Applied Energy 88 (2011) 3557–3566

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

A review of physical modelling and numerical simulation of long-term

geological storage of CO2
Xi Jiang ⇑
Engineering Department, Lancaster University, Lancaster LA1 4YR, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: Numerical simulations are essential to the understanding of the long-term geological storage of CO2.
Received 27 December 2010 Physical modelling of geological storage of CO2 has been based on Darcy’s law, together with the equa-
Received in revised form 30 April 2011 tions of conservation of mass and energy. Modelling and simulations can be used to predict where CO2 is
Accepted 2 May 2011
likely to flow, to interpret the volume and spatial distribution of CO2 under storage conditions, and to
Available online 31 May 2011
optimise injection operations. The state of the art of physical modelling and numerical simulation of
CO2 dispersion is briefly reviewed in this paper, which calls for more accurate and more efficient model-
Keywords:
ling approaches. A systematic evaluation of the numerical methods used and a comparison between the
Carbon capture and storage (CCS)
Darcy’s law
streamline based methods and the grid based methods would be valuable. Multi-scale modelling may
Modelling prove to be of great value in predicting the long-term geological storage of CO2, while highly accurate
Numerical simulation numerical methods such as high-order schemes may be employed in numerical simulations of CO2 dis-
persion for local transport calculations.
Ó 2011 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3557
2. Modelling and simulation of carbon storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3559
3. Theoretical modelling and governing equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3559
3.1. Physical modelling and governing equations for the flow in porous media . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3560
3.2. Modelling of the chemical processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3561
3.3. Modelling limitations, uncertainties and issues for investigation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3561
4. Numerical simulations: methods and challenges. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3562
4.1. Overview of simulators for carbon storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3563
4.2. Numerical issues for investigation and challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3564
5. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3565
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3565

1. Introduction policies [5–7]. The geological storage of CO2 currently represents

The potential role of carbon abatement technologies in reducing
greenhouse gas emissions has gained much increased recognition
and importance internationally in recent years [1–4]. Early rapid
deployment of carbon dioxide (CO2) capture and storage (CCS)
technologies is now recognised as an important issue in meeting
climate change mitigation targets and providing a serious option
worldwide. The development and deployment of CCS technology
can have a profound impact on the energy sector including energy
⇑ Tel.: +44 1524 592439; fax: +44 1524 381707.
E-mail address: x.jiang@lancaster.ac.uk
the best and likely the only short-to-medium term option for sig-
nificantly enhancing CO2 sinks, thus reducing net carbon emissions
into the atmosphere [8]. CCS can be effectively integrated into var-
ious energy systems. For instance, a liquefied energy chain for
transport and utilisation of natural gas for power production with
CCS was investigated [9–12]. Other investigations included inte-
gration of carbon capture onto electric power generation for off-
shore operations [13], power generation combining solid oxide
fuel cell and oxy-fuel combustion for carbon capture [14], as well
as an industrial test and techno-economic analysis of carbon cap-
ture in a coal-fired power station [15]. As it stands, CCS is the only
industrial scale process capable of capturing large quantities of CO2
at source and burying it beneath the earth’s surface.

0306-2619/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2011.05.004
3558 X. Jiang / Applied Energy 88 (2011) 3557–3566
Nomenclature
A reaction surface area
C specific heat capacity
D diffusivity
Ea activation energy
f function
g magnitude of gravitational acceleration
g gravitational acceleration assuming in the negative
coordinate direction
h grid spacing in the computational domain
H specific enthalpy
I kinetic rate
k relative permeability
k permeability tensor
K rate constant of chemical reaction
p pressure
q filtration velocity (Darcy flux)
Q ion activity product
R universal gas constant
s saturation
S source/sink term
SH source/sink term of energy
In recent times, potential CO2 storage sites are being extensively
investigated globally. The capacity for CO2 storage in geological
media is significant and the likely retention time is more than ade-
quate [16]. Many countries now have cadastres showing suitable
storage regions, and these cadastres are currently being given a
more precise shape. Candidate CO2 storage facilities include deep,
salt-water-bearing rock layers, as well as former natural-gas and
depleted oil deposits. Such depositories can be found both onshore
and offshore (below the seabed). By making possible the continued
use of coal as a fuel for power generation and the production of
hydrogen or synthetic fuels (hydrogen-enriched syngas), CCS is a
technology that could provide a bridge from the current fossil-
fuel-based economy to a future low-carbon energy system such
as a hydrogen-based economy with cleaner energy.
Understanding CO2 dispersion in storage conditions is the pre-
requisite for the development of CCS technology. Since the storage
of CO2 in geological media shares many similar features with oil
and gas accumulations in hydrocarbon reservoirs and with meth-
ane in coal beds, the technology for storage could be derived from
the experience gained in oil and gas exploration and production,
natural gas storage and deep disposal of liquid wastes and acid
gas [8], or more closely, from the CO2-enhanced oil recovery
(EOR) techniques. Although there is extensive experience in similar
areas from a technological point of view and the individual compo-
nents of this emerging technology all exist separately, they have
not been implemented in an integrated CCS system and/or on the
scale needed to reduce CO2 emissions in the atmosphere. More-
over, there are concerns on the long-term fate of geologically
stored CO2. In considering deep ground storage of CO2 from power
stations and other large sources one has to account for the poten-
tial leakage during the injection as well as the leakage over time,
either through porous ground layers, or through the various seals.
Understanding the long-term fate of stored CO2 is of crucial impor-
tance that can help answering the question: can it be guaranteed
that the CO2 will remain underground for many years? Meanwhile,
it is important that the necessary standards, legal bases and regu-
lations for storing CO2 are created for wide adoptions of the tech-
nology. The scientific understanding of CO2 storage provides the
necessary basis for the creation of the legal framework.
Geological media with the porosity needed to provide storage
capacity, the permeability required for injectivity, and confined
t time
T temperature
U specific internal energy
v velocity vector
X mole fraction
x, y, z Cartesian coordinates
k conductivity
l dynamic viscosity
m stoichiometric reaction coefficient
q density
R summation
s tortuosity
/ porosity
r gradient operator
Subscripts/superscripts
c capillary, critical
eq equilibrium
i, j, m, n index
s solid
a, b fluid phase
low-permeability barriers to prevent CO2 migration and/or leakage
out of the intended storage unit can be effectively used for CO2
storage. The geological storage of CO2 involves several mechanisms
[8,16], as summarised in Table 1. Physical trapping occurs when
CO2 is immobilized as a free gas or supercritical fluid. There are dif-
ferent types of physical trapping. In static trapping, the flow of CO2
is impeded by a physical low-permeability barrier. In this case, if a
pathway is found, CO2 will flow driven by its own buoyancy and
other forces. The residual-gas trapping occurs largely after injec-
tion has stopped, when water (the wetting phase) moves back into
the pore space after the high-pressure injection process of CO2 (the
non-wetting phase) has stopped. Chemical trapping occurs when
CO2 adsorbs onto organic materials contained on coals and shales
(adsorption trapping), or when it dissolves in subsurface fluids
(solubility and ionic trapping), or when CO2 reacts with possible
minerals in the rock matrix (mineral trapping).
Among the various trapping mechanisms, ‘‘hydrodynamic trap-
ping’’ refers to a combination of several mechanisms. Where CO2 is
injected into reservoirs, or into saline formations, it can remain in
the reservoir moving very slowly for a long time until eventually it
is trapped by residual, solubility or mineral trapping. This is re-
ferred to as hydrodynamic trapping. In this process, saline forma-
tions generally have low flow velocities (of the order of cm/year).
The CO2 that remains free-phase migrates upwards through per-
meable pathways in the rock. Because CO2 is normally less viscous
than the formation water it moves by a process called viscous fin-
gering, which is the formation of patterns in a morphologically
unstable interface between two fluids in a porous medium. Some
CO2 is dissolved in the formation water through solubility. The dis-
solved CO2 migrates with the formation water. The relationship be-
tween the dissolved CO2 and the free-phase CO2 determines how
far the CO2 will migrate before all of the CO2 is eventually trapped
residually or in solution. Under favourable circumstances, injected
CO2 may migrate in the subsurface at extremely low velocities
such that it would take time on a geological scale (tens of thou-
sands to millions of years) to potentially reach the surface, before
which, under the right conditions, it is most likely to be securely
trapped. Very large amounts of CO2 could be potentially stored in
this way. Our future economy will remain largely carbon based
in the foreseeable future. CCS is a key technology in our efforts
to avoid dangerous climate change, which certainly has an
 X. Jiang / Applied Energy 88 (2011) 3557–3566 3559

