservoir.
The static model for the Farnsworth Unit (FWU) was constructed from geophysical, geological
and engineering data. The model has been utilized by the SWP Simulation (2016), was extracted
from the SWP geological model, which has been history matched. The model, which describes
the west half of the FMU, has a size of 81 x 77 x 5 grid blocks with grid block dimensions of 200
ft x 200 ft. This model included thirteen-finger limestone, Marrow shale and Marrow B sandstone
(see stratigraphy and log of FMU in appendix).
A geomechanical study on several core samples within the FMU was performed and potential
fracture pressure was reported to the range of 5400 – 5600 psia. These data guided the SWP
simulation efforts within the FWU. A thorough reservoir fluid evaluation on an FWU oil sample
that has been used in various SWP reservoir simulation models. Reservoir fluid was tuned to an
equation of state (EOS) using the three-parameter Peng Robinson EOS with a Penleoux volume
correction. The Lohrenz-Bray-Clark correlation was used for viscosities calculations. Sensitivity
analyses were conducted to study the effects of using recycled CO2 with or without impurities on
MMP predictions. These analyses enabled the modeling of CO2-EOR performance incorporating
the real-world use of both purchased and recycled CO2.

Immiscible Displacements and Capillary Trapping in CO2 storage


Experimental conditions
The cylindrical Berea core-plug used was 0.0384 m in diameter and 0.0754 m in length. The
wetting phase in the experiment was 5wt% NaCl, 1% wt.KCl synthetic brine. Petrophysical
properties of the core plugs were: porosity 22.2%, formation factor 14, and brine permeability 4.4
x 10 -13 m2. The core plug was placed I a Hassler type core holder. Experimental pressure and
displacement rates were managed by syringe pumps for high accuracy. The super critical CO2
was generated inside the piston accumulator (Pentland, et al. 2011).
Experimental Procedure: Contact angle measurement, phase equilibration, Initial saturation
primary drainage, water flooding, and residual saturation measurement was conducted.

Estimation of Three-phase relative permeability Isoperms in Heavy Oil/Water/Carbon Dioxide


and Heavy Oil/Water/Methane Systems
An algorithm (see appendix) was employed for two and three –phase unsteady state
displacements in order to ascertain relative permeability isoperms for a fluid system of heavy
oil/water/gas. By exploiting residual oil saturation (Sor) and irreducible water saturation (Swi)
gathered from two-phase heavy oil/water floods, a three – phase flow zone ternary illustration
was allocated. However, three-phase transposition was conducted in the form of gas injection into
a consolidated Brea core inundated with hydrocarbons (heavy oil) and water. A three-phase on
1D numerical simulator was established to replicate a three-phase displacement experiment. A
suitable three-phase relative permeability data was selected to correlate a saturation path drawn
across the three-phase flow zone in the ternary diagram. This relative permeability data was
incessantly re-worked until a differential pressure; heavy oil production and water production
from the numerical simulator match those from the three-phase displacement experiment. This
procedure was repeated for different saturated paths that provided a set of relative permeability
statistics to plot relative permeability isoperms of each phase in the ternary diagrams through
interpolation techniques. Saturation paths were selected so that they include the three-phase flow
zone. By using this method, the final isoperms was stabilized so that the curvature was observed.
Displacement experiments
Experimental setup
Two and three phase displacement experiments were conducted with a high pressure, 2.54-cm
core holder. The key elements were a Teledyne Isco syringe pump (500D series), core holder,
transfer cylinder for injecting heavy oil, temperature controller, back pressure regulator with a
nitrogen cylinder and a Validyne UPC2100 data acquisition system for a precise account of
pressure across the core holder. The temperature controlling system comprised of a heat gun,
temperature controller with a temperature probe and two fans to maintain constant and
homogeneous temperature within the air bath.
Rock/fluid Properties
Rock properties and fluid utilized in two and three phase displacement experiments were outlined
as follows: Length (cm) 29.7, Diameter (cm) 2.54, Pore volume (cm3) 29.01, Porosity (%) 19.27,
Absolute Permeability (Darcy) 1.5636, Oil viscosity (cp) 1174, and water viscosity (cp) 0.84.
Experiments have been performed in Berea consolidated sandstone at a constant temperature of
28 0C. Porosity measured by both weighing and gravity saturation gave a value of 19.27 percent.
Absolute permeability was estimated to be 1.56 Darcy by brine injection at 28 0C. 1wt% NaCl in
deionized brine solution was used as the water phase. The heavy oil was filtered upon receiving
and the viscosity was measured at 1174 cp at 28 0C. In this experiment CO2 and CH4 was used as
the gas phase. The viscosity and compressibility factor versus pressure @ 28 0C was retrieved
from the WINPROP module of the CMG reservoir simulator for CO2 and methane.
Two phase Displacement.
Two-phase displacement experiments were conducted to determine Swi and Sor. A clean dried core
was first weighed and placed into the core holder. After 750 psi of overburden pressure applied,
the temperature was set on the desired temperature of 28 0C. The transfer cylinder was filled with
heavy oil and allowed equilibrating for twenty-four hours. The core was vacuumed for two hours
and inundated with brine to measure porosity and to establish the initial conditions of 100% brine
saturation. Backpressure was sustained by an EQUILIBAR backpressure regulator set at 150 psi.
The core was aged with 20 PVs of brine at a low rate of 0.05 ml/min. Oil was then injected at a
constant rate of 0.1 ml/min via a transfer cylinder. Oil injection continued until irreducible water
saturation was established. During oil injection, effluent fractions were gathered in the graduated
tubes while recording time. Oil injection was then stopped and the core assembly was allocated
12 hrs for the pressure gradient along the core to reach equilibrium.
Three phase Displacement
Consolidated Berea core was saturated with heavy oil and water and was subjected to three-phase
displacement in the form of gas injection. Preparation for this test was identical as the two-phase
displacement test. It was desirable to establish two-phase saturation in the core before gas
injection. According to Salem (1966), with unsteady state experiments oil was usually stopped a
few milliliters prior to breakthrough to allow more of the water phase to remain in the core. After
the two-phase region in the core was determined, the core assembly was allocated twelve hours
for the pressure gradient in the core to achieve equilibrium. Subsequently, gas was injected using
a HIGH-TECH BRONKHORST gas flow controller at a constant rate of 5 mls/min.
Numerical Simulation
A one-dimensional three-phase numerical simulator was developed from a MATLAB software. It
employed the continuity equation for immiscible flow of each phase through porous media, which
included the Darcy equation as a momentum term. Equations established (Akhlaghinia, Torabi
and Chan 2013) have been mathematically elucidated with techniques that implicitly eliminate
uncertainties with numerical modeling portion of the experiment. These derived equations are
presented in the appendix of this paper.