Table 1
Mechanisms of CO2 sequestration in geological media.

Mechanisms Duration after injection

Physical Static trapping (using structural and stratigraphic traps or man-made caverns, etc.): the flow Duration is up to dozens of years after injection.
of CO2 is impeded by a physical low-permeability barrier.
Residual CO2 trapping: the CO2 is trapped in the pore space at irreducible gas saturation; the Duration can be up to thousands of years.
flow of CO2 is not possible because of the interfacial tension between CO2 and formation
water.
Hydrodynamic trapping: a combination of different mechanisms, including all the possible Primary trapping is up to dozens of years while secondary
physicochemical mechanisms. trapping is up to a geological scale after injection.
Chemical Adsorption trapping: the CO2 is adsorbed onto organic materials contained on coals and Duration is up to dozens of years after injection.
shales.
Dissolution trapping (solubility and ionic trapping): Duration is up to hundreds of years.
Solubility: CO2 (gaseous) ? CO2 (aqueous) and CO2(aqueous) + H2O ? H2CO3 (aqueous).
Ionic: H2CO3 (aqueous) + OH ? HCO 3ðaqueousÞ + H2O.
Mineral trapping: chemical reactions with the rock matrix in rich of Ca and Mg minerals, e.g. Duration is up to a geological scale (tens of thousands to
HCO  ¼ ¼
3ðaqueousÞ + OH ? CO3ðaqueousÞ + H2O and CO3ðaqueousÞ + Ca
2+
? CaCO3 (solid) millions of years).