Minimum Miscibility Pressure Determination for Systems Carbon Dioxide & Hydrocarbon (N-
Eicosane) & Light Gas (Ethane or Propane) Using Peng-Robinson Equation of State
Prediction of Miscibility using PVT data
In this experiment by Salem et al., (2009) the Benham et al (1960) pseudo-ternary
conceptualization diagram was employed to investigate and envisage the development of
minimum miscibility pressure (see appendix for diagram, figure 27).
The ternary system of carbon dioxide with light hydrocarbon components (methane, ethane
propane) and n-eicosane were investigated. N-Eicosane was chosen to denote the heavy
constituent element of the experiment. The consequence of light hydrocarbon type on attaining
carbon dioxide oil miscibility in crude oils was investigated. The experiment elucidated the
degree to which changes in the maximum miscibility composition at constant pressure and
temperature as light substituent of the ternary system change from methane to ethane to propane.
The applicability of the cubic equation of state to model the three-phase liquid-liquid vapor
(LLV) region for three ternary mixtures i.e. CO2 + CH4 + n-eicosane, CO2 + ethane + n-eiscosane
and CO2 + propane + n-eicosane were studied. The Peng-Robinson equation of state was used in
phase behavior calculations, because this equation of state adequately provided a reasonable
description of the vapor-liquid equilibria (VLE) and was well known in the oil and gas industry.
Experimental set-up
The experimental device used was a standard PVT laboratory equipment. This equipment
comprises of several main components; JEFRI PVT cell, air bath, charge coupled device (CCD)
camera, magnetic stirrer, viscometer, densitometer and high-pressure positive displacement
pumps. This allowed maximum pressures of up to 1000 pressure gauge and temperatures of up to
200 0 C attainable. Phase transitions were detected visually. The DBR piston with sampling port
was a unique piston and endcap assembly, coupled with a sample port and line through the top of
the PVT cell. The piston and sampling port enabled recovery of samples from either end without
inverting the cell. With this design, gas and liquid phases could be sampled without interrupting
the system. Thus, this designed proved to be more reliable for vapor-liquid equilibrium studies.
Additionally, this design accommodated complete displacement of the vapor phase and reduces
the error connected to sampling as well as reduces sample loss throughout sampling.

Phase equilibria calculations


Knapp et al.,(1982) decided to use four equations of state; to ascertain binary interaction
conditions, Knapp et al. calculated vapor-liquid equilibria to empirical ones. These are presented
in the appendix of this paper.
Mixing Rules
Traditional mixing rules were not utilized for mixtures that contain polar molecules. Thus for
systems that contained CO2 and heavy hydrocarbons two binary interaction parameters were
necessary and are presented in the appendix of this paper.

Reducing heavy oil carbon footprint and enhancing production through CO2 injection
The micromodel rig
A high-pressure micromodel rig was employed to conduct a sequence of direct flow visualization
experiments. This was to further elucidate the knowledge of physical processes underlying CO 2
injection in heavy oil reservoir by revealing the mechanisms of interaction between the injected
CO2 and the reservoir fluids and rock. To quantify the level of heavy oil recovery enhancement,
displacement experiments were conducted in a sand pack. The experiments have been performed
using a heavy crude oil at an average pressure of 600 pisa and a temperature of 50 0 C.
The core rig.The high-pressured core-flood rid employed comprised of high-pressure high
temperature oven; injection pumps and sand pack core holder.
Fluids.Aqueous phase: for the flow visualization experiments, distilled water was utilized as the
aqueous phase, whereas, the core test were conducted using brine solution containing a total
dissolved salt concentration of 10,000ppm. The synthetic brine solution had the following
components: 8000 ppm Sodium Chloride and 2000 ppm of calcium chloride. The liquids were de-
aired before being injected into the storage cell. CO2 utilized had 99.8% purity. Crude oil used
was 11.5 API with asphaltene content of 11.6 (wt/wt%), and viscosity of 8679 @ 50 0 C.
Properties of the core
Depth 0.5 cm, Width 3.7 cm, Length 31.9 cm, Core pore volume 23.5 cm3, ∅ = 40% K = 1.4D
Experimental procedure
Preparation stage: the porous medium was inundated with the aqueous phase of DW or brine @
600 psia at 50 0C. Heavy oil was injected in the core or micromodel to establish Swi and Soi
respectively; in order to mimic the initial migration of oil in a water-bearing reservoir.
Pre-water flood stage: this was the secondary mode (of test simulation) of CO2 injection. Carbon
dioxide was injected for eight days in the core and two days thereafter in the micromodel test.
Then water was injected to strip the dissolved carbon dioxide out of the oil from the porous
medium.
Post-water flood: this was the tertiary mode, which involved injection of the aqueous phase to
mimic the process of water-flood in a heavy oil reservoir. This continues until oil production was
extremely low or stopped. Then, carbon dioxide injection initiated through the porous medium to
simulate tertiary injection of CO2.The duration was two days for the micromodel test and seven
days for the core test. This method extended the period of CO2 injected which was followed by a
second duration of water injection, which lasted until all dissolved CO2 contained in the oil was
stripped by fresh water.

Comparison of WAG and Water Over Injection for Carbon Storage and Oil Recovery in a
Heavy Oil Field
Displacement efficiency
Empirical evidence, correlations and models of CO2 mobility mechanisms were based on the
principle that CO2 and heavy oil was in physical contact and in thermodynamic equilibrium. In
this scenario, the most prominent operational challenge to heavy oil CO2-EOR was the low
macroscopic sweep efficiency being less than unity. This was due to unfavorable mobility ratio
between carbon dioxide and heavy oil at reservoir temperature, pressure and saturation.
Gravity-Dominated Displacement
Parameter used in simulations as well as fluid properties at reservoir conditions are listed in table
3 in the appendix of this paper.
Reservoir Simulation
The equation of state (EOS) package PVTi within the Schlumberger Eclipse software suite was
employed to depict oil phase behavior in-situ. The parameters of the Peng-Robinson EOS (1976)
and the Lohrenz-Bray-Clark (1964) equation were reverted to PVT data. Assumptions were as
follows: the reservoir system has an open outer boundary confined by no flow barriers above or
below. Newtonian mobilities in all phases; there was a direct correlation between gas mobility
and water saturation, as gas mobility decreases and increases monotonically with water
saturation. Reservoir heterogeneity, mass transfer between phases, incompressible phases, fluid
distribution and unsteady state injection was taken into consideration in this simulation.
Results
Capillary trapping for geologic carbon dioxide storage-From pore scale physics to field
scale implications

Figure 1 showing capillary pressure curves, the process of primary drainage and secondary
imbibition. Residual trapped CO2 saturation is shown as the limit of CO2 saturation achieved at
increasingly negative capillary pressure. For water-wet scenario, the residual is almost attained by
Pc= 0 during imbibition whereas for mixed-wet scenario, significant CO2 desaturation occurs at
negative values of capillary pressure (Krevor, et al. 2015).

Figure 2 showing on the left IR characteristic residual trapping curves using the model of Land
(1968) for various values of the constant C derived from equation 1. Central and right columns
imbibition curves departing from the primary drainage curves are illustrated for the values of C
for the capillary pressure derived from equation 3 and relative permeability characteristic curves
respectively equation 2.

Figure 2a. Upper plot shows reported observations of residual trapping with scCO2 made on Brea
sandstones. The lower plot shows residual trapping of scCO2 between sandstone and carbonate
rocks (Krevor, et al. 2015).

Figure 3 showing results of an example of the sharp interface with key characteristics: 2D permits
for three values of saturation and includes an initial injection condition in which injection is
uniform across the entire height of the reservoir body. In this model, residual trapped saturation is
expressed as a single value and aggregate trapping is proportionate to the reservoir sweep of the
plume (Krevor, et al. 2015).
Figure 4 showing results of a numerical simulation of 10,000 years of CO2 migration in an open
aquifer under the North Sea (Goater, et al 2013).
The Nanoscale Basis of CO2 Trapping for Geologic Storage

Figure 5 showing schematic illustration (on the left) of distribution of CO2 near an injection well
roughly one decade after end of injection and four trapping mechanisms that enable GCS. On the
right shows plot of Sgr vs initial CO2 saturation Sgi from measured core samples (Bourg,
Bechingham and DePaolo 2015).
Capillary Trapping of CO2 in Oil Reservoirs: Observations in a Mixed Wet Carbonate
Rock

Figure 6a showing (on the left) results from the forced imbibition part of the of the Amott test
showing oil saturation as a function of the pore volume of brine injected, applied after 30 days of
spontaneous imbibition. On the right (6b), are the initial and residual CO2 and N2 –water
saturations from the mixed wet rock. The solid lines show the best fit Land trapping model with
their respective values for the parameterization constant C (Al-Menhali and Krevor 2016).

Figure 6c showing C values calculated as two times the standard deviation of bet fit C (Al-
Menhali and Krevor 2016).
Evaluation of CO2 Storage Mechanisms in CO2 Enhanced Oil Recovery Sites: Application
to Morrow Sandstone Reservoir
Table 1a on the left gives summary results for injection scenarios in Cases A and B. On the right,
table 1b gives summary results for effects of WAG cycles on CO2 Storage (Ampomah, et al.
2016).

Table 1c (on the left) shows summary for effects of WAG cycles on CO2 Storage and table 1d on
the right shows summary effects of Hysteresis on CO2 Storage (Ampomah, et al. 2016).