economic impact on the energy sector. Since we are tackling an
unprecedented engineering process, the understanding of CO2
dispersion will be the most important first step forward for the
technology development.
2. Modelling and simulation of carbon storage
Understanding the geological storage of CO2 can be achieved by
experimentation and careful monitoring of the storage sites [17].
Although geological carbon storage has been reviewed from mon-
itoring, experimentation and operation perspectives, e.g.
[8,17–20], it has not been fully reviewed from the perspective of
numerical modelling and simulation. For the prediction of CO2
migration or dispersion, analytical and numerical approaches can
be particularly useful. Analytical and/or semi-analytical solutions
of CO2 sequestration in geological formations, e.g. [21,22], can be
valuable for improving understanding of the process, but they
use significant simplifications and are limited in their scope of
applications. Computer simulations based on physical modelling
and numerical solution of the governing equations may prove to
be the only possible means to address the principal public and
environmental concern related to the long-term fate of the carbon
storage. However, simulating CO2 flow behaviour in geological
media is difficult because of the interplay between the possible
phase change, composition, reservoir heterogeneity, and the com-
putational demands these aspects impose. Recently, the results of a
substantial benchmark study that compared a number of mathe-
matical and numerical models applied to specific problems in the
context of CO2 storage in geological formations were reported
[23], where the processes modelled comprise advective multi-
phase flow, compositional effects due to dissolution of CO2 into
the ambient brine and non-isothermal effects due to temperature
gradients. An aspect that became evident from this benchmark
study is that the participating models revealed strong differences
in their numerical performances. This is an issue which is very rel-
evant for engineering practice. The study concluded that improving
the numerical performance by optimising discretisation methods,
solvers, and parallelisation methods still remains a crucial field of
research.
Modelling and simulation can play a significant role in the
development of CCS technologies. If the greenhouse gas CO2 injec-
tion into geological formations is undertaken on a large scale, low
cost yet physically-accurate numerical simulations with high-
resolutions are required. Such simulations will be used to predict
where CO2 is likely to flow, to interpret the volume and spatial dis-
tribution of CO2, and to optimise injection operations. Such ele-
ments are essential if geological sequestration were proven to be
feasible and to gain public acceptance. The process of carbon stor-
age involves flow and transport phenomena in porous media,
which occur at different space and time scales [24]. For instance,
the transport phenomena such as species diffusion and viscous fin-
gering take place in small scales, while the macroscales for CO2
storage can be larger than several kilometres and longer than many
years. The conventional computational fluid dynamics (CFD) ap-
proach is not suitable for the modelling and simulation of CO2 stor-
age because of the large time and length scales involved, especially,
where grid dimensions need to be made sufficiently fine to begin to
resolve the coupling between flow and phase behaviour. Stream-
line-based methods [25] have been used in the oil industry, which
may be applied in problems with large time and length scales and
hold great promise for aiding the design of efficient injection and
storage processes [26,27]. However, the numerical discretisation
methods used in streamline methods tend to be of lower-order
accuracy based on single-point upstream weighting, and there is
also no detailed comparison between streamline simulators and
conventional grid-based CFD codes. It remains unclear how
streamline simulators compare with conventional grid-based
codes in terms of computational costs and simulation accuracy. A
significant amount of research is still required to effectively predict
CO2 dispersion using numerical methods in the context of CCS.
In the following sections, theoretical modelling of the flow and
transport phenomena in carbon storage is firstly discussed with
commonly used governing equations for the flow in porous media
presented, where the focus has been taken as the fundamental
assumptions used in the physical models and characteristics of
the governing equations. Modelling of the chemical processes is
briefly discussed as part of the theoretical modelling. Modelling
limitations, uncertainties and issues for investigation are also dis-
cussed. Secondly, the numerical methods used in simulations of
CO2 storage are briefly reviewed. An overview of several simulators
used in carbon storage simulations including their discretisation
methods is presented, followed by a discussion on the numerical
issues for further investigation and the numerical challenges. Fi-
nally, conclusions are drawn.
3. Theoretical modelling and governing equations
As shown in Table 1, CO2 can be stored in geological media by
various means through a variety of physical and chemical trapping
mechanisms, as a result of its properties at the pressure and tem-
perature conditions found in earth’s subsurface. At normal stan-
dard conditions CO2 is a gas with a density slightly heavier than
air. The critical temperature and pressure for CO2 are Tc = 31.1 °C
and pc = 7.38 MPa, respectively. Under normal geological storage
conditions, for T < Tck and pressures above the vapourization curve,
CO2 is a liquid, while for temperatures and pressures above the
3560 X. Jiang / Applied Energy 88 (2011) 3557–3566
critical point CO2 is a supercritical fluid, which possesses the high-
density characteristic of liquids and occupies the entire available
volume like a gas. Both temperature and pressure generally in-
crease with depth in the subsurface but have opposite effects on
CO2 density. In most cases CO2 injected deep in the subsurface will
be a buoyant fluid lighter than water. Other relevant CO2 charac-
teristics include its solubility in water which increases with
increasing pressure and decreases with increasing temperature
and water salinity.
For carbon storage, the ‘‘long-term’’ normally refers to the per-
iod after injection has been stopped at the storage site, while
‘‘short-term’’ refers to the period of active injection of CO2 into
the storage site which is usually less than 100 years. When CO2
is injected in the subsurface, it is firstly trapped by primary mech-
anisms, including static and hydrodynamic trapping below the
caprock in oil and gas reservoirs and deep saline aquifers, and
adsorption onto the coal surface in coal beds. Over time, a series
of secondary trapping mechanisms start operating, which are
mechanisms that do not necessarily increase the CO2 storage
capacity, but increase the storage security (i.e. diminish the poten-
tial for leakage and/or the amount of CO2 that may migrate or leak)
[16]. This is due to the fact that these secondary trapping mecha-
nisms, such as dissolution in reservoir oil or formation water,
in situ mineral carbonation and CO2 retention as an immobile
phase trapped in the pore space of the storage formation, are much
slower and have a much longer timeframe for operating, in the or-
der of centuries to millennia, than the primary trapping mecha-
nisms, as shown in Table 1. The contribution of these trapping
mechanisms is almost negligible during the operational (injection)
phase of CO2 geological storage but they contribute to increasing
storage security because the buoyant CO2 is immobile in the pore
space or it has been disappeared as a free phase, being either dis-
solved in formation water or precipitated as a carbonate mineral
[16]. Therefore storage security may increase in time because these
secondary trapping mechanisms increase their contribution to the
process.
The geological storage of CO2 is a complex physicochemical pro-
cess, which normally involves flow and transport phenomena in
porous media together with slow chemical reactions. A theoretical