Immiscible Displacements and Capillary Trapping of CO2 Storage


Pressure 𝜃(𝑑𝑒𝑔𝑟𝑒𝑒𝑠)
(MPa)
26.6 10±5
29.7 32 ± 2
32.0 30 ± 2
39.5 39 ± 2
47.0 40 ± 2
48.9 40 ± 3

Table 2 showing contact angle measurements at 354.5K between de-ionized water and ScCO2
phase interface on a porous aluminum silicate plate.
Figure 5 (to the right above) showing A drop of ScCO2 generated from a capillary tube brought
into contact with the porous plate substrate at 21 0 (Pentland, et al. 2011)

Table 3 showing Coreflood results and comparison with literature capillary trapping data
(Pentland, et al. 2011)

Table 4 showing oil-brine and ScCO2-brine saturation Coreflood data (Pentland, et al. 2011).
Estimation of Three-Phase Relative Permeability Isoperms in Heavy Oil/Water/Carbon
Dioxide and Heavy Oil/Water/Methane Systems

Figure 6 showing oil relative permeability isoperms (oil/water/CO2) (Akhlaghinia, Torabi and
Chan 2013). Generated by 3Relperm plot

Figure 7 showing water relative permeability isoperms (oil/water/CO2) generated by 3Relperm


plot (Krw * E-03) (Akhlaghinia, Torabi and Chan 2013)
Figure 8 showing CO2 relative permeability isoperms (Oil/water/CH4) (Generated by 3RelPerm
Plot (Akhlaghinia, Torabi and Chan 2013).
Figure 9 showing results from matching 3-phase displacement experiment (oil/water/CO2) with
numerical simulator for saturation path 1, top (pressure drop), centre (oil production), and last
(water production) (Akhlaghinia, Torabi and Chan 2013).
Minimum Miscibility Pressure Determination for Systems CO2 + heavy hydrocarbon (N-
Eicosane) + light gas (ethane or propane) using Peng-Robinson Equation of State

Figure 10 showing Ternary Phase Diagram for CO2/ethane/n-eicosane ternary system at 1514.7
psia and 65.5 0C Al-Marri et al 2009.

Figure 11 showing Ternary Phase Diagram for CO2/propane/n-eicosane ternary system at 1514.7
psia and 65.5 0C Al-Marri et al 2009.
Reducing heavy oil carbon footprint and enhancing production through CO2 injection

Table 5 showing summary of results of the tertiary CO2 injection test (Emadi, et al. 2011)
Figure 12 showing (on the left) oil recovery vs CO2 injection during the CO2 flooding; oil
recovery vs CO2 injection ( on the left) after CO2 breakthrough during secondary and tertiary
CO2 flood core test (Emadi, et al. 2011)

Table 6 showing summary of results of the secondary CO2 injection test (Emadi, et al. 2011)

Figure 13 showing comparison of the recovery factor at different stages of the secondary and
tertiary CO2 injection experiments (Emadi, et al. 2011)
Figure 14 showing saturation of the fluids in the core during secondary CO2-flooding test and
comparison with that of tertiary injection (Emadi, et al. 2011)

Figure 15 showing comparison of the amount of the stored CO2 in different forms (free or
dissolved) during tertiary and secondary core tests (Emadi, et al. 2011)

Comparison of WAG and Water Over Injection for CO2 storage and oil recovery in a
Heavy Oil Field

Table 7 showing performance of CO2 injection strategies (Sobers, SPE and Univesity of the
West-Indies 2012) (Sobers, SPE and Univesity of the West-Indies 2012)
Figure 18 showing oil recovery profile for WAG, waterflood, gas flood, horizontal and vertical
water over gas injection asymptotic to pore volume of injected 5.0 x 10 6 kg-mole of CO2 @ rate
of 50,000 sm3/day (gas gravity 150-200) (Sobers, SPE and Univesity of the West-Indies 2012).

Figure 19 showing CO2 retention for gas flood, WAG, horizontal and vertical gas as a function of
PV of fluid injected after injecting 5.0 x 10 6 kg-mole CO2 at a rate of 50,000 sm3/day (gas
gravity 150-200) (Sobers, SPE and Univesity of the West-Indies 2012).

Design of Simultaneous Enhanced Oil Recovery and Carbon Dioxide Storage Applied to a
heavy oil field Offshore Trinidad

Table 8 showing summary of results (Sobers, et al. 2011)


Discussion and Analysis

The following empirical studies involve experiments, equations of state as well as simulations
that delves into the concepts of carbon dioxide geo-sequestration and enhance oil recovery. This
involves the conceptualization of capillary trapping of carbon dioxide for geologic storage along
with the evaluation of the mechanisms that govern such a phenomenon.

Capillary trapping for geologic carbon dioxide storage-From pore scale physics to field scale
implications.
The amount of capillary trapping was established by observed rivalry between flow in wetting
layers ( water that clings to the corners and roughness of the pore space) and frontal or piston-like
advance, where water directly pushes out from the center of the pore space. Substantial degree of
trapping was therefore contingent on the frontal advance trapping and associated displacement of
the wetting layer also known as “snap-off”. Consequently, the amount of trapping was controlled
by pore structure, flow rate and wettability (the contact angle between the CO2 and solid surface)
(Krevor, et al. 2015). Frontal advance or piston like advance occurred where adjacent pore throats
filled with the wetting phase pushes out the non-wetting phase from the center of the throat.
Moreover, the wetting phase preferentially fills the narrowest regions of the pore space (the
capillary pressure- the pressure difference between CO2 and water- was greatest, which was
indicative of displacement occurring at a low water pressure). A wetting phase front, on
contacting a pore would not spontaneously advance until water pressure in-situ increased
significantly. This enabled more pore throats connected to their respective pores, imbibed with
water. Consequently, a cooperative process was obtained, where filling was increasingly favored
when more connected throats were already saturated with the wetting phase.
The principle “snap off” occurred when the non-wetting phase lose contact with the solid surface.
As this situation becomes unstable, the center of the throat rapidly fills with water. At the point of
capillary equilibrium, this occurrence takes place at the narrowest part of the smallest pore throat.
Thus the “snap off” mechanism was the filling of pore throats in order of increasing size, which
traps the non-wetting phase in the porous media.
Both frontal advance and “snap off” mechanisms, gave rise to residual trapped CO2 saturation.
These phenomena form the premise for core analysis for reservoir characterization and flow
modeling (Krevor, et al. 2015). The residual saturation of the non-wetting phase showed that it
was asymptotic to negative capillary pressure as demonstrated in figure 1 for water wet and
mixed wet CO2-brine systems. Figure 1 shows capillary pressure curves for primary drainage and
secondary imbibition. This curve was used to describe the residual trapping character of a rock.
As such, by virtue of designation, the residually trapped CO2 saturation was illustrated as the
limit of CO2 saturation attained at a progressively negative capillary pressure. For the water wet
scenario, the residual was achieved approximately when Pc= 0 during imbibition whereas in the
mixed wet scenario substantial CO2 desaturation occurs at negative capillary pressure values.
Figure 2 shows IR curves for different values of C using Land (1968) model. The graphs in the
center of figure 2 shows imbibition curves departing from the primary drainage curves for
different values of C for the capillary pressure and relative permeability characteristic curves for
different values of C were shown for the graphs on the extreme right in figure 2. With this model,
the residual CO2 saturation was an increasing function of the initial saturation prior to imbibition,
but the slope decreases with increasing initial saturation. This reveals a marginal decreasing
efficacy of trapping with increasing initial saturation, because higher saturations were obtained
through the influx of increasingly small pores.
Regarding residual trapping and hysteries in multiphase flow, residual trapping was proven to be
a competent method for describing hysteresis in relative permeability and capillary pressure. In
this method, the non-wetting phase saturation Snw was termed as parts that were connected (i.e.
pore throats), Snw,c contributed to flow but termed as parts disconnected and Snw,d did not
contribute to flow. Consequently, Snw = Snw,c + Snw,d and Snw,c ≤Snw. Basically, the disconnected
phase saturation was equivalent to the residual saturation when Snw,c = 0. It was anticipated that
relative permeability to the non-wetting phase, kr,nw, would be a function only to the connected
saturation. Along a bounding drainage curve all of the non-wetting phase was assumed to be
connected, Snw = Snw,c , however, on an imbibition curve the connected saturation must be
calculated from a model that uses observations of residual trapping for its parameterization as
shown previous in equations 2 to 4 above ( theory section).

Figure 2a showed observations of trapping with super critical CO2-brine systems and this was a
complied IR (initial residual) plot of literature data for CO2-brine systems at pressures and
temperatures above the plait point for carbon dioxide. Curves that used the Land model (equation
1) with appropriate bounding values of the constant C illustrated an overall range of 0.2 < C > 5.
In this plot, the difference between sandstone and carbonate rocks samples that were tested
showed that carbonate rocks have a wider scatter between the overall range of 0.2<C>5 than
sandstone rocks; the authors of this experiment, attributed this phenomenon due to greater degree
of heterogeneity by carbonate rocks as oppose to sandstone specimens (Krevor, et al. 2015).

Figure 3 showed impact of capillary trapping at the field scale by the use of theoretical models.
Theoretical models of this type was found on the basis of fluid mechanics and assumed that the
pressure distribution was hydrostatic and lateral movement dominated was fluid migration and
thus they were two-dimensional. Figure 3 showed the sharp interface model, where CO2
saturation, Sg, was either at a maximum, Sg = 1-Swc, where Swc is connate water saturation, or at a
single residual saturation, Sgr. Figure 3 showed as the plume (i.e. the mobile component of the
CO2) migrates and water subsequently imbibes the trailing end, the plume decreases in size as
residually trapped CO2 was lost during migration. Eventually, the entire plume was consumed by
this process and as a result, constraints on the total distance and time over which the plume
migrates.

Figure 4 illustrated results of numerical simulation of 10,000 years of CO2 migration in an open
aquifer under the North Sea: the extent of the domain shown was around 40 km with a natural
aquifer in the direction of the green arrow as shown. Carbon dioxide was trapped under local
traps in the top surface of the aquifer due to capillary trapping as it migrates, slowly upwards. The
injection wells were shown as black lines and the CO2 saturation on the top surface of the aquifer
was shown. After injection, the CO2 will migrate under combined influence of buoyancy and
local groundwater flows. Nevertheless, CO2 was rendered immobile- at a larger scale- under the
influence of local traps on the top surface of the aquifer and more extensively, by capillary
trapping mechanism mentioned earlier as it migrates away from the injection wells.