description of the long-term geological storage of CO2 needs to ad-
dress both the primary and secondary mechanisms, involving all
the relevant physical and chemical processes that may take place.
In addition, CO2 properties as well as the properties of the geolog-
ical media need to be taken into account in the theoretical ap-
proach. Since the carbon storage takes place in an extraordinary
long time scale as well as in a large spatial scale involving a variety
of mechanisms, it poses a significant challenge to theoretical mod-
elling and numerical simulation.
3.1. Physical modelling and governing equations for the flow in porous
media
The most commonly used physical model for porous media flow
is Darcy’s law, which is a phenomenologically derived constitutive
equation that describes the flow of a fluid through a porous med-
ium. The law was formulated by Henry Darcy based on the exper-
imental results of the flow of water through sand beds [28]. It can
be given in a vector form as:
k ponents considered can be different depending on the applications.
q¼ ðrp  q gÞ; ð1Þ
l
where q is a vector quantity in a three-dimensional (3D) coordinate
system representing discharge per unit area, with the unit of veloc-
ity. In Eq. (1), the permeability tensor k represents the ability of the
medium to transmit fluids through the pore spaces, q is not the
velocity which the fluid travelling through the pores is experienc-
ing, but it can be linked to the pore (interstitial) velocity through
the porosity / of the medium.
q k
v¼ ¼ ðrp  q gÞ ð2Þ
/ l/
The effects of anisotropy of the medium can be accounted for in
the symmetric tensor of permeability, in a 3D Cartesian coordinate
system, given by:
0 1
kxx kxy kxz
B C
k ¼ @ kyx kyy kyz A; where kij ¼ kji : ð3Þ
kzx kzy kzz
Darcy’s equation for single-phase flow is an approximate form
of the fluid momentum balance in creeping flow through porous
media. Darcy’s law is only valid for steady, slow viscous flow.
Although it was originally determined experimentally by Henry
Darcy [28], it can be derived from the Navier–Stokes momentum
equations, which can be viewed as the application of Newton’s sec-
ond law to fluid flow, when the acceleration terms are neglected
(the flow is steady when a moving fluid element is followed). It
is typically accepted that flow regimes with values of Reynolds
number (based on a pore size length scale) up to 10 may be de-
scribed by Darcy’s law. It is worth noting that it is not a fundamen-
tal physical law.
The application of Darcy’s law to porous media flow encoun-
tered in carbon storage is a straightforward multi-phase extension
of Darcy’s equation. Carbon storage involves phases such as brine,
carbon and solid. For multi-phase fluid flow, an approximation is to
use Darcy’s law for each fluid phase, with permeability replaced by
phase permeability. Underlying the extension of the motion equa-
tion of a single fluid to the simultaneous flow of two or more fluids
is the concept of relative permeability. This approximation is valid
if the interfaces between the fluids remain static, which is not true
in general, but it is a reasonable approximation under steady-state
conditions. Relative permeability accounts for the reduction in the
flow of each phase due to the mutual interaction of the different
flowing phases. Taking the positive z-direction as vertically up
(opposite to gravity), the multi-phase extension of Darcy’s law,
for an individual fluid phase, can be given as:
qa k ka
va ¼ ¼ ðrpa þ qa g rzÞ: ð4Þ
/ la /
The governing equations for the mathematical description of
geological carbon storage are similar to those used to describe
oil, water, and gas flows through porous reservoirs. Darcy’s law, to-
gether with the equations of conservation of mass and energy are
employed. The equation of mass conservation for an individual ith
species or component can be given as:
" #
@ X a
X
/ qa sa X i þ r  ðqa X ai qa Þ
@t a a
X  
 r  /sa sa Da qa rX ai ¼ Si : ð5Þ
a
For carbon storage, the flow needs to be modelled is a multi-
phase (CO2, brine, porous solid matrix, etc.) and a multi-compo-
nent (CO2 and water, etc.) system. The number of phases and com-
In Eq. (5), the conservation of mass is expressed by the balance of
four terms representing all the possible mechanisms for mass
transfer, which are the time rate of change of mass at a fixed point
(or the local derivative or storage term), convective and diffusive
transports, and source/sink term of mass respectively. The tortuos-
ity s refers to the ratio of the diffusivity in the free space to that in
 X. Jiang / Applied Energy 88 (2011) 3557–3566
the porous medium and is generally larger than unity. The source/
sink term Si in the mass conservation equation is due to the geo-
chemical reactions.
Similar to mass conservation, the conservation of energy is
based on the balance of the time rate of change of energy or the en-
ergy storage in the fluid phases and in the formation matrix, con-
vection or advection, conduction, and the possible source/sink
term of energy. The equation of energy conservation can be given
as:
" #
@ X X
/ ðqa sa U a Þ þ ð1  /Þqs C s T þ r  ðqa Ha qa Þ
@t a a
 r  ðkrTÞ ¼ SH :
In the energy conservation equation, the energy transport due
to species diffusion which is normally insignificant has been ne-
glected. By neglecting the dissipative effects such as the work done
by the viscous forces and the heat transport due to molecular dif-
fusion of the species, the energy equation is much simplified. The
assumption of local thermal equilibrium is acceptable since flow
velocities are very small. In Eq. (6), the source/sink term of energy
SH can be related to possible geo-chemical reactions that may take
place, as that in the mass conservation equation.
Eqs. (4)–(6) constitute the fundamental governing equations for
the numerical simulations of the multi-phase flow in porous media
for carbon storage. They are a coupled nonlinear system involving
the geo-mechanical effects such as permeability and porosity of
the solid rock matrix, multi-phase fluid properties such as density
and viscosity, as well as possible contributions from the geo-
chemical reactions, which all affect the flow and transport behav-
iour. The governing equations need to be closed by constitutive
relationships and supplementary constraints for saturations, com-
ponent compositions and pressures [29]. For instance, assuming
the fluid saturations, which are the measure of the gross void space
in a reservoir rock occupied by the fluids, fill the media would lead
to:
X and accurate approximations for both transient and equilibrium
sa ¼ 1:
a concentrations. Their analysis identified six different time scales
The difference of pressures between two phases satisfies the
relation:
pa ¼ pb  pc;ab ;
where pc,ab refers to the capillary pressure that is function of satu-
ration. Depending on the complexity of the system, mainly the
number of phases and number of components considered, there
can be many more auxiliary equations. These equations, which
are normally semi-empirical relations for the solid rock phase and
relations between different fluid properties for the fluid phases,
are an integral part of the governing equations. The impurities of
CO2 [30,31] can have implications in carbon storage. In addition,
the equations of state (EOS) to calculate the densities of CO2 mix-
tures can be important to modelling and simulation of CCS. Recently
Li and Yan [32,33] evaluated several cubic formulations of EOS,
which had different calculation accuracy. Table 2 shows the depen-
dence of fluid properties of a simple carbon–brine system with CO2
and water as the considered components. Clearly the functional
dependence or the accuracy of the auxiliary equations can play a
major role in numerical simulations of carbon storage.
3.2. Modelling of the chemical processes
The chemical mechanisms for carbon storage are important to
the prediction of the long-term fate of stored CO2. The source/sink
terms in the conservation equations of mass and energy can be
3561
attributed to the chemical processes. For instance, the source/sink
term for the mass of the ith species can be given as:
X
Si ¼  mi m Im : ð9Þ
m
The kinetic rate may be modelled using a semi-empirical Arrhenius-
type general equation [34], given by:
  
Ea Q
I ¼ KA exp  1 : ð10Þ
RT Q eq
The last term in Eq. (10) takes into account the rate of reaction
depends on how far the system is from chemical equilibrium, that
ð6Þ is, the degree of over- or under-saturation. Rate constants may be
obtained from the literature based on laboratory experiments.
Equilibrium constants, rate constants, and other model inputs are
vital to the accuracy of the kinetic modelling. However, their accu-
rate determination can be challenging due to the complexity in-
volved in the geo-chemical processes especially the extremely
long duration of some of the mechanisms, as indicated in Table 1.
Modelling of the chemical processes occurring in long-term car-
bon storage involves several difficulties. The detailed chemical pro-
cesses can be far more complex than those listed in Table 1,
involving dozens sometimes hundreds of minerals with very com-
plex multi-step chemical reactions. In addition, the time scales of
different reactions can be hugely different, where the rate con-
stants can differ by many orders of magnitudes [35], leading to
numerical stiffness in the mathematical description. To accurately
predict the spatial and temporal distributions of geologically
stored CO2, the chemical processes must be accounted for together
with the fundamental governing equations for the multi-phase
flow in porous media, such as those given in Eqs. (4)–(6).
Recently, Mitchell et al. [35] constructed a mathematical model
for the kinetics of the system of reactions using the mass action
law and known rate and equilibrium constants. Although the mod-
el involved coupled fifth-order nonlinear ordinary differential
equations, their asymptotic approach yielded remarkably simple
ð7Þ
within the system, each exhibiting a different dominant balance
of terms representing locally rate-limiting reactions. However,
the model has not been coupled with the flow system of a porous
medium to obtain the spatial distributions of different chemical
ð8Þ
species. It is still challenging to incorporate such a model into
the flow governing equations of the porous media, allowing effi-
cient time-dependent three-dimensional numerical simulations
of the physicochemical processes of carbon storage. More research
efforts are needed to fully investigate the coupling of chemical
kinetics with the fluid flow equations in porous media, as well as
improving the accuracy of the constants used in the kinetic models.
3.3. Modelling limitations, uncertainties and issues for investigation
CO2 dispersion in geological storage is a complex physicochem-
ical process, involving a multi-phase and multi-component system.
The formulation of mathematical models needs to take into ac-
count the relevant processes in the subsurface such as the flow
and transport behaviour of multiple phases, geo-chemical reac-
tions and geo-mechanical effects. The hydraulics of the fluid flow
Table 2
The dependence of fluid properties for a carbon–brine system.
Fluid property qCO2 HCO2 lCO2 qbrine Hbrine lbrine
Dependence f(T, p) f(T, p) f(T, p) f ðT; p; s; X CO2 Þ f ðT; p; s; X CO2 Þ f(T, s)
water water
3562 X. Jiang / Applied Energy 88 (2011) 3557–3566
of CO2 dispersion is strongly influenced by the properties of the
porous medium such as permeability and porosity. Furthermore,
the interaction between fluid phases and rock matrix needs to be
expressed by constitutive relationships, including those for capil-
lary pressure and relative permeability as functions of saturation.
Fig. 1 shows the necessary physicochemical sub-processes need
to be considered in the physical modelling of carbon storage.
Apparently, the accuracy of numerical simulation depends on the
geological input, kinetic modelling of the geo-chemical reactions,
and the properties of fluids. Among the various model inputs, per-
haps the kinetic modelling is currently the most immature because
of the extremely long duration of some of the reactions such as the
mineral carbonation. These input parameters also play different
roles in different types of simulations. For instance, geo-chemical
modelling will be less important in simulations of the ‘‘short-term’’
injection process than that in the ‘‘long-term’’ storage process. The
various processes involved lead to very complex mathematical
problems, involving strongly coupled non-linear partial differential
equations, which cannot be solved analytically, at least not in their
full complexity. Apart from the numerical issues which may arise
when solving these equations, there are limitations and uncertain-
ties behind the mathematical formulations.
One major limitation of the formulations is associated with the
momentum balance based on the multi-phase extension of Darcy’s
law. Classical macroscopic descriptions of multi-phase flow rely on
the continuum approximation: the porous medium is regarded as a
superposition of several continua, each filling the entire medium.
This approximation is also often employed in general studies of
multi-phase flows at higher speeds in non-porous media for many
other applications [36]. The key ingredient of such a continuum
formulation for flows in porous media for carbon storage is a
straightforward multi-phase extension of Darcy’s equation. Darcy’s
law is an empirical relation that replaces – at the macroscopic level
– the equations of momentum conservation, or the Navier–Stokes
momentum equations. However, while Darcy’s law for single-
phase flow has been obtained from fundamental principles (the
Navier–Stokes momentum equations) under assumptions, its
extension to multi-phase systems is not rigorous, therefore limit-
ing its potential applicability. For the period of active injection of
CO2 into the storage site, the assumption of steady-state can be
questionable. In such cases, the flow may experience unsteadiness
with relatively high speeds and Darcy’s equation will be no longer
valid. Nevertheless, there is still a great interest in Darcy-like for-
mulations, and they are almost universally used in hydrogeology
and petroleum engineering, because alternative approaches have
not yet been well established. Solving the fully unsteady multi-
phase Navier–Stokes momentum equations may prove to be
computational prohibitive for the complex flow system. The
Fig. 1. Schematic of the physical modelling of geological carbon storage.
multi-phase extension of Darcy’s equation can be considered as a
working assumption, rather than a physical law. Mathematical
models on the relative permeability can be developed to improve
the representation of the physics of multi-phase flow [37]. In gen-
eral, the applicability of the traditional formulation relies heavily
on appropriateness of the continuum approximation, validity of
Darcy’s equation and its extension to multi-phase flow, as well as
proper models for the relative permeability.
The most prominent feature of the flow and transport phenom-
ena in porous media for carbon storage is that a broad range of
time and length scales are involved. A possible means to deal with
such vast scale differences is a multi-scale approach. Recently, a
multi-scale model of CO2 dispersion leakage from seafloor off the
Japanese coast was reported [38], where a meso-scale hydrostatic
model was coupled with small-scale full 3D two-phase model
but the up-scaling issue still needs to be fully addressed. The most
appealing reason for investigating CO2 dispersion using multi-scale
modelling is that it may provide accurate prediction with afford-
able computational costs. The approach of multi-scale modelling
of CO2 dispersion is to model complex multi-phase, multi-species
heterogeneous systems in a computationally efficient manner with
locally occurring complex processes taken into account. The
macroscales will be dealt with on a coarse grid which may contain
a number of fine-scale elements, which can be modelled using
approximations or resolved using a fine resolution, i.e. a fine grid.
To establish the governing equation on a coarse grid, an up-scaling
approach has to be applied [24,39,40], where variables will be
decomposed into their coarse-grid averages and local fluctuating
parts, in a manner similar to the concept of filtering in large-eddy
simulations of CFD. The up-scaled equations are then solved on the
coarse mesh, whereas fine-scale processes are only considered in a
small domain of interest, where phase interface exists or mass-
transfer processes have a major influence. Although approaches
at different levels have been proposed, e.g. [41], the development
of such a formulation is still an open issue and, it becomes more
challenging when the contributions of geo-chemical reactions need
to be fully accounted for.
4. Numerical simulations: methods and challenges
The governing equations for carbon storage simulations are a
set of coupled, non-linear partial differential equations involving
first- and second-order, temporal- and spatial-derivatives. Since
analytical solutions are generally not available, numerical solu-
tions based on discretisation of the computational domain and
governing equations are needed. In numerical simulations, effi-
cient use of computing resources is very high on the priority list
 X. Jiang / Applied Energy 88 (2011) 3557–3566 3563