The Nanoscale Basis of CO2 Trapping for Geologic Storage


Figure 5 (diagram on the left) illustrates a schematic diagram of the distribution of CO2 near an
injection well approximately one decade after the end of injection and four mechanisms than
facilitate carbon dioxide geo-sequestration at the molecular level (Bourg, Bechingham and
DePaolo 2015). From figure 5, supercritical CO2 was injected in previously brine – filled,
micrometer scale pore spaces of a highly permeable geologic formation (usually sandstone) at
depths > 800 m, where it was approximately 30% less dense than the resident brine. The storage
formation was overlain by a thick fine-grained geologic formation, the top seal or caprock,
typically a shale or mudstone. The storage formation may contain layers or lenses of fine-grained
rock (secondary seals). The vertical migration of CO2 plume was retarded by vertical seal
confinement (stratigraphic trapping). During the migration of the plume, a fraction of the CO2
remains trapped as disconnected droplets at the trailing edge of the plume (residual trapping). In
order to predict CO2 trapping, four mechanisms were investigated: vertical permeability kv of
seals, the residual CO2 saturation Sg,r in reservoir rocks and the reactive surface area of silicate
solids.
Stratigraphic Trapping: Vertical Permeability (Kv) of Fine-Grained Rock Formations. The fluid
transport properties of seals (vertical permeability, capillary breakthrough pressure Pc,b) strongly
influence the rate of dissipation of reservoir overpressure, plume shape (i.e. sweep efficiency),
upward plume migration velocity, the rate of CO2 dissolution in brine, and eventually, the rate of
CO2 entry into the caprock.
The vertical permeability of seals was determined by fluid flow through preferential flow paths
such as faults, fractures, and microfractures. Studies have shown (Bourg, Bechingham and
DePaolo 2015), that fluid flow through fractures and faults in shale and mudstones (fine-grain
lithology) comprises the majority of aquitards and caprocks to geologic carbon storage sites. The
presence of faults and fractures in seals prior to CO2 injection implied that vertical permeability
and capillary breakthrough pressure were sensitive to the type of seal insitu. That is, once major
constituents of the seal was made up of increasing clay content, the SGR (shale gouge ratio) fault
permeability decrease from approximately 10-15 to 10 -19 m2 , but capillary breakthrough pressure
increased from .01 MPa to 10 MPa (Bourg, Bechingham and DePaolo 2015).
Residual Trapping: Residual CO2 Saturation (Sg,r) in Reservoir Rocks. Residual CO2 saturation
(Sg,r) was the key parameter that determined the extent of residual trapping and strongly
influenced plume migration velocity, storage capacity and storage security. Figure 5 on the right
showed a plot of Sgr vs initial CO2 saturation Sg,I measured in core samples at capillary numbers
Ca ≤ 1010−6 (Bourg, Bechingham and DePaolo 2015). The yellow and blue diamonds in figure 5
𝑆
(on the right) were consistent with 𝑆𝑔,𝑟,𝑚𝑎𝑥 = 0.166/∅0.63 where Sg,i,max and Sg,r,max were the
𝑔,𝑖,𝑚𝑎𝑥
maximum achievable initial and residual CO2 saturation. Residual CO2 saturation Sg,r also
depended on pore to core scale heterogeneity and on the topology of the CO2 phase. Moreover,
this study further suggested that in mixed-wettability systems, Sgr was smaller than in water-wet
systems and may have a non-monotone dependence on Sgi. The contact angle 𝜃 also has influence
on Sg,r .i.e during imbibition at the pore network scale, small values of 𝜃 favor imbibition by
“snap-off” (i.e. by filling of pore throats in order of increasing size, which traps the non-wetting
phase in the pore bodies), whereas larger contact angles favor imbibition by piston-type or frontal
advance displacement which reduces capillary trapping capability of the reservoir. This Finding
confirms studies conducted by (Krevor, et al. 2015) –mentioned above-, which stated that the
degree of capillary trapping overall was controlled by the extent of the wetting layer flow and
snap-off leading to more trapping. Figure 5 also suggested that geologic carbon storage site with
relevant rocks and minerals were water wet during CO2 invasion where 𝜃 ∼ 0 𝑡𝑜 500 however,
during brine imbibition there were high residual gas saturation which was indicative of water-wet
systems. Bourg et al,. continued to suggest that rocks may be intermediate –wet during brine
imbibition exhibiting 𝜃𝑎 ∼ 900 . This value was indicative of intermediate –wet conditions, which
also showed less trapping capability.
Moreover, direct measurement of 𝜃 by micromodels and molecular simulations showed that
carbon-rich solids such as anthracite, limestone and calcite may exhibit lower 𝜃 angles than
sandstone solids and therefore this maybe another reason why carbonate rocks have higher
trapping capabilities that sandstone rocks as illustrated earlier in figure 2a above.
Mineral Trapping: Reactive surface Areas in situ depended on the fraction of the mineral surface
area that was accessible for reaction with carbon dioxide, the geometry of the surface area as well
as the fraction of the particle size or grain size that was smooth or rough.
Capillary Trapping of CO2 in Oil Reservoirs: Observations in a Mixed wet Carbonate Rock
Figure 6a showed (on the left) results from the forced imbibition part of the of the Amott test
showing oil saturation as a function of the pore volume of brine injected, applied after 30 days of
spontaneous imbibition. The water wet sample (E2) produced negligible oil after breakthrough,
while the mixed-wet sample (E1) continued oil production with a reducing remaining oil
saturation trend as a function of PV injected. Figure 6b illustrated best-fit curves for the Land
model from equation 1 (see theory section), CO2 trapping was observed in both altered and non-
altered specimens (i.e. Limestone and carbonate rocks) in order to determine which state of CO2
were more susceptible to capillary trapping. It was observed that supercritical carbon dioxide
(scCO2) relative to gaseous CO2 in limestone was more susceptible to capillary trapping.
Furthermore the investigators (Al-Menhali and Krevor 2016) observed that the Land constant “C”
from figure 6c, was larger for sandstone, which was indicative of less trapping capabilities than
limestone (a carbonate rock specimen). The investigators attributed this occurrence due to pore
structure and possibly the wetting state of the specimens involved in the experiment.
Furthermore, they observed that more trapping for supercritical CO2 in carbonate rocks resulted
from differences in rock structure leading to more favorable sensitivities to contact-angle changes
between the supercritical carbon dioxide and the substrate (i.e. surface of carbonate rocks than
sandstone).