for computational practitioners working in all areas. Simulating
geological carbon storage is particularly challenging because of
the broad range of time and length scales involved. The numerical
treatment of non-linearity and the discretisation in space and time
are important computational issues. In the process of discretisa-
tion and numerical solution of the discretised equations, accuracy,
stability, and computational speed are the main concerns. These
issues are relevant to both spatial discretisation and temporal dis-
cretisation or integration. The existing simulators for geological
carbon storage are mainly inherited from codes developed in the
oil and gas industry, for simulations of the multi-phase flow in
porous media with and without geo-chemical reactions. Simula-
tors have also been developed for the computation of the chemical
processes only. The simulators are wide-ranged with varying de-
grees of modelling approximations and rely on different discreti-
sation schemes with varying orders of numerical accuracies,
which are briefly discussed in the following. The section is then fo-
cussed on discussions of the numerical challenges for simulations
of long-term carbon storage.
4.1. Overview of simulators for carbon storage
All simulation codes are dependent on the types of numerical
methods used to translate the governing equations into a finite
form, appropriate for computational manipulation and analysis.
The commonly used numerical methods can be classified into finite
difference, finite element and finite volume methods. All of these
methods have been used in the available simulators for carbon
storage, which are wide ranged in terms of the physical models
considered and numerical methods used. Table 3 shows the main
features of some available packages/simulators for geological car-
bon storage. The complexity of the simulators depends heavily
on the number of fluid phases and the number of components con-
sidered, as well as the discretisation methods used. It is clear that a
variety of physical models and numerical methods have been em-
ployed in the non-exhaustive list.
The outcomes of numerical simulations depend on the simula-
tor used, characterised by the physical models implemented and
numerical methods employed. The choice of simulators such as