Evaluation of CO2 storage Mechanisms in CO2 Enhanced oil recovery sites: Application to
Morrow Sandstone Reservoir.
This experiment conducted by (Ampomah, et al. 2016) demonstrated the effects of CO2 injection
profiles on storage namely, at constant carbon dioxide purchase (26350 lb.mol/day and at
decreasing CO2 purchase from 2022 to 2030 and injection of only recycled gas after 2030. The
first scenario (Case A) involved continuous injection of 26350 lb.mol/day of purchased carbon
dioxide after recycled gas for a 21-year period. The second scenario (Case B) involved
continuous injection of 26350 lb.mole/day in addition to recycled gas until year ending 2021.
Table 1a above showed concise results between both scenarios. In the first scenario (Case A),
fifteen percent of carbon dioxide volume (MMlb.mol) was stored more than the second scenario
case B (Ampomah, et al. 2016). However, in comparison to case B, more CO2 produced was
recycled and hence stored in Case B than in Case A. The main cause for this disparity was
bottlenecking constraints experienced in case A; also in terms of long-term storage planning, both
cases displayed adequate pressures will above the minimum miscible pressure (MMP).
This paper also investigated the effect on WAG cycles on storage mechanism. Since
modifications in carbon dioxide and alternate water cycling in a CO2 flood mechanism can affect
both the volume of CO2 stored and the storage mechanism simultaneously. It observed that in
order to get optimum oil recovery and volume of CO2 stored, and hence maximum use of
purchased CO2, a WAG cycle to the ratio of 3:1 should be employed. This was due to lower
bottomhole pressures at the producer wells, which lead to the increase in larger volumes of CO 2
injected. However, this could be impeded if bottomhole pressures were maintained higher than
desired due to larger volume of water at the producer wells resulting in more dissolution of
supercritical CO2 as shown in table 1b above. Table 1c illustrated the residual trapping for two
cases where in case B2, carbon dioxide stored due to residual trapping was more significant
because of hysteries accounted for in the specimen. This phenomenon makes the wetting phase
bypass a non-wetting phase; it usually renders the nonwetting phase immobile and entrapped.
Thus during the imbibition process, relative permeability of the wetting phase increases
considerably compared to that of the non-wetting phase, resulting in entrapment.

Immiscible Displacements and Capillary Trapping in CO2 storage


Table 2 gave a summary of the contact angle measurements conducted. While figure 5 showed
the CO2-water porous plate contact angle at the maximum pressure (i.e. 48.9 MPa). The smaller
contact angles were due to negligible contact force between the drop and the substrate (i.e. the
drop marginally reached the substrate) whereas, at higher pressures, contact angles were larger at
40 0 due to good contact being achieved. Another reason for the variation in contact angles was
the solubility in of CO2 in brine and subsequent shift in chemical reactions i.e. CO2 + H2O
↔HCO3- 2H+ + CO3 2- the drop in pH value and the increase in bicarbonate and carbonate ion
concentrations may have change the surface chemistry of the substrate and the electric double
layer on it, influencing the spreading of the CO2 (Pentland, et al. 2011).
The preceding experiments above delved into the mechanisms experienced in CO2 entrapment in
various reservoirs, core experiments as well as simulations. One common denominator amongst
nearly all of them was the use of the Land model equation 1 from 1986 to show the effectiveness
and the carbon dioxide storage character of rock specimens especially between carbonate and
sandstone cores.

Estimation of Three-Phase Relative Permeability Isoperms in Heavy Oil/Water/CO2 and Heavy


Oil/Water/Methane systems
A 3Relperm Plot software was used to generate relative permeability isoperms for two three-
phase systems, i.e. heavy oil/water/CO2 and heavy oil/water/methane illustrated in figures 6
through 8. Results from the three-phase displacement experiments (i.e. pressure drop, oil
production and water production) corresponded with results from the simulator. The ternary
diagrams showed that the 3-phase flow zone for the heavy oil system was quite small due to high
values of residual oil saturation. Also the shapes of relative permeability isoperms were different
in the presence of Carbon dioxide. Additionally, values (i.e. 0.81 vs. 0.71856 for CO2 and CH4
respectively) from the ternary figures illustrated that oil relative permeability in the presence of
carbon dioxide was higher than methane. The investigators of this experiment (Akhlaghinia,
Torabi and Chan 2013) purported that since CO2 was more miscible in heavy oil than methane,
this accounted for the difference due to the absorption of carbon dioxide in the oil phase, which
reduces oil relative permeability. Also CO2 has a substantially lower minimum miscibility
pressure than methane, which contributed to the higher permeability values in carbon dioxide
than methane. Furthermore, it was found that water relative permeability in oil/water/methane
system was greater than the oil/water/CO2 system. This was as a result of the tendency for water
to be absorbed by carbon dioxide, which reduces mobility of the CO2.

Minimum Miscibility Pressure Determination for Systems Carbon Dioxide + Heavy Hydrocarbon
(N-Eicosane) + Light Gas (Ethane or Propane) Using Peng-Robinson Equation of State.
The objective of this research paper conducted by (Al-Marri and Kuwait Institute for Scientic
Research 2009) was to ascertain the minimum displacement using carbon dioxide for ethane +
CO2 + n-eicosane and propane + CO2 + n-eicosane using carbon dioxide displacement. The tie
line was shown in ternary diagram figures 10 and 11 above. In figure 10, ethane/CO 2/n-eicosane
system was examined. At point C, the maximum miscibility composition (MMC) was 93.7%
ethane and 6.3% n-eicosane. The composition point D was 99.2% ethane and 0.8% n-eicosane. If
n-eicosane concentration in the ethane/n-eicosane binary mixture were in the range of 0.0 to
0.8%, the first contact miscible with CO2 would be obtained. Also if n-eicosane falls within the
composition range of 0.8 to 6.3% multiple miscible contacts would be obtained in the gaseous
phase. However, beyond composition range of 6.3 (i.e. 6.3 to 100%) miscibility will not be
achieved with CO2.
The compositions of the vapor and liquid phases for propane/CO2/n-eicosane were compared with
results of the PT flash calculations using the Peng-Robinson EOS, which showed moderate
agreement between results. For figure 11, point C was shown to be the maximum miscibility
composition (MMC), which was 63.768% propane and 36.232% n-eicosane. The composition at
location D was 97.391% propane and 2.609% n-eicosane. In this system, if n-eicosane
concentration falls within the propane/n-eicosane binary mixture of 0.000-2.609%, the first
miscible contact with CO2 would be obtained. N-eicosane in the composition range 2.609-
36.232% could achieve miscibility by multiple equilibrium contacts within the gaseous state.
However, beyond 36.232% miscibility with carbon dioxide would not be achieved. This was due
to the high C3 mole fraction, however to date it is not feasible because of the high associated cost
on a field scale.