Table 3
Overview of the simulators for geological carbon storage.

Simulators Main applications Numerical features (methods for discretisation/integration)

CHILLER [42,43] Multi-component multi-phase equilibrium geochemical calculation Newton–Raphson method for solving a system of mass balance and
(companion to software based on minimum free-energy mass action equations
SOLVEQ)
CODE-BRIGHT Solution of the flow, heat and geo-mechanical model equations Finite element method for spatial discretisation; implicit finite-
[44,45] difference for temporal discretisation
COORES [23] Multi-component three-phase and 3D fluid flow in heterogeneous porous Finite volume method for spatial discretisation; implicit temporal
media discretisation
DUMUX [23,41] Multi-scale multi-physics toolbox for the simulation of flow and transport Vertex-centred finite volume method for spatial discretisation;
processes in porous media implicit temporal discretisation
ECLIPSE [23] Three-phase and 3D fluid flow in porous media with cubic EOS, pressure Integrated finite difference method (IFDM) with irregular spatial
dependent permeability values, etc. discretisation; implicit temporal discretisation
ELSA [22,23] Semi-analytical tool to estimate fluid distributions and leakage rates Spatial discretisation is essentially grid free; several schemes for
involving vertically integrated sharp-interface equations and local 3D well temporal discretisation including implicit pressure explicit
models saturation, etc.
FEFLOW [46] Solving the groundwater flow equation with mass and heat transfer, Finite element method for spatial discretisation; implicit/explicit/
including multi-component chemical kinetics Crank–Nicolson temporal discretisation
FEHM [23,47] Fully coupled heat, mass and stress balance equations for 3D, non- Control volume finite element method for spatial discretisation;
isothermal, multi-phase fluid flow in porous media implicit temporal discretisation
GEM [23] EOS compositional reservoir simulator IFDM for spatial discretisation; implicit temporal discretisation
Geochemist’s Interactive aqueous geochemistry tools Equilibrium modelling, reaction path modelling calculations, etc.
workbench
[48,49]
IPARS-CO2 [23,50] Parallel multi-block, multi-physics approach for multi-phase flow in Mixed finite element method for space discretisation; implicit
porous media pressure, explicit concentration sequential algorithm for temporal
discretisation
MIN3P [51,52] Multi-component reactive transport modelling in variably saturated Finite volume method for spatial discretisation; implicit temporal
porous media discretisation
MODFLOW [53] Solving the groundwater flow equation to simulate the flow through Finite difference method for spatial discretisation; implicit or
aquifers Crank–Nicolson for temporal discretisation
MT3DMS [54] Modular 3D transport model simulating convection, dispersion, and Finite difference/particle-tracking based Eulerian–Lagrangian/finite-
chemical reactions of dissolved constituents volume method for spatial discretisation; implicit/explicit temporal
discretisation
MUFTE [23,55,56] Isothermal and non-isothermal multi-phase flow problems including Vertex-centred finite volume method for spatial discretisation;
compositional effects implicit temporal discretisation
PFLOTRAN [57,58] Parallel 3D reservoir simulator for subsurface multi-phase, multi- Finite element method for spatial discretisation; implicit/semi-
component reactive flow and transport based on continuum scale mass implicit time integration
and energy conservation
PHAST [59,60] Simulating groundwater flow, solute transport, and multi-component Finite difference method for spatial discretisation; implicit or
geochemical reactions Crank–Nicholson for temporal discretisation
PHREEQC [61] Low-temperature aqueous geochemical simulator Based on an ion-association aqueous model; chemical equilibrium,
kinetic, transport, and inverse-modelling calculations
RETRASO [62] Reactive transport of dissolved and gaseous species in non-isothermal Direct substitution approach for solving the reactive transport
saturated or unsaturated problems equations
ROCKFLOW [23] Multi-phase flow and solute transport processes in porous and fractured Finite element method for spatial discretisation; implicit temporal
media discretisation
RTAFF2 [23] 2D/3D non-isothermal multi-phase and multi-component flow Finite element method for spatial discretisation; implicit temporal
discretisation
SUTRA [63,64] Fluid movement and transport of either energy or dissolved substances in Hybrid finite element and integrated finite difference method for
a subsurface environment spatial discretisation; implicit temporal discretisation
TOUGHREACT [65] Chemically reactive multi-component, multi-phase, non-isothermal flows IFDM for spatial discretisation; implicit temporal discretisation
in porous and fractured media
3564 X. Jiang / Applied Energy 88 (2011) 3557–3566
those listed in Table 3 would largely depend on the specific appli-
cations. For instance, if one would like to examine theory based
semi-analytical solution, simulators such as ELSA [22,23] may suit
this purpose. On the other hand, if one would like to examine the
aqueous geochemistry, the Geochemist’s workbench [48,49] may
be employed. The recent benchmark study [23] using different
simulators revealed large deviation in their predictions. Perhaps
the ‘‘best’’ simulator or an optimised simulator is the one yet to
be identified or developed. It is worth noting that the final arbiter
for the performance of simulators remains to be well-defined reli-
able experimental data and/or large scale field data, which is not
readily available in the literature. In the short term, the field data
may be provided from well-monitored CO2-EOR or CCS projects
[17].
The numerical methods used can have a major influence on the
performance of the simulators, including both computational accu-
racy and costs. The advantage of finite difference method, which
approximates the solutions to differential equations by replacing
derivative expressions with approximately equivalent difference
quotients, is that it can reach high-order accuracy without using
over-complex formulations. Many finite difference schemes can
be established from Taylor series expansion. In contrast to finite
difference method, finite volume method is based on an integral
form of the governing equation, where divergence terms are con-
verted to surface integrals. These terms are then evaluated as
fluxes at the surfaces of each control volume. It can be conve-
niently formulated to allow for unstructured meshes for complex
geometries. The finite element method is suitable for solving par-
tial differential equations over complicated domains, which can
be advantageous for carbon storage simulations involving domain
or phase changes as those occur during a fluid phase migration. It is
based on rendering the partial differential equations into an
approximating system of ordinary differential equations, which
are then numerically integrated using standard techniques such
as Euler’s method and Runge–Kutta method. The formulations of
these standard numerical techniques as well as many other
numerical algorithms and their programming can be readily found
in the literature such as the numerical recipes [66].
In the recent benchmark study of CO2 storage in geological for-
mations [23], the participating simulators, which are mostly listed
in Table 3, revealed strong differences in their numerical perfor-
mance, as shown in Fig. 2. This is not surprising considering the
wide range of numerical methods employed. State of the art liter-
ature does not reveal a systematic evaluation on the performance
of the numerical schemes in terms of their accuracy, computing
costs, equivalence, and deficiency/shortcomings. Therefore it be-
comes difficult to transfer numerical simulations to industry for
practical purposes, especially for long-term carbon storage involv-
ing a broad range of scales. Numerical accuracy is one of the pri-
mary concerns, which depends on the discretisation schemes and
the number of grid points or computational cells/volumes used.
For numerical simulation of CO2 dispersion, the time integration
is an integral part of numerical methods. The overall time scales
of problem are very large, yet physical processes of small time
scales are still important. Some of the numerical issues including
challenges for numerical simulations of geological carbon storage
are discussed as follows.
4.2. Numerical issues for investigation and challenges
The challenge of physical modelling of CO2 dispersion is closely
related to the numerical issues: it is prohibitive to solve for the de-
tails of the fluid flow using any numerical methods with the most