Reducing heavy oil carbon footprint and enhancing production through CO2 injection
Table 5 and 6 showed, that the ultimate oil recovery averaged to 30% due to water and CO2
injection under stable gravity conditions (Emadi, et al. 2011). This was due to the viscosity
reduction of heavy oil by carbon dioxide. Figure 13 gave comparisons between oil recovered
during secondary CO2 injection with a first cycle tertiary CO2 cycle injection. The results
obtained showed that ultimate oil recovery was higher in the secondary CO2 injection scenario
(29.1%) of oil produced than 26% obtained under tertiary carbon dioxide recovery. The following
reasons attributed to disparity between injection strategies: continuity of the oil phase in the
porous medium which aides in the recovery process by gravity drainage in secondary CO2
flooding. Secondly, in secondary CO2 injection, water injected following the CO2 would displace
the CO2 diluted with oil with significantly lower viscosity than the original oil as in the case of
tertiary –post water-flood- CO2 injection. Figure 15 shows CO2 storage in the core as free CO2
and dissolved CO2. A significant of CO2 stored as dissolved in oil (62%) vs 38% as free CO2.
Notwithstanding greater saturation of free CO2 in the tertiary recovery, the lower capacity of
water to dissolve CO2 compared to oil makes the final volume of stored CO2 very similar in both
scenarios. In both scenarios, the following mechanisms were identified which contributed to CO2
storage: direct displacement, oil/brine swelling/viscosity reduction and gravity drainage.

Comparison of WAG and Water Over Injection for Carbon Storage and Oil Recovery in a Heavy
Oil Field
This study performed by (Sobers, SPE and Univesity of the West-Indies 2012), illustrated that the
displacement of heavy oil by water over gas injection hinders the rising of CO2 and facilitates
substantial displacement of injection CO2 as well as water underride. However when compared
with WAG, water over injection provides greater sweep efficacy and consequently greater
ultimate hydrocarbon recovery than WAG. Furthermore, results continued to illustrate that water
over injection greatly diminish producing GOR and water cut as to oppose to WAG. When
customary WAG injection was used for CO2 storage, substantial volumes of CO2 could not be
stored during a CO2 flooding, because of gravity override resulting from gravity segregation and
as a result 1/3 of injected carbon dioxide would be left in the mobile phase, thereby compounding
the risk of seepage over geologic time.

Conclusion
The main objective of this paper was to highlight the core mechanisms that are pertinent to the
simultaneous design of carbon dioxide geo-sequestration with enhance heavy oil recovery.
Experiments investigating from the nanoscale of the rock grains to field / reservoir implications
have been highlighted with the aim to conceptualizing various principles discovered throughout
this paper. Most importantly, this paper serves to elucidate the utilization of various equations of
state (for example the Peng-Robinson) and simulations that were the source of results obtained
from all papers researched.
Recommendations
 Key understanding of the overall picture of the importance of capillary trapping in carbon
dioxide storage is need; however this process can be limited to laboratory experiments
and simulations since field scale observations cannot 100% be effectively modeled by
simulations and laboratory experiments.
 Laboratory experiments will need to be outfitted with real time dynamic modeling
devices in order to reduced uncertainty from in-situ high pressure high temperature
conditions.
 Future work is needed for investigating system wettability further and measuring the
shape of the trapping curve for CO2-brine systems and different rock types (Pentland, et
al. 2011).
 Further research is needed to elucidate why carbonate rocks hold more CO2 than
sandstone and what is the geochemical and geomechanical implications of CO2 storage
over time.
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Appendix

Figure A1 showing a schematic of a core flooding method purposed by (Pentland, et al.


2011).

Figure A2 showing schematic of storage in open acquifers. The injection well is shown as
the vertical black line. CO2 migrate upwards beneath the cap rock on the left, but the aquifer
is not closed. On the right CO2 is trapped in a dome shaped caprock, however migration is
still possible laterally after further injection Goater et al (2013).
A3. Estimation of Three-Phase Relative Permeability Isoperms in Heavy Oil/Water/CO2 and
Heavy Oil/Water/Methane Systems equations used in numerical simulation.

Estimation of Three-Phase Relative Permeability Isoperms in Heavy Oil/Water/Carbon Dioxide


and Heavy Oil/Water/Methane Systems

Figure A4 saturation path selection across the (Akhlaghinia, Torabi and Chan 2013) three-phase
zone.
A5. Algorithm proposed to estimate three-phase relative permeability data from unsteady state
displacement experiments (Akhlaghinia, Torabi and Chan 2013)

A6 showing Pseudoternary conceptualization of Benham et al. (1960) (Al-Marri and Kuwait


Institute for Scientic Research 2009).
Table 1 showing average properties of unconsolidated Forest Reserve sands found in
several accumulations across the Soldado Field (Sobers, et al. 2011).

Table 2 showing compositional description of crude oil constituents (Sobers, et al. 2011).
Table 3 showing parameters used in simulations (Sobers, SPE and Univesity of the West-
Indies 2012).
Figure A7. Showing Stratigraphy and type log of the FMU (Ampomah, et al. 2016)