powerful computers, yet the simulations have to be of high fidelity
with the employment of highly accurate numerical methods.
Numerical simulations of CO2 dispersion depend on the suitability
of the numerical methods and physical models used. Numerical
accuracy can be measured by the order of the truncation or discret-
isation error of the discretisation scheme. In general, lower-order
discretisation schemes use fewer grid or mesh points in space
and fewer data points in time, thus require less computing re-
sources and the computational time leading to the solution is usu-
ally shorter than using higher-order schemes. However, they are
less accurate than higher-order numerical schemes which are at
least third-order accurate and require more data points and gener-
ally require more computing resources [67,68]. It has been a con-
sensus that high-order numerical schemes should be used in
advanced numerical simulations, such as direct and large-eddy
simulations of turbulent flows in the context of CFD. While there
are studies on numerical simulations of CO2 dispersion under geo-
logical storage conditions, currently there is no common under-
standing of the behaviour of numerical algorithms for these
simulations covering a broad range of scales. Modern high-order
numerical schemes like those typically used in direct and large-
eddy simulations [68,69] and computational aeroacoustics [70]
have not been employed in the existing numerical studies of CO2
dispersion.
In a higher-order scheme, the error in the functional approxi-
mation decreases faster with the grid spacing in the computational
domain than that in a lower-order scheme since the error is pro-
portional to hn for a n th order accurate numerical scheme. When
considering local transport calculations, h has to be a small quan-
tity to allow sufficient resolution. In a practical simulation, the
computing time depends mainly on the complexity of the method
and the grid resolution. When accuracy is a crucial requirement of
the simulation and a minimal truncation error has to be achieved,
the application of high-order schemes allows the use of a coarser
mesh compared to lower-order schemes which may require exces-
sively fine mesh to achieve the same accuracy. The employment of
high-order numerical schemes may reduce the computing costs to
achieve the required accuracy compared with using lower-order
numerical schemes, provided that the high-order numerical
schemes are not overly complex in formation and can be efficiently
implemented. Although high-order schemes normally require
more calculations at individual points such as involving more
neighbouring data points, this computational penalty could be
effectively compensated by the use of a coarser mesh. Higher-order
finite difference schemes including the compact schemes
Fig. 2. Computed leakage rates for CO2 plume evolution and leakage through an
abandoned well from the benchmark study [23] (reproduced with permission).
 X. Jiang / Applied Energy 88 (2011) 3557–3566
[67,71,72] may have a scope for application in numerical simula-
tions of geological carbon storage. Many of these modern high-
order finite difference schemes are non-dissipative, which are
particularly suitable to the simulations of geological flow that is
normally quite slow and dominated by diffusion. On the contrary,
first-order up-winding scheme that is broadly used in the existing
simulators can have large numerical diffusion, which deteriorates
the simulation accuracy. For complex geometry applications, the
spectral volume method [73,74] also provides an option for high-
order computation of the flow.
In numerical simulations of CO2 dispersion, the issues of
numerical methods and physical modelling are complex and cou-
pled together. For CO2 geological storage, the physical modelling
has to deal with a multi-phase and multi-component system,
which requires efficient numerical algorithms to solve the large
number of governing equations. There are many other numerical
challenges, such as the fluid phase front capturing [75] and the
treatment of discontinuities in pressure across phase interface
due to capillary effects. Moreover, the streamline-based simula-
tions, e.g. [25–27,76], need to be evaluated against the grid-based
simulations. When modelling phenomena of flow and transport on
different scales, it is also possible to directly include the different
scales in the numerical scheme, e.g. [77,78]. For parallel computa-
tions, the efficiency of parallelisation is crucially important to the
computational costs. Above all, numerical resolution and computa-
tional costs are the biggest challenge: solving a 1 km sized cubic
domain with 1 m spacing (typical length scale for viscous figuring)
would require a mesh size of 109 that is hardly affordable for the
most powerful parallel supercomputers, let alone the simulations
have to be run for enormous time steps to represent thousands
of years in the physical domain. Currently the simulation tech-
niques are mainly based on simulators used by the oil and gas
industry. Although the physics of CO2 dispersion has been rela-
tively well represented, the numerical accuracy of the schemes
used is predominantly of low-order accuracy. Efficient high-order
numerical schemes have a scope for applications in numerical sim-
ulations of CO2 dispersion, especially for local transport
calculations.
5. Concluding remarks
As a technology for reducing carbon dioxide emissions into the
atmosphere and thereby mitigating the greenhouse effect, CO2
sequestration in geological formations has drawn a significant
amount of research efforts. It is essential to investigate this tech-
nology with all available scientific means to assess its feasibility,
problems, and limitations. Simulating CO2 flow behaviour in geo-
logical media is difficult because of the interplay between phase
change, composition, reservoir heterogeneity, and the computa-
tional demands these aspects impose. The flow relevant to the
long-term geological storage of CO2 has its distinctive features: it
is a multi-phase multi-species flow dominated by diffusion. The
flow can be modelled by the multi-phase extension of the empiri-
cal Darcy’s law, together with conservation of mass and energy in
the system.
To properly account for the physics of multi-phase and multi-
component flow in porous media and the large spatial and tempo-
ral scales, it is likely that one has to resort to a multi-scale formu-
lation. In a multi-scale modelling approach, the issue of scales is
also related to the discretisation scheme. To ensure multi-scale
CFD benefits from the best capability of numerical schemes, one re-
quires robust numerical algorithms to serve as the backbone of the
simulators. In reported numerical studies of CO2 dispersion, the
contributions of small scales were not taken into account fully,
or an up-scaling process was not accounted for, apart from a lack
3565
of a systematic investigation on the numerical algorithms. The
essential up-scaling process requires robust and accurate numeri-
cal methods to work effectively with a coarse mesh and the numer-
ical algorithms need to be systematically evaluated. In addition,
the relation between the order of numerical accuracy and the
up-scaling process of multi-scale modelling needs to be explored.
For CO2 storage, multi-scale modelling incorporating advanced
numerical methods such as the high-order schemes may provide
reliable prediction results at affordable costs, which are impossible
or difficult to obtain using experimental and analytical methods. It
is important to understand these advanced numerical methods
comprehensively in order for them to be used effectively for real
world applications.
For accurate and efficient numerical simulations of the long-
term geological storage of CO2, the extremely wide range of time
and length scales has to be accounted for. Multi-scale modelling
provides a direction for future exploration. It can be effectively uti-
lised to predict the long-term fate of geologically stored CO2, to
guide the design of storage facilities, as well as to predict the CO2
dispersion for altered operating conditions. Further developments
are needed to lead to the implementation of advanced numerical
schemes in the multi-scale modelling codes for improvements in
computational accuracy, capability and efficiency. Accurate physi-
cal modelling and numerical simulation provide a possibility to en-
hance our understanding on the long-term storage of CO2, which
could influence the industrial procedures of CCS. The direct eco-
nomic impact of physical modelling and numerical simulations of
CO2 dispersion can be ultimately realised through the CCS industry.
